1 POST-MINERAL NORMAL FAULTING IN ARIZONA PORPHYRY SYSTEMS By Phillip A. Nickerson _________________ A Dissertation Submitted to the Faculty of the DEPARTMENT OF GEOSCIENCES In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 2012 2 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Dissertation Committee, we certify that we have read the dissertation prepared by Phillip A. Nickerson entitled Post-Mineral Normal Faulting in Arizona Porphyry Systems and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy _______________________________________________________________________ Date: 04/30/2012 Eric Seedorff _______________________________________________________________________ Date: 04/30/2012 Mark Barton _______________________________________________________________________ Date: 04/30/2012 George Davis _______________________________________________________________________ Date: 04/30/2012 Peter Reiners _______________________________________________________________________ Date: 04/30/2012 Charles Ferguson Final approval and acceptance of this dissertation is contingent upon the candidate’s submission of the final copies of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. ________________________________________________ Date: 04/30/2012 Dissertation Director: Eric Seedorff 3 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: Phillip A. Nickerson 4 ACKNOWLEDGEMENTS I would like to thank my major advisors, Eric Seedorff and Mark Barton for their guidance, assistance, and patience. I also greatly appreciate valuable feedback from my committee members, George Davis, Peter Reiners, and Charles Ferguson. I’d like to recognize my many geologic predecessors--in particular the contributions from the USGS, AZGS, and other graduates students who generated an invaluable archive of geologic maps heavily utilized in this study. Without this high-quality geologic framework, this work would not have been possible. Financial support for this project came from the Sciences Foundation Arizona, Lowell Institute for Mineral Resources, Eurasian Minerals, and the Society of Economic Geology Hugh E. McKinstry Student Reasearch Fund. Logistical support including drillhole information, helicopter access, and some regional data compilation was provided by Bronco Creek Exploration. 5 DEDICATION To my wife Laura, and my family. 6 TABLE OF CONTENTS LIST OF FIGURES .............................................................................................. 12 ABSTRACT.......................................................................................................... 13 INTRODUCTION ................................................................................................ 15 Laramide porphyry systems in the Basin and Range province ......................... 15 Extension in the Basin and Range province ................................................. 17 Regional geologic framework ........................................................................... 19 PRESENT STUDY ............................................................................................... 23 Methodology ..................................................................................................... 23 Key results ........................................................................................................ 24 Appendix A: “Domino-style” tilting in metamorphic core complexes: Evidence from radial dikes in the Pinaleño Mountains, Arizona ................. 24 Appendix B: Sodic-(calcic) alteration in two Arizona porphyry copper systems: Hybrid hydrothermal systems of Laramide and mid-Tertiary ages 25 Appendix C: Dismembered porphyry systems near Wickenburg, Arizona: District-scale reconstruction with an arc-scale context ................................ 27 FIGURE CAPTIONS............................................................................................ 29 REFERENCES ..................................................................................................... 32 7 APPPENDIX A: “DOMINO-STYLE” TILTING IN METAMORPHIC CORE COMPLEXES: EVIDENCE FROM RADIAL DIKES IN THE PINALEÑO MOUNTAINS, ARIZONA .................................................................................. 49 Abstract ................................................................................................................. 50 Introduction ........................................................................................................... 51 Pinaleño MCC....................................................................................................... 52 Porphyry Dike Swarm..................................................................................... 53 Dike Orientations and Their Use as a Paleo-Vertical Indicator ...................... 54 Folding of footwall rocks ................................................................................ 56 Hydrothermal Alteration ................................................................................. 56 Interpretation of Oligocene Regional Stress Patterns in Southeastern Arizona ... 56 Implications for the formation of the Pinaleño MCC ........................................... 58 Discussion ............................................................................................................. 60 Conclusions ........................................................................................................... 61 Acknowledgments................................................................................................. 62 References ............................................................................................................. 62 Appendix A.1 ........................................................................................................ 79 References ............................................................................................................. 81 8 APPENDIX B: SODIC-(CALCIC) ALTERATION IN TWO ARIZONA PORPHYRY COPPER SYSTEMS: HYBRID HYDROTHERMAL SYSTEMS OF LARAMIDE AND MID-TERTIARY AGES ............................................... 88 Abstract ................................................................................................................. 89 Introduction ........................................................................................................... 90 Geologic Setting.................................................................................................... 92 Geochronology...................................................................................................... 95 Tea Cup system ............................................................................................. 96 Eagle Pass system ......................................................................................... 97 Hydrothermal alteration assemblages ................................................................... 97 Tea Cup system ................................................................................................. 98 Eagle Pass system ........................................................................................... 100 Compositions of hydrothermal minerals ............................................................. 102 Tea Cup system ............................................................................................... 102 Eagle Pass system ........................................................................................... 103 Gains and losses in sodic alteration ............................................................... 104 Comparison of sodic (-calcic) and greisen hydrothermal alteration assemblages at Tea Cup and Eagle Pass with other localities ..................................................... 104 Origin of sodic (-calcic) and iron oxide-rich alteration ...................................... 107 9 Source of fluids ............................................................................................... 107 Relationship of sodic-(calcic) alteration to iron oxide-rich alteration ............ 110 Discussion ........................................................................................................... 111 Hybrid hydrothermal systems ......................................................................... 111 Implications for exploration............................................................................ 115 Summary and Conclusions ................................................................................. 117 Acknowledgments............................................................................................... 118 References ........................................................................................................... 118 APPENDIX C: DISMEMBERED PORPHYRY SYSTEMS NEAR WICKENBURG, ARIZONA: DISTRICT-SCALE RECONSTRUCTION WITH AN ARC-SCALE CONTEXT ............................................................................ 162 Abstract ............................................................................................................... 163 Introduction ......................................................................................................... 164 Location and Geologic Setting............................................................................ 166 Location .......................................................................................................... 166 Laramide porphyry copper province ............................................................... 166 Extension in western Arizona ......................................................................... 167 Rock types ....................................................................................................... 169 Economic Geology.............................................................................................. 171 10 Hydrothermal Alteration ..................................................................................... 173 Greisen ............................................................................................................ 173 Potassic ........................................................................................................... 174 Transitional greisen-potassic .......................................................................... 174 Structural Geology .............................................................................................. 175 Structural Interpretation and Palinspastic Reconstruction of Normal Faults...... 177 Tertiary tilting ................................................................................................. 177 Style of extension............................................................................................ 179 Interpretation of the normal faults .................................................................. 179 Approach to restoring movement on normal faults ........................................ 180 Examination of the district-scale reconstruction............................................. 181 Exploration targets .......................................................................................... 182 Classification of porphyry systems near Wickenburg ........................................ 183 Arc-Scale Reconstruction of Tertiary Extension in the Laramide Porphyry Copper Belt ...................................................................................................................... 185 Discussion ........................................................................................................... 189 Style of extension in western Arizona ............................................................ 189 Comparison of the scale and geometry of the Laramide magmatic arc to other arcs .................................................................................................................. 191 11 Conclusions ......................................................................................................... 192 Acknowledgments............................................................................................... 193 References ........................................................................................................... 194 Figure Captions ................................................................................................... 203 APPENDIX D: ELECTRON MICROPROBE TABLES ................................... 225 APPENDIX E: TEA CUP U-PB GEOCHRONOLOGY ................................... 289 References ........................................................................................................... 291 APPENDIX F: (U-TH)/HE DATING OF HEMATITE FROM TEA CUP AND EAGLE PASS ..................................................................................................... 297 Introduction ......................................................................................................... 297 Results ................................................................................................................. 298 Tea Cup ........................................................................................................... 298 Eagle Pass ....................................................................................................... 299 Significance of Ages ........................................................................................... 301 References ........................................................................................................... 302 12 LIST OF FIGURES Figure 1. Location map ......................................................................................... 41 Figure 2. Schematic cross section showing a typical pattern of hydrothermal alteration in a porphyry copper system ................................................................. 42 Figure 3. Three models proposed to explain the link between upper-crustal and mid-crustal extension in the Basin and Range province ....................................... 43 Figure 4. Index maps of porphyry deposits in southwestern North America ....... 44 Figure 5. Three-stage model for the formation of the Pinaleño MCC .................. 45 Figure 6. Diagram depicting variation in peripheral styles of alteration in composite porphyry systems ................................................................................. 46 Figure 7. Panels depicting the palinspastic reconstruction of a district-scale cross section through the Sheep Mountain porphyry system ......................................... 47 Figure 8. Comparison of porphyry systems of the reconstructed Laramide magmatic arc to other porphyry belts and magmatic arcs .................................... 48 13 ABSTRACT 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 14 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. 15 INTRODUCTION The Basin and Range province of western North America is one of the great metallogenic provinces of the world, as well as a one of the world’s best studied extensional terrains. Normal faults and ore deposits commonly are superimposed upon one another here (Fig. 1) (Seedorff, 1991; Wilkins and Heidrick, 1995), which creates challenges and advantages for the study of both metallogensis and extension. For example, challenges arise where syndeformational hydrothermal alteration destroys critical structural markers near the associated fault zones and where key parts of ore bodies are dismembered by normal faults. Benefits of this juxtaposition are brought to light when products of one of the geologic processes are used to constrain the other. For example, predictable patterns in hydrothermal alteration zoning can be used as structural markers (Stavast et al., 2008), which may better constrain structural reconstructions and, in turn, aid in better discriminating between different styles of extension. Conversely, the deep levels of ore-forming systems exposed in the footwalls of normal faults can be examined at the surface to better constrain ore forming processes (Carten, 1986). In this dissertation, I focus on the benefits brought about by the superposition of postmineralization normal faults on porphyry systems in Arizona in order to simultaneously advance the understanding of extension and ore deposits in the Basin and Range province. Laramide porphyry systems in the Basin and Range province Precious metal (Au, Ag) and base metal (Cu, Mo, Pb, Zn, Sn, W, Fe) ore deposits of many different styles occur throughout the Basin and Range province. This study will 16 focus on the porphyry copper deposits of Arizona that constitute one of the richest copper metallogenic provinces on earth (Titley, 1982a). The deposits are commonly spectacularly exposed in the arid climate of the Sonoran Desert and lie within a region that has been well described in the geologic literature for more than a century (e.g., Ransome, 1903; Titley and Hicks, 1966; Davis, 1979; Dickinson, 1991). The combination of the high degree of exposure, vast literature on the regional geology and mineral deposits, as well as the ease of access to this geology, make southern Arizona an ideal laboratory to advance the understanding of porphyry copper deposits. Porphyry systems are magmatic-hydrothermal systems that include the dike- and plug-like intrusions of porphyry texture which lend their name to the deposit type, a pluton or batholith which is the source of the dikes and plugs, and various styles of hydrothermal alteration which typically metasomatize 10’s to 100’s of km3 of the intrusive bodies and surrounding country rock (Seedorff et al., 2005b; Sillitoe, 2010). The hydrothermal fluids are derived both from the intrusive bodies and by circulation of meteoric and connate waters in the country rock (Carten, 1986; Dilles et al., 1992, 1995). Temperature, fluid chemistry, and pressure control the style of hydrothermal alteration in a given part of a system. In a vertical progression from deep to shallow, proximal parts of the system are dominated generally by greisen, potassic, sericitic, and advanced argillic styles of alteration, whereas the distal parts of the system generally are dominated by propylitic, sodic-calcic, sodic, and iron-oxide rich acid styles of hydrothermal alteration (Fig. 2), although other variations also occur. 17 Whereas the overall footprint of hydrothermal alteration is quite large (10’s km3) in porphyry systems, the sizes of the ore bodies are only a few km3. Mineralization occurs in a range of settings, including near the transition from potassic to sericitic alteration (Lowell and Guilbert, 1970) at moderate to high temperature (~700°C-350°C). Copper-bearing minerals include sulfides at depth and oxides in the shallower, weathered horizon and are either disseminated in the rock or in veins. The relatively small size of the ore bodies compared to large size of the porphyry copper systems requires the exploration geologist to use knowledge of zoning patterns in hydrothermal alteration and textures in intrusive igneous rocks to identify vectors toward mineralization. However, despite decades of study on specific porphyry copper deposits, certain alteration styles found on the flanks and roots of porphyry copper systems have only recently been identified (e.g., Seedorff et al., 2008), and a system-scale understanding of their evolution remains to be developed. Examining porphyry systems in extended terrains, such as southern Arizona, offers the ability to map and to characterize the distal and deep parts of the systems, as normal fault blocks commonly expose them at the surface (Dilles and Einaudi, 1992; Maher, 2008; Stavast et al., 2008; Nickerson et al., 2010). These exposures are utilized in this study to help further the system-scale understanding of porphyry systems. Extension in the Basin and Range province Many fundamental insights into upper- and mid-crustal extension were uncovered in the Basin in Range province (Ransome et al., 1910; Armstrong, 1972; Proffett, 1977; Crittenden et al., 1980; Lister and Davis, 1989), and the area continues to an important 18 study area for research into the debate surrounding the manner in which it the crust responds to large-magnitude extension (Brady, 2002; Wong and Gans, 2008; Arca et al., 2010; Colgan et al., 2010). Much of the controversy surrounding extension in the Basin and Range province focuses on normal faults that currently dip at low angles (< 30°). Where these relationships were first identified in the hinterland of the Sevier fold and thrust belt, they were thought to be contractional features (Misch, 1960). However, Armstrong (1972) showed that because the faults placed younger rocks on older rocks, they must be normal faults accommodating extension. Reinterpretation of contractional features as extensional features swept across the Basin and Range and culminated with the elucidation that mylonitic fabrics found in what would be called metamorphic core complexes (Coney, 1980) were products of extension in the middle crust (Davis, 1980). Three competing models have emerged to explain the relationships between midcrustal mylonitic fabrics observed in core complexes and upper-crustal brittle normal faulting that is widespread in the Basin and Range (Fig 3A-C). The first model (Fig. 3A) proposes that the mylonitic fabrics are down-dip expressions of normal faults that initiated at low angles (less than 30°) and accommodated 10’s of km of displacement (Wernicke, 1981; John, 1987). A second model(Fig. 3B), known as the rolling hinge model, states that strongly listric normal faults in the upper crust, with 10’s km of displacement, are folded by isostatic uplift during extension to expose mid-crustal mylonitic fabrics at the surface (Spencer, 1984; Buck, 1988). The first two models agree that during extension a master fault serves as a detachment into which smaller scale faults solein the upper crust and transfer their displacement. The final model (Fig. 3C) puts 19 forth that a set of “domino–style” faults break at high angles (60°-70°) and rotate to low angles during extension (Davis, 1983). When the nearly-planar faults rotate to low angles (~20-30°), slip on the faults becomes kinematically unfavorable (Anderson, 1951), and a new set of faults forms at high angles. Through repetition of the process, mylonitic rocks in the down-dip toes of abandoned low-angle faults can be brought to the surface. These three models each make different predictions regarding the geometry, magnitude, and timing of normal faulting that can be tested. Studies utilizing reflection seismology (Gans, 1987), modern earthquake focal mechanisms (Jackson, 1987; Abers et al., 1997), thermochronology (John and Foster, 1993; Howard and Foster, 1996; Reiners et al., 2000), and paleomagnetism (Livaccari et al., 1995; Stavast et al., 2008) have all furthered the understanding of large-magnitude extension but have not synthesized a cogent model for the formation of metamorphic core complexes. This study uses knowledge derived from studies in economic geology to place constraints on deformation in crystalline rocks that commonly occur in the footwall of normal faults to further this debate. Regional geologic framework The porphyry copper deposits of Arizona include some of the best-studied porphyry systems in the world and have been the focus of over a century of scientific study (Ransome, 1903; Titley and Hicks, 1966; Titley, 1982a; Pierce and Bolm, 1995). However, the new ages on porphyry copper systems in Arizona (Seedorff et al., 2005a; Nickerson and Seedorff, this study Appendix A), as well as the recognition and description of the flanks and roots of these complex hydrothermal systems (Seedorff et al, 20 2005b, 2008; Barton et al., 2005; Stavast et al., 2008; Nickerson et al., 2010), continue to advance the understanding of porphyry copper systems. The Tea Cup, Eagle Pass, and Sheep Mountain porphyry systems examined in this study are located in the heart of the porphyry copper belt of southwestern North America in the state of Arizona (Fig. 4). Exploration for porphyry copper deposits in the region has ebbed and flowed in tandem with copper prices (Lowell, 1978; Paul and Manske, 2005), with times of intense exploration occurring mainly in the late 19th and middle 20th centuries. The discovery of the Resolution deposit near Superior in the mid-1990s has renewed the interest of both junior and major mining companies in the region. The Laramide (~80-50 Ma) and younger magmatism in Arizona intruded a thin (~2 km) cratonal section of sedimentary rocks (Titley, 1982b). As summarized by Dickinson (1989), the metamorphic basement of central and southeastern Arizona consists of the Mesoproterozoic Yavapai Supergroup (ca. 1.8 Ga) and Pinal Schist (ca. 1.7 Ga). These crystalline rocks were intruded at 1.6 Ga by arc plutons of the Madera Diorite and at 1.4 Ga by widespread anorogenic granitic plutons. Before 1.1 Ga, the crystalline basement was beveled and unconformably overlain by approximately 1 km of dominantly siliciclastic sedimentary rocks of the Proterozoic Apache Group and Troy Quartzite. Near the time of deposition of the Troy Quartzite, the siliciclastic sedimentary sequence and the underlying crystalline rocks were intruded by diabase sheets, sills, and dikes that are dated at ~1.1 Ga (Shride, 1967; Wrucke, 1989). The diabase sheets are most abundant in sedimentary rocks of the Apache Group and in the upper one km of the underlying crystalline rocks (Howard, 1991). The Proterozoic strata of the Troy Quartzite 21 and Apache Group are disconformably overlain by approximately 1.0-1.5 km of Paleozoic strata, mainly carbonate rocks. During Laramide time, regional contraction produced basement-cored uplifts similar to those of the central Rocky Mountains (Davis, 1979), and a large magmatic arc was built on the western margin of the North American plate (Drewes, 1976; Dickinson and Snyder, 1978; Dickinson, 1989). The arc formed between about 84 and 61 Ma and shows an overall progression to more felsic compositions over time (Cornwall, 1982; Lang and Titley, 1998; Seedorff et al., 2005a). Contraction clearly postdates early relatively mafic magmatism (Willden, 1964). Porphyry copper formation is related to somewhat younger (74-61 Ma) arc magmatism of intermediate to silicic composition (Titley, 1982b; Lang and Titley, 1998), which, in the cases of at least certain deposits, postdates reverse faulting (Seedorff et al., 2005a). A period of tectonic quiescence and erosion characterized the post-Laramide period until Oligocene time (Dickinson, 1991), when bimodal volcanism and extension swept across the region formerly occupied by the Laramide arc (Coney and Reynolds, 1978). Large-magnitude extension dismembered and tilted porphyry systems and formed a northwest-southeast striking belt of metamorphic core complexes in Arizona (Davis, 1980). Extension and magmatism continued through the Miocene, but by 15 Ma was of lesser magnitude and was more silicic, respectively. In many cases, sedimentation accompanied extension in the newly formed basins. Following extension, Tertiary and Quaternary gravels were deposited to form widespread pediment surfaces on older rocks 22 (Dickinson, 1991). Today, the landscape is undergoing incision as the pediment surfaces are exhumed by down-cutting along the Gila River (Richard and Spencer, 1997). 23 PRESENT STUDY The methods, results, and conclusions of this study are presented in the three manuscripts appended to this dissertation/thesis, Appendices A to C. In addition, further information and documention is contained in supplementary material, which is included as Appendices D to F. The following is a summary of the most important findings in this document. Methodology This study combines field mapping, structural analysis, palinspastic reconstruction, mineral characterization via petrography and electron microprobe, U-Pb geochronology, (U-Th)/He thermochronology, and compilations of pre-existing geologic mapping to constrain formation of porphyry systems, and crustal extension in Arizona. Original geologic mapping was used to identify the nature and timing of structural features, as well as, the geometry and relative ages of different styles of hydrothermal alteration in three study areas: the Tea Cup porphyry system, the Eagle Pass porphyry system, and the Sheep Mountain porphyry system. These observations are combined with data from pre-existing geologic maps to palinspastically reconstruct Oligo-Micoene extension in an iterative manner. The resulting product constrains both the style of extension and the zoning patterns of hydrothermal alteration in the porphyry systems. Mineral compositions determined by electron microprobe are used to characterize hydrothermal mineral assemblages, and the thermo- and geochronologic techniques are used to place quantitative constraints on the timing of both porphyry system formation and extension. 24 Key results Appendix A: “Domino-style” tilting in metamorphic core complexes: Evidence from radial dikes in the Pinaleño Mountains, Arizona In this appendix, geologic mapping in the Eagle Pass porphyry system and stereographic analysis of its radial porphyry dike swarm are used to place new constraints on the style of extension in the Pinaleño metamorphic core complex (MCC) of southeastern Arizona. Three new U-Pb dates, coupled with field and petrographic relationships, reveal that the porphyry system is the first well documented Oligocene porphyry system in Arizona. A method for determining paleo-vertical in radial dikes swarms is demonstrated and then used to show that both the footwall and hanging wall of the Pinaleño MCC were homogeneously tilted ~83° SW during Oligo-Miocene extension. Mapped patterns of hydrothermal alteration that are intimately associated with the intrusion of the dike swarm also are consistent with significant southwesterly tilting of footwall rocks. A previous interpretation of the Pinaleño MCC contends that the MCC formed via isostatic upwarp of a strongly listric normal fault (Figure 5D), implying different amounts of tilting in hanging wall and footwall rocks and folding of the footwall rocks about a horizontal axis perpendicular to the extension direction; neither style of deformation is recorded by the dike swarm. The constraints on footwall deformation instead favor a “domino- style” model of MCC formation that produces similar amounts of tilting in hanging wall and footwall rocks. A new interpretation for formation of this MCC involves at least two independent sets of nearly planar normal faults that were 25 sequentially superimposed (Fig. 5A-C). These results suggest that warping of normal faults by localized isostatic uplift is not required for MCC formation. Appendix B: Sodic-(calcic) alteration in two Arizona porphyry copper systems: Hybrid hydrothermal systems of Laramide and mid-Tertiary ages The distal expressions of hydrothermal alteration on the periphery of porphyry systems vary significantly from system to system, including a diversity of distal alteration types, intensity of distal alteration, and geometry of distal alteration patterns. Distal alteration in porphyry systems, including sodic-calcic and propylitic, can host significant base or precious metal mineralization, and the spatial distribution of distal hydrothermal alteration can be used as a vector toward the center of the system. In this appendix the flanks and cores the Laramide Tea Cup and Oligocene Eagle Pass porphyry copper systems in Arizona are examined here using U-Pb geochronology, as well as field and petrographic studies, to better characterize sodic (-calcic) and iron oxide-rich alteration found in porphyry systems. New U-Pb ages of zircons from Tea Cup reveal that the porphyry system dates from between ~72 and 70 Ma. Sodic assemblages at Tea Cup and Eagle Pass contain quartz, albite, chlorite, and epidote, whereas sodiccalcic assemblages found only at Tea Cup contain actinolite, andesine, epidote and, in areas of leaching of quartz, local garnet. Feldspar-destructive, sulfide-poor, iron oxiderich alteration intensely developed at Tea Cup is characterized by the assemblage quartz + chlorite + albite ± specular hematite. Previously documented occurrences of these alteration styles in the Yerington district, Nevada, at the Ann-Mason deposit and the Yerington mine, and at Sierrita- 26 Esperanza in the Pima district, Arizona, provide a basis of comparison for the new work. Sodic (-calcic) alteration at the Tea Cup is developed 2 - 4 km outboard from the most intense potassic alteration at paleodepths ranging from ~6 - 8 km. Iron oxide-rich alteration developed structurally higher at paleodepths of ~2 - 4 km. Sodic (-calcic) alteration at Eagle Pass is most intense 3 - 6 km outboard from the most intense potassic alteration across 4 km of paleodepth, and a spatially and mineralogically distinct zone of sodic alteration occurs in the immediate footwall of the Eagle Pass fault. The diverse manifestations of distal hydrothermal alteration in porphyry systems can be rationalized if all porphyry systems are conceptually regarded as hybrid hydrothermal systems: a magmatic-hydrothermal portion best developed in the proximal or core region, and a non-magmatic portion dominated by externally derived fluids of various compositions on the flanks (Fig. 6). The non-magmatic portion may be weakly developed to intense, and the associated alteration patterns may range spatially from completely outboard of the magmatic-hydrothermal alteration products in certain systems to intimately interfingering with or overprinting the magmatic-hydrothermal products in other systems. When dilute meteoric external fluids, which are characteristic of temperate climates, are circulated, propylitic alteration develops on the periphery. When saline brines, which are characteristic of arid regions, are convected on the periphery of a porphyry system, sodic (-calcic) alteration forms as the fluid descends on the warming path. After the externally-derived fluids eventually turn toward the surface, iron oxiderich alteration (with or without metals other than Fe, such as Cu and Au) forms at shallow structural levels on the cooling path. Nonetheless, the sodic (-calcic) and iron oxide-rich 27 alteration also can be developed without being associated with a magmatic-hydrothermal system as long as there is a thermal drive for fluid circulation, as likely occurred along the Eagle Pass fault and in many IOCG systems worldwide. Appendix C: “Filling in a gap in the Laramide porphyry belt: Porphyry prospects near Wickenburg, Arizona, with district- and arc-scale restorations of Tertiary extension” This study examines the effects of Tertiary extension on the geometry of porphyry deposits of the Laramide magmatic arc of southwestern North America at the district and arc scales. Building upon previous work, we combine results from reconnaissance scale mapping of hydrothermal alteration, rock types, and structures, to provide a district-scale cross section and associated palinspastic reconstruction through a poorly understood segment of the Laramide magmatic arc near Wickenburg, Arizona. Extension at the scale of the magmatic arc is quantified using a compilation of the amount of tilting recorded by Tertiary sedimentary and volcanic rocks across the modern expression of the Laramide magmatic arc. Extension is then restored across the arc to reveal the geometry of the porphyry belt prior to extension. At the district scale, cross cutting relationships between normal faults, and tilting of hanging wall and footwall rocks indicate that five sets of nearly planar normal faults are superimposed upon one another in the study area. The normal faults initiated at angles between 60 and 70° and rotated to angles as low as 20° during slip. The amount of displacement on the largest faults is no greater than 4 - 6 kilometers. A fault-by-fault palinspastic reconstruction of displacement along the various normal faults reveals the 28 presence of two spatially distinct hydrothermal systems sourced from different cupolas of a Late Cretaceous pluton (Fig. 7). Hydrothermal alteration zones from greisen to potassic to transitional greisen-potassic assemblages from deep to shallow structural levels. The reconstruction also reveals two exploration targets centered on potassic alteration in two porphyry systems that are now covered by younger Tertiary and Quaternary rocks. Igneous source rock compositions, and styles of alteration suggest that the prospects may be porphyry molybdenum systems of the Mo-Cu subclass, similar to previously identified nearby porphyry resources. At the scale of the Laramide porphyry belt, a compilation of strikes and dips of Tertiary units is utilized to delineate post-porphyry mineralization extensional domains across the porphyry belt. Extension is quantified by calculating the β factor in each extensional domain, and an arc-scale reconstruction reveals the pre-extension geometry of the Laramide porphyry belt. This arc-scale reconstruction reveals that the Laramide porphyry displayed a variably well defined axis, approximately 100 km wide prior to extension with gaps and clusters of deposits along the 700-km strike length of the arc (Fig. 8). The majority of porphyry deposits occur within the axis of the arc, but others lie in forearc or rear-arc settings. The geometry of the porphyry belt related to the Laramide arc, once extension is restored, closely resembles other magmatic arcs and associated porphyry belts formed at convergent oceanic-continental plate boundaries. 29 FIGURE CAPTIONS Figure 1. Location map depicting selected ore deposits which lie in the Basin and Range province of western North America. MCC = metamorphic core complex. Figure 2. Schematic cross section showing a typical pattern of hydrothermal alteration in a porphyry copper system. Figure 3. Three models proposed to explain the link between upper-crustal and midcrustal extension in the Basin and Range province. A. Extension accommodated along a “detachment” fault which initiates slip at a dip angle of < 30° (after Wernicke, 1985). B. Extension accommodated along a strongly listric “detachment” fault that is up-warped by isostasy during extension (after Spencer, 1984). C. Extension accommodated along two sets of planar normal faults which rotate to shallower dips during extension. Figure 4. Index maps of porphyry deposits in southwestern North America. The Tea Cup, Eagle Pass, and Sheep Mountain study areas are indicated by bolded and italicized text. Figure 5. A-C: Three-stage model for the formation of the Pinaleño MCC. A: Eagle Pass fault (EPF) breaks at a high angle to the surface and begins tilting to lower angles during extension. B: Pinaleño detachment fault (PDF) and another fault break also at high angles, cutting the abandoned Eagle Pass fault, and begin tilting to lower angles during continued extension. C: Modern cross section through Pinaleño MCC. D: Cross section 30 through Pinaleño MCC after Naruk (1987) using ‘rolling hinge’ model for MCC formation, which predicts different amounts of hanging wall and footwall tilting in the MCC that is not supported by new evidence presented here. QTg = Quaternary and Tertiary gravels; Tu= Tertiary volcanic and sedimentary rocks; YX = Proterozoic rocks, shades in purple reflect the depth of the rocks prior to extension. Figure 6. Diagram depicting variation in peripheral styles of alteration in composite porphyry systems created by variation in external fluid compositions. A: Propylitic alteration is generated by circulating fresh external fluids. B: Sodic (-calcic) and ironoxide rich alteration is created by circulating saline fluids derived from ancient evaporitebearing sedimentary rocks. C: Sodic (-calcic) and iron-oxide rich alteration is created by circulating saline fluids derived from modern evaporite-bearing sedimentary rocks. Figure 7. Panels depicting the palinspastic reconstruction of a district-scale cross section through the Sheep Mountain porphyry system. A. Modern cross section. B. Restoration of the 5th set of normal faults. C. Restoration of the 4th set of normal faults. D. Restoration of the 3rd set of normal faults. E. Restoration of the 2nd set of normal faults. The fault in this set strikes nearly perpendicular to the line of section. The true orientation of this fault prior to slip was 110°, 60° SW. F. Restoration of the 1st set of normal faults. Figure 8. Comparison of porphyry systems of the reconstructed Laramide magmatic arc to other porphyry belts and magmatic arcs. A. The reconstructed location of porphyry 31 systems of the Laramide magmatic arc. B. Porphyry copper systems of Miocene-Early Pliocene magmatic arc of central Chile (after Sillitoe and Perelló, 2005). C. The Quaternary Cascade magmatic arc of northwestern North America (after Hildreth, 2007), showing major volcanic centers. 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Willden, R., 1964, Geology of the Christmas quadrangle, Gila and Pinal Counties, Arizona: U.S. Geological Survey Bulletin 1161-E, 64 p. 40 Wong, M.S., and Gans, P.B., 2008, Geologic, structural, and thermochronologic constraints on the tectonic evolution of the Sierra Mazatán core complex, Sonora, Mexico: New insights into metamorphic core complex formation: Tectonics, v. 27, no. 4, TC4013. Wrucke, C.T., 1989, The Middle Proterozoic Apache Group, Troy Quartzite, and associated diabase of Arizona: Arizona Geological Society Digest 17, p. 239-258. 41 Figure 1. 42 Figure 2. 43 Figure 3. 44 Figure 4. 45 Figure 5. 46 Figure 6. 47 Figure 7. 48 Figure 8 49 APPENDIX A: “DOMINO-STYLE” TILTING IN METAMORPHIC CORE COMPLEXES: EVIDENCE FROM RADIAL DIKES IN THE PINALEÑO MOUNTAINS, ARIZONA Phillip A. Nickerson* Eric Seedorff Lowell Institute for Mineral Resources Department of Geosciences University of Arizona 1040 East Fourth Street Tucson, Arizona 85721-0077, USA To be submitted to Lithosphere 50 ABSTRACT Geologic mapping and stereographic analysis of a radial porphyry dike swarm in the footwall of the Pinaleño metamorphic core complex (MCC) of southeastern Arizona place constraints on competing interpretations for formation of MCCs. Three new U-Pb dates confirm that the dikes are Oligocene in age (~26.5 Ma). A method for determining paleo-vertical in radial dikes swarms via stereographic analysis on a π diagram is demonstrated and then used to show that both the footwall and hanging wall of the Pinaleño MCC were homogeneously tilted ~83° SW during Oligo-Miocene extension. Mapped patterns of hydrothermal alteration that are intimately associated with the intrusion of the dike swarm also are consistent with significant southwesterly tilting of footwall rocks. A previous interpretation of the Pinaleño MCC contends that the MCC formed via isostatic upwarp of a strongly listric normal fault, implying different amounts of tilting in hanging wall and footwall rocks and folding of the footwall rocks about a horizontal axis perpendicular to the extension direction; neither style of deformation is recorded by the dike swarm. The constraints on footwall deformation instead favor a “domino- style” model of MCC formation that produces similar amounts of tilting in hanging wall and footwall rocks. A new interpretation for formation of this MCC involves at least two independent sets of nearly planar normal faults that were sequentially superimposed. These results suggest that warping of normal faults by localized isostatic uplift is not required for MCC formation. 51 INTRODUCTION Metamorphic core complexes (MCCs) are widespread in highly extended continental and oceanic crust (e.g., Verdel et al., 2007; John and Cheadle, 2010). Constraints placed on the geometry, timing, and style of deformation of rocks in the footwall of MCCs place important limitations on the applicability of competing models for formation of MCCs (Roberts and Yielding, 1994). For instance, if a MCC were formed only via slip on an initially low-angle normal fault (e.g., Wernicke, 1981), rocks in the footwall of the MCC would experience minimal tilting or folding during exhumation. If isostatic warping of a strongly listric normal fault were the principal mechanism (i.e. the “rolling-hinge” model, Wernicke, 1992), rocks in the footwall would be folded about a horizontal axis perpendicular to the extension direction (Spencer, 1984). If “domino-style” faulting (e.g., Proffett, 1977; Davis, 1987) were the principle process (Wong and Gans, 2008), the amount of tilting of footwall and hanging wall rocks would be similar. Magmatic-hydrothermal systems (dikes, stocks, and associated hydrothermal features) developed in the Basin and Range province (e.g., Seedorff et al., 2008) offer a powerful set of constraints on the magnitude, geometry, and timing of extensional features. For example, the orientations of porphyry dikes can be used to constrain structural deformation of crystalline rocks (Wong and Gans, 2008). Also, mapped patterns of hydrothermal alteration can be used as markers in a structural column because vertical and lateral zoning patterns in porphyry systems, though variable between deposits, are nonetheless reasonably predictable (e.g., Sillitoe, 2010). 52 In this study, the magmatic-hydrothermal system associated with a pre-extension radial porphyry dike swarm exposed in the footwall of the Pinaleño MCC in southeastern Arizona was mapped, analyzed, and compared with other key localities. The results expand the utility of radial dike swarms in the structural analysis of deformation in crystalline rocks and are then used to test several competing models for MCC formation. PINALEÑO MCC The footwall of the Pinaleño MCC (Fig. 1A) is bounded on the west by the Eagle Pass fault and on the east by the Pinaleño detachment fault (Davis, 1980; Naruk, 1987; Kruger and Johnson, 1994). Mylonitic fabrics, produced by northeast-southwest extension, are only present on the eastern margin of the MCC structurally below the Pinaleño detachment fault (Naruk, 1987). In its current orientation, the Eagle Pass fault dips gently (12° SW) and separates Tertiary rocks in the hanging wall that dip 80-85° SW from Proterozoic crystalline rocks in the footwall (Fig. 1A). Kinematic indicators show that fault motion was up dip to the northeast. The fault was first mapped as a thrust fault (Blacet and Miller, 1978) but was reinterpreted by Davis and Hardy (1981) as a normal fault that has been tilted through horizontal. Naruk (1987) argues that this tilting was the result of isostatic uplift during the formation of the Pinaleño MCC and that the Eagle Pass fault is the warped, up-dip, expression of the Pinaleño detachment fault. Alternatively, Lister and Davis (1989) suggested that the geometry of the Pinaleño detachment fault was nearly planar and that the Pinaleño MCC formed by the dominolike “shear zone” model of Davis (1983, 1987). Subsequent studies in this MCC have 53 favored the Naruk (1987) interpretation (i.e., Kruger and Johnson, 1994; Long et al., 1995). Porphyry Dike Swarm The Eagle Pass dike swarm is exposed in the footwall of the MCC (Fig 1A, 1D). The composition of dikes in the swarm varies from rhyolitic porphyry, to quartz latitic porphyry, to andesitic porphyry, in order of decreasing abundance. One dike from the swarm yielded a K-Ar age of 24.66 ± 0.60 Ma (Shafiqullah et al., 1980). However, the KAr age may record the exhumation of the dike swarm during Oligo-Miocene extension, not the age of intrusion of the dike. To better constrain the magmatic age of the dike swarm, U-Pb zircon geochronology by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was conducted at the University of Arizona LaserChron Center. Methods are discussed in Appendix A.1. Three dikes were selected for analysis; one rhyolite porphyry dike cut by quartz veins (Fig. 2A), one unaltered andesite porphyry dike (Fig. 2B), and one quartz latite porphyry dike (Fig. 2C) containing secondary biotite and chalcopyrite (e.g., indicators of potassic alteration and copper mineralization). Results show that the rhyolite dike intruded at 26.46±0.11 Ma, the andesite dike at 26.7±1.2 Ma, and the quartz latite dike at 26.3±1.2 Ma. The ages represent the first well documented occurrence of a post-Laramide (80-50 Ma) porphyry system in Arizona. The ages of the dikes also place a maximum age for the initiation of normal faulting in the MCC of ~26.5 Ma, as the dikes are cut by the Eagle Pass fault. 54 Dike Orientations and Their Use as a Paleo-Vertical Indicator Orientations of dikes within radial dike swarms have been used to determine paleo-stress fields during dike emplacement (Nakamura, 1976; Muller and Pollard, 1977). Paleo-stress fields are determined using fundamentals of rock mechanics (Pollard, 1987) which state that the least principal stress (σ3) is orientated perpendicular to the plane of the dike, and the principal and intermediate stress (σ1 and σ2 respectively) are perpendicularly oriented somewhere within the plane of the dike. Anderson’s (1942) theory of dike’s and sills observes that the solid-liquid interface at the surface of the earth is unable to support shear stress; therefore, at near surface conditions the principal stresses must be oriented perpendicular or parallel to the earth’s surface (neglecting impacts from topography). Thus, dikes are vertical at the surface when either σ1 or σ2 are vertical. Near a magma chamber, principal stresses are oriented such that σ1 is perpendicular to the wall of the magma chamber (Roberts, 1970). As a dike propagates toward the surface its path will adjust to any changes in the orientations σ1, σ2, and σ3 (e.g. Muller and Pollard 1977). When dikes intrude above a magma chamber with a magma pressure greater than the regional stress field, as in the porphyry forming environment (e.g., Koide and Bhattacharji, 1975), changes in the orientations of σ1, σ2, and σ3 along an individual dike’s path are minimal, producing a nearly planar vertical dike (e.g.; Suppe 1985, p 225). The attitudes of individual dikes can be used to characterize the geometry of the collective swarm of dikes (Fig. 3) and can provide an indicator of the paleo-vertical direction at the time of the intrusion of the dikes. If dikes are thought to have intruded 55 with vertical or nearly vertical dips, the intersections of the dikes within a swarm will be vertical or near-vertical lines. The lines of intersection are determined by measuring the orientations of dikes from within a swarm. The orientation can then be plotted stereographically to determine their mean intersection (π axis) which constitutes a mean paleo-vertical indicator at the time of intrusion of the dikes. To demonstrate the technique, π axes were calculated for the dike swarms from localities where the amount (if any) of post-emplacement deformation is well constrained. The first example is the Spanish Peaks, Colorado, dike swarm (Fig. 4A), where most of the nearly 500 exposed dikes dip vertically, and only a few dip less than 80° (Odé, 1957). Due to the lack of any geologic evidence for post-emplacement deformation, the Spanish Peaks dike swarm is considered to be untilted. The distribution of dike attitudes on the π diagram suggests a symmetrical radial dike pattern (Fig. 3A). The line representing the intersection of the planes of the dikes, equal to the π axis on a π diagram, is nearly vertical (plunge of 88°; Fig. 4A), confirming that the π axis is an effective measurement of paleo-vertical. The second example is from the Yerington district of western Nevada, where the Ann-Mason porphyry dike swarm is known to be tilted ~90° to the west-northwest (Proffett, 1977). Here, the π axis has been tilted from vertical 88° west-northwest to an orientation of 02/110 (Fig. 4B). This orientation lies in the extension direction of the Yerington district and is interpreted to demonstrate that the paleo-vertical indicator in the dike swarm records the same west-northwest tilting observed in strata of similar age and by paleomagnetism (Geissman et al., 1982; Proffett and Dilles, 1984). When rotated to 56 their pre-tilting orientations, the distribution of the dikes in the Ann-Mason swarm (Fig. 4C) suggests a knotted radial dike pattern (Fig. 3B). For the Pinaleño MCC, this technique reveals a π axis oriented 07/055 (Fig. 4E). This orientation plots in the extension direction of the Pinaleño MCC and indicates that the Eagle Pass dike swarm in the footwall of the MCC has been tilted (83° SW) a similar amount as the most tilted Tertiary hanging wall rocks (~80°-85° SW; Fig. 4D). When the dike data are rotated to restore paleo-vertical indicator to vertical (Fig. 4F), the dikes exhibited a knotted radial pattern (Fig. 2B), consistent with the variation documented in the dips of the dikes (Fig. 1A; Fig. 1D) but inconsistent with a sheeted pattern (Fig. 3C). Folding of footwall rocks The orientations of the Eagle Pass dikes can also be used to determine if footwall rocks were folded during MCC formation as proposed by Naruk (1987). The southern cluster of dikes within the main dike swarm (near dip marker of 62° SE in Fig. 1A) all dip to the southeast at ~60°. If these dikes represented rocks in the southwestern limb of a northwest-southeast striking antiform (as proposed by Naruk, 1987), the strike of these dikes would diverge to the north as they traverse the MCC. This systematic deviation is not observed over the 7 km strike length of the dikes (Fig 1A). Hydrothermal Alteration Zoning patterns in hydrothermal alteration are created by changes in the pressure, temperature, and composition of hydrothermal fluids as they circulate in and adjacent to intrusions (Seedorff et al., 2005) and can be used to constrain deformation in crystalline rocks (Fig. 5A). Where hydrothermal alteration patterns are observed to progress from 57 deeper styles to shallower styles across a fault block, the direction and relative amount of tilting of the porphyry system can be determined. In the Pinaleño MCC the general distribution of hydrothermal alteration was mapped, revealing systematic patterns (more detailed description and analysis of mineral assemblages and phases is given in Appendix B). Potassic alteration developed proximal to the dike swarm, and its intensity dissipates to the north and south (Fig. 5B). Sodiccalcic alteration developed ~5 km distal to the potassic alteration to the northwest and southeast (i.e., perpendicular to the extension direction). Near the fault zone, sodic alteration characterized by the assemblage quartz-chlorite-albite-specular hematite alteration is superimposed upon the other styles of alteration. The localization of the quartz-chlorite-albite-specular hematite alteration along the fault zone as previously identified by Davis and Hardy (1981), coupled with the fact that it overprints other styles of alteration, suggests that this alteration style was genetically associated with the Eagle Pass fault and thus is unrelated to the ~26.5 Ma porphyry system. The observed relationship between hydrothermal alteration zoning patterns and the extension direction is similar to what has been documented in tilted porphyry systems in Arizona (i.e., sodic-calcic and sodic alteration developed distal to potassic alteration only perpendicular to the extension direction; Seedorff et al., 2008; Stavast et al., 2008; Nickerson et al., 2010) and corroborates the hypothesis that the footwall of the Pinaleño MCC is significantly tilted to the southwest. 58 INTERPRETATION OF OLIGOCENE REGIONAL STRESS PATTERNS IN SOUTHEASTERN ARIZONA The northeast-southwest preferential strike direction of dikes in the Eagle Pass dike swarm has interesting implications for the Oligo-Miocene regional stress pattern in southeastern Arizona. Throughout Arizona, Oligocene and Miocene dikes are observed to have a strong northwest-southeast preferential strike direction; whereas, Laramide aged dikes (~75-55Ma) are known to have a strong northeast-southwest preferential strike direction (Heidrick and Titley, 1982). Regional stress patterns are known to control dike orientations, because except under isotropic stress conditions, the strikes of dikes run perpendicular to σ3 (Pollard, 1987). Thus, the strong correlation of dike strike direction with age in Arizona is thought to be a manifestation of the change from northwestsoutheast compression in the Late Cretaceous-Early Tertiary, to northwest-southeast extension in the Oligocene and Micoene (Heidrick and Titley, 1982). The orientation of regional stress in southeastern Arizona can be examined by constraining the onset of extension. Less than 40 km to the southwest on the western slope of the Galiuro Mountains (Fig. 1C), and 80 km to the northeast near Morenci, Arizona, northeast-southwest extension is known to have begun by 35 Ma (Dickinson, 1991) and 29 Ma (Ferguson et al., 2000), respectively. As described above, dikes intruding under these stress conditions would strike northwest-southeast, perpendicular to the strike of Dikes in the Eagle Pass dike swarm. Thus, the new U-Pb ages for the Eagle Pass dike swarm (Fig. 2) can be interpreted to suggest that regional stress fields varied widely over just tens of km during 59 the late Oligocene in southeastern Arizona. Furthermore, the data indicate that the Eagle Pass dike swarm intruded under a stress regime similar to the Laramide episode of northeast-southwest compression (Heidrick and Titley, 1982). In fact, when the orientations of the dikes are rotated so that the paleo-vertical indicator is oriented vertically (Fig. 4E), the orientations match very closely what is observed in magmatichydrothermal features from the Laramide Safford district (Dunn, 1978) 50 km to the east (see Appendix B Fig. 5), an area for which there is no evidence of post-Laramide tilting. IMPLICATIONS FOR THE FORMATION OF THE PINALEÑO MCC Both the paleo-vertical indicator preserved in the radial dike swarm, and the documented zoning patterns in hydrothermal alteration associated with the late Oligocene porphyry copper system in the footwall of the Pinaleño MCC indicate that the hanging wall and the footwall of the MCC were tilted congruently during MCC formation. These results require the amount of down-dip curvature on the Eagle Pass fault to be minimal, which matches predictions of a “domino-style” model of MCC formation and controverts the involvement of listric faulting in the formation of this MCC. A reinterpretation of the formation of the Pinaleño MCC is needed to respect the new evidence for congruent hanging wall and footwall tilting. It is proposed that the Pinaleño MCC formed by the superposition of two major sets of normal faults in a “domino-style” model (Fig. 6A-C). Whereas faults within each set are loosely kinematically linked to one another, the two fault sets were discrete in time and not kinematically linked. The transition from nearly horizontal, untilted strata to significantly tilted rocks (“breakaway zone”) on the eastern side of the Galiuro Mountains is formed 60 by the superposition of two footwall synclines that are related to each fault set (Fig. 6AC). The Eagle Pass fault achieved its current orientation by first tilting to lower angles during slip, and then by passively tilting in the hanging wall of a fault in the subsequent set. The second set of faults includes the Pinaleño detachment fault, and an unnamed fault which is covered by Tertiary and Quaternary gravels. A fault in the location of the unnamed fault has been imaged seismically (Kruger and Johnson, 1994). The Pinaleño detachment fault cuts and offsets the Eagle Pass fault, and the mylonites of the Pinaleño MCC are located in the footwall of both major normal faults. The new interpretation incorporates previous constraints placed on the geometry and magnitude of normal faulting in the Pinaleño MCC from seismic reflection (Kruger and Johnson, 1994) and shear strain (Naruk, 1987) analyses. DISCUSSION Subsequent to the identification of MCCs as manifestations mid-crustal extension (Crittenden et al., 1980), geologists have attempted to pinpoint what geologic processes are critical to MCC formation. The “rolling hinge” model (e.g., Wernicke, 1992) that has been widely applied to explain the formation of continental and oceanic MCCs globally (e.g. Verdel et al., 2007; Kapp et al. 2008; John and Cheadle, 2010), including the Pinaleño MCC (Naruk, 1987) requires several kilometers of isostatic uplift to be focused over an area ~10-20 km wide in the footwall of detachment faults. Deformation of this type would fold rocks in the footwall of MCCs and create differential tilting between hanging wall and footwall rocks. 61 Evidence presented above for the Pinaleño MCC argues against such deformation. In additions recent seismic studies in the Catalina-Rincon MCC, Arizona (Arca et al., 2010), and numerous lines of geologic and thermochronologic evidence in the Sierra Mazatán MCC, Mexico (Wong and Gans, 2008) demonstrate that narrowly focused isostatic uplift was not important in the formation of these MCCs either. Without question thinning of the upper- and mid-crust to the degree observed in MCCs would be isostatically compensated in some manner, but evidence from these three MCCs suggests that isostatic compensation must have occurred over a much wider area. Such a scenario implies that the assumption of Airy isostacy in MCC formation (e.g. Spencer, 1984) is not valid, and instead indicates that the upper crust possesses some finite amount of flexural strength (Kusznir and Ziegler, 1992) even while undergoing severe extension. Future work in all MCCs should attempt to place constraints on footwall deformation and understand the implications, both geometric and mechanical, for SMCC formation. CONCLUSIONS Geologic constraints placed on the geometry, timing, and style of deformation in the Pinaleño MCC indicate that rocks in the hanging wall and footwall of the MCC were tilted similar amounts during formation of the MCC. The “domino-style” model for MCC formation appropriately replicates the uniform tilting of hanging wall and footwall blocks. This work suggests that more constraints can be placed on the footwall geology of MCC using geologic techniques, especially the examination of paleo-vertical indicators preserved in dike swarms and mapping of hydrothermal alteration. These 62 results taken together with recent work in other MCCs suggest that warping of normal faults by localized isostatic uplift is not an essential mechanism required for MCC formation. ACKNOWLEDGMENTS The manuscript benefitted from earlier reviews by M. D. Barton and G. H. Davis. Conversations with D. A. Johnson and D. J. Maher were also helpful. Financial support of this project came from a Society of Economic Geologists Hugh E. McKinstry student research award and Science Foundation Arizona. REFERENCES Anderson, E. 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A: Geologic map of the northern portion of the Pinaleño MCC including endpoints of cross section A-A’ through the dike swarm. EPF = Eagle Pass fault; PDF=Pinaleño detachment fault. B: Location map of MCCs in western North America. C: Location of cross section B-B’ in Fig. 5. Dashed box is area shown in Fig. 1A. D. Cross section oriented perpendicular to the Eagle Pass dike swarm. A-A’ located in Fig. 1A. Figure 2. Best age results for U-Pb geochronology of zircons from three dikes in the Eagle Pass radial dike swarm. A. Rhyolite porphyry dike. Location: 32°45'18.25"N, 110° 8'9.21"W. B. Andesite porphyry dike. Location: 32°45'18.25"N, 110° 8'9.21"W. C. Quartz latite porphyry dike. Location: 32°45'20.17"N, 110° 7'21.67"W. Figure 3. Idealized geometries of steeply-dipping dike swarms in map view. A. Symmetrical radial dikes. B. Knotted radial dikes. C. Sheeted dikes. Radial dikes of A and B intersect in a vertical line; sheeted dikes of C do not intersect. Figure 4. Contoured poles to planes of dikes and bedding. All stereonets are equal area plots. Contour intervals are per 1% area. Black circle = π axis (i.e., the average intersection of the planes) unless otherwise noted. A. Orientation of dikes in the Spanish Peaks dike swarm. Data from Smith (1978). B. Orientation of dikes in the Ann-Mason dike swarm at Yerington. Dashed line = plane to π axis. Data from Dilles (1983). C. Orientation of Ann-Mason dikes with paleo-vertical indicator rotated to vertical D. Orientation of the most steeply dipping sedimentary and volcanic rocks in the hanging wall of the Eagle Pass fault. Here the black circle = pole to mean plane. E. Orientation of dikes in the footwall of the Eagle Pass fault. Dashed line = plane to π axis. Both hanging 70 wall and footwall rocks show similar amounts of tilting (compare pole to mean plane in panel D to π axis in panel E). Both lines were vertical prior to extension. F. Orientation of dikes in the Pinaleño MCC with π axis rotated to vertical. Figure 5 A: Schematic cross section showing a typical pattern of sericitic, potassic, and sodic-calcic hydrothermal alteration in a porphyry copper system. Dashed grey line is the proposed surface exposure in the Pinaleño MCC. Dashed brown lines indicate areas were sodic-calcic alteration may be superimposed on potassic alteration in a porphyry setting. B: Mapped pattern of hydrothermal alteration in the Pinaleño MCC; compare with distribution of rocks and structures of Fig. 1A. Figure 6. Three-stage model for the formation of the Pinaleño MCC. Dashed line marks a structural horizon at 12 km depth prior to extension. A: Eagle Pass fault (EPF) breaks at a high angle to the surface and begins tilting to lower angles during extension. B: A new fault set breaks at high angles (PDF= Pinaleño detachment fault). The PDF cuts the now dormant Eagle Pass fault, and begins tilting to lower angles during continued extension. Label 1: Rocks above and below the Eagle Pass fault are rotated such that they take the form of a hanging wall anticline and footwall syncline. C: Present day cross section through Pinaleño MCC. Label 2. Rocks in the footwall of this unnamed inferred fault are rotated such that they take the form of a footwall syncline. Label 3. Rocks previously rotated in the footwall of the Eagle Pass fault are further tilted during slip on the unnamed fault. D: More detailed cross section from the Galiuro Mountains to the Pinaleño Mountains. Location of the line of section indicated by dashed lines in Panel C. Abbreviations: QTg = Quaternary and Tertiary gravels; Tu= Tertiary volcanic and 71 sedimentary rocks; YX = Proterozoic rocks, shades in purple reflect the depth of the rocks prior to extension. Figure 7. A: Cross section through Pinaleño MCC after Naruk (1987) using “rolling-hinge” model for MCC formation, which predicts different amounts of hanging wall and footwall tilting in the MCC that is not supported by new evidence presented here. The dashed line marking rocks originally at 12 km depth has been added to the original figure. B: New model for the formation of the Pinaleño MCC. The new model replicates the structural features of the previous model, but also honors the new data suggesting similar hangingwall and footwall tiling in the MCC. Rock labels same as Figure 6. 72 Figure 1. 73 Figure 2. 74 Figure 3. 75 Figure 4. 76 Figure 5. 77 Figure 6. 78 Figure 7. 79 APPENDIX A.1 Zircon crystals were extracted from samples by traditional methods of crushing and grinding, followed by separation with a Wilfley table, heavy liquids, and a Frantz magnetic separator. Samples were processed such that all zircons were retained in the final heavy mineral fraction. A split of these grains (generally 50-100 grains) were selected from the grains available and incorporated into a 1” epoxy mount together with fragments of our Sri Lanka standard zircon. The mounts were sanded down to a depth of ~20 microns, polished, imaged, and cleaned prior to isotopic analysis. U-Pb geochronology of zircons was conducted by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) at the Arizona LaserChron Center (Gehrels et al., 2008). The analyses involve ablation of zircon with a New Wave UP193HE Excimer laser (operating at a wavelength of 193 nm) using a spot diameter of 30 microns. The ablated material is carried in helium into the plasma source of a Nu HR ICPMS, which is equipped with a flight tube of sufficient width that U, Th, and Pb isotopes are measured simultaneously. All measurements are made in static mode, using Faraday detectorswith 3x1011 ohm resistors for 238U, 232Th, 208Pb206 Pb, and discrete dynode ion counters for 204Pb and202Hg. Ion yields are ~0.8 mv per ppm. Each analysis consists of one 15-second integration on peaks with the laser off (for backgrounds), 15 one-second integrations with the laser firing, and a 30 second delay to purge the previous sample and prepare for the next analysis. The ablation pit is ~15 microns in depth. 80 For each analysis, the errors in determining 206Pb/238U and 206Pb/204Pb result in a measurement error of ~1-2% (at 2-sigma level) in the 206Pb/238U age. The errors in measurement of 206Pb/207Pb and 206Pb/204Pb also result in ~1-2% (at 2-sigma level) uncertainty in age for grains that are >1.0 Ga, but are substantially larger for younger grains due to low intensity of the 207Pb signal. For most analyses, the cross-over in precision of206Pb/238U and 206Pb/207Pb ages occurs at ~1.0 Ga. 204 Hg interference with 204Pb is accounted for measurement of 202Hg during laser ablation and subtraction of 204Hg according to the natural 202Hg/204Hg of 4.35. This Hg is correction is not significant for most analyses because our Hg backgrounds are low (generally ~150 cps at mass 204). Common Pb correction is accomplished by using the Hg-corrected 204Pb and assuming an initial Pb composition from Stacey and Kramers (1975). Uncertainties of 1.5 for 206Pb/204Pb and 0.3 for 207Pb/204Pb are applied to these compositional values based on the variation in Pb isotopic composition in modern crystal rocks. Inter-element fractionation of Pb/U is generally ~5%, whereas apparent fractionation of Pb isotopes is generally <0.2%. In-run analysis of fragments of a large zircon crystal (generally every fifth measurement) with known age of 563.5 ± 3.2 Ma (2-sigma error) is used to correct for this fractionation. The uncertainty resulting from the calibration correction is generally 1-2% (2-sigma) for both 206Pb/207Pb and 206Pb/238U ages. Concentrations of U and Th are calibrated relative to our Sri Lanka zircon, which contains ~518 ppm of U and 68 ppm Th. 81 Locations of samples are shown in Table 1 and analytical data are reported in Table 2. Uncertainties shown in these tables are at the 1-sigma level and include only measurement errors. Inheritance was tested in the samples by examining both the core and tip of each zircon where possible. Ages older than Oligocene were interpreted to represent inheritance in the samples. Many of these ages are Proterozoic in age, which would be expected due to the Proterozoic age of the country rock in the study area. The resulting interpreted ages are shown on weighted mean diagrams using the routines in Isoplot (Ludwig, 2008) (Fig. 2). The weighted mean diagrams show the weighted mean (weighting according to the square of the internal uncertainties), the uncertainty of the weighted mean, the external (systematic) uncertainty that corresponds to the ages used, the final uncertainty of the age (determined by quadratic addition of the weighted mean and external uncertainties), and the MSWD of the data set. REFERENCES Gehrels, G.E., Valencia, V., Ruiz, J., 2008, Enhanced precision, accuracy, efficiency, and spatial resolution of U-Pb ages by laser ablation-multicollector-inductively coupled plasma-mass spectrometry: Geochemistry, Geophysics, Geosystems, v. 9, Q03017 doi:10.1029/2007GC001805. Ludwig, K., 2008, Isoplot 3.6: Berkeley Geochronology Center Special Publication 4, 77 p. 82 Stacey, J.S., and Kramers, J.D., 1975, Approximation of terrestrial lead isotope evolution by a two-stage model: Earth and Planetary Science Letters, v. 26, p. 207-221. 83 TABLE 1. Location of U-Pb geochronology samples Sample Latitude Longitude EP 017d 32°45'18.25"N 110° 8'09.21"W EP 017e 32°45'18.25"N 110° 8'09.21"W EP 038b 32°45'20.17"N 110° 7'21.67"W 84 TABLE 1. U-Pb geochronologic analyses Isotope ratios Analysis U 206Pb U/Th 206Pb* ± 207Pb* ± 206Pb* Apparent ages (Ma) ± error 206Pb* ± 207Pb* ± 206Pb* ± Best age ± (ppm) 204Pb 207Pb* (%) 235U* (%) 238U (%) corr. 238U* (Ma) 235U (Ma) 207Pb* (Ma) (Ma) (Ma) EP 017D 1C 212 46400 1.7 11.2709 1.7 1.1318 17.2 0.0925 17.2 1.00 570.4 93.7 768.6 93.2 1398.2 31.7 1398.2 31.7 EP 017D 1T 544 300090 5.2 11.0776 0.4 2.9355 1.4 0.2358 1.3 0.95 1365.0 16.3 1391.1 10.5 1431.3 8.3 1431.3 8.3 EP 017D 2C 320 7275 2.0 20.6222 18.1 0.0764 18.5 0.0114 3.9 0.21 73.3 2.8 74.8 13.3 123.3 428.6 73.3 2.8 EP 017D 3T 283 4231 1.9 24.3784 41.3 0.0243 43.0 0.0043 12.2 0.28 27.6 3.4 24.4 10.4 -286.3 1091.9 27.6 3.4 EP 017D 4C 156 42913 4.2 10.6470 0.9 3.2274 2.5 0.2492 2.3 0.93 1434.4 30.0 1463.8 19.4 1506.6 17.1 1506.6 17.1 EP 017D 5C 299 4845 0.5 1.3681 4001.9 0.3930 4001.9 0.0039 13.0 0.00 25.1 3.3 336.5 NA 0.0 1589.0 25.1 3.3 EP 017D 6C 218 98580 1.3 10.9945 1.0 3.1314 3.1 0.2497 2.9 0.95 1436.9 37.5 1440.4 23.6 1445.6 18.2 1445.6 18.2 EP 017D 6T 300 126179 1.3 11.0116 0.7 3.1349 1.0 0.2504 0.7 0.70 1440.4 8.6 1441.3 7.4 1442.7 13.1 1442.7 13.1 EP 017D 7C 475 282996 1.9 9.8943 0.4 4.0266 1.8 0.2889 1.8 0.98 1636.3 25.7 1639.6 14.8 1643.8 7.2 1643.8 7.2 EP 017D 9C 223 112663 2.4 10.1921 0.7 3.4606 5.9 0.2558 5.9 0.99 1468.4 77.2 1518.3 46.7 1588.6 13.0 1588.6 13.0 EP 017D 10T 384 455 0.6 23.7621 34.3 0.0230 34.7 0.0040 5.4 0.16 25.5 1.4 23.1 7.9 -221.5 885.8 25.5 1.4 EP 017D 11C 288 106965 2.0 11.0715 0.8 2.9062 2.4 0.2334 2.2 0.94 1352.1 26.9 1383.5 17.8 1432.3 15.8 1432.3 15.8 EP 017D 12C 189 3931 0.5 9.9549 48.7 0.0572 51.8 0.0041 17.6 0.34 26.6 4.7 56.5 28.5 1632.5 968.3 26.6 4.7 EP 017D 13C 20 8803 1.0 10.6689 6.6 2.7422 7.6 0.2122 3.9 0.50 1240.4 43.6 1340.0 56.9 1502.7 124.9 1502.7 124.9 EP 017D 14C 23 14665 1.1 11.1561 2.2 3.0765 3.0 0.2489 2.0 0.68 1432.9 25.6 1426.8 22.6 1417.8 41.5 1417.8 41.5 EP 017D 14T 24 13330 1.1 10.9079 3.7 3.1949 4.8 0.2528 3.1 0.65 1452.7 40.6 1455.9 37.2 1460.7 69.5 1460.7 69.5 EP 017D 15C 102 105897 1.4 9.9106 1.5 3.8992 2.1 0.2803 1.4 0.68 1592.7 19.7 1613.5 16.7 1640.8 28.1 1640.8 28.1 EP 017D 17T 229 1747 0.4 17.3649 76.9 0.0328 78.0 0.0041 12.8 0.16 26.5 3.4 32.7 25.1 514.1 2047.9 26.5 3.4 EP 017D 18C 183 1367 0.7 10.5284 102.5 0.0552 103.0 0.0042 10.1 0.10 27.1 2.7 54.5 54.8 1527.7 21.9 27.1 2.7 EP 017D 19T 570 6350 0.5 21.0800 28.5 0.0287 28.9 0.0044 5.1 0.18 28.3 1.4 28.8 8.2 71.3 689.2 28.3 1.4 EP 017D 20C 694 439 0.3 22.6986 22.0 0.0251 22.3 0.0041 3.5 0.16 26.6 0.9 25.1 5.5 -107.6 546.6 26.6 0.9 EP 017D 21C 34 25136 1.3 10.9826 3.1 3.1615 4.3 0.2518 2.9 0.69 1447.9 38.2 1447.8 33.1 1447.7 59.3 1447.7 59.3 EP 017D 22T 191 1541 0.5 7.9846 144.4 0.0699 145.0 0.0040 13.2 0.09 26.0 3.4 68.6 96.4 2032.2 126.1 26.0 3.4 EP 017D 22T2 117 1448 0.3 6.5470 58.8 0.0886 61.4 0.0042 17.4 0.28 27.1 4.7 86.2 50.7 2376.8 1122.7 27.1 4.7 EP 017D 23C 224 1905 0.4 13.4285 32.5 0.0449 34.4 0.0044 11.4 0.33 28.2 3.2 44.6 15.0 1054.2 671.5 28.2 3.2 EP 017E 1C 2953 18797 0.9 21.5161 11.0 0.0265 11.2 0.0041 2.1 0.18 26.6 0.5 26.6 2.9 22.4 265.1 26.6 0.5 EP 017E 2C 5223 27095 0.8 21.3609 3.3 0.0263 3.3 0.0041 0.5 0.14 26.2 0.1 26.4 0.9 39.8 78.6 26.2 0.1 EP 017E 3C 5731 34936 0.6 21.1227 2.8 0.0268 2.9 0.0041 1.0 0.33 26.4 0.3 26.8 0.8 66.5 66.2 26.4 0.3 85 EP 017E 3T 3158 7845 0.9 20.7528 9.1 0.0276 9.7 0.0042 3.3 0.34 26.7 0.9 27.7 2.6 108.4 215.9 26.7 0.9 EP 017E 4C 5093 27319 0.5 21.3187 3.2 0.0265 3.3 0.0041 0.9 0.28 26.4 0.2 26.6 0.9 44.5 75.7 26.4 0.2 EP 017E 5C 5000 31010 0.7 20.9426 4.8 0.0273 5.1 0.0042 1.9 0.37 26.7 0.5 27.4 1.4 86.9 113.1 26.7 0.5 EP 017E 6C 4961 44815 0.7 21.0631 3.8 0.0274 4.0 0.0042 1.3 0.31 26.9 0.3 27.4 1.1 73.2 91.4 26.9 0.3 EP 017E 7C 2929 6794 1.0 21.1598 8.1 0.0269 8.4 0.0041 2.2 0.27 26.5 0.6 26.9 2.2 62.4 192.9 26.5 0.6 EP 017E 8C 4321 5887 0.6 21.4210 2.5 0.0259 5.0 0.0040 4.3 0.87 25.9 1.1 26.0 1.3 33.1 59.6 25.9 1.1 0.3 EP 017E 9C 5983 49193 0.6 21.2579 2.8 0.0265 3.1 0.0041 1.2 0.41 26.3 0.3 26.6 0.8 51.3 67.1 26.3 EP 017E 10C 3741 24652 0.7 21.0362 3.0 0.0269 3.2 0.0041 1.2 0.38 26.4 0.3 27.0 0.9 76.3 70.6 26.4 0.3 EP 017E 11C 5149 72618 0.6 21.1808 5.5 0.0262 5.7 0.0040 1.7 0.29 25.9 0.4 26.3 1.5 60.0 130.7 25.9 0.4 EP 017E 12C 6142 43279 0.6 21.6115 2.4 0.0256 3.1 0.0040 1.9 0.62 25.8 0.5 25.7 0.8 11.8 57.8 25.8 0.5 EP 017E 12T 5986 43381 0.6 21.1893 3.6 0.0265 7.0 0.0041 6.0 0.85 26.2 1.6 26.6 1.8 59.1 87.0 26.2 1.6 EP 017E 13C 6414 32190 0.5 20.4154 3.1 0.0295 4.2 0.0044 2.9 0.67 28.1 0.8 29.5 1.2 147.0 73.6 28.1 0.8 EP 017E 14T 5276 41898 0.7 21.0984 4.4 0.0265 4.6 0.0041 1.0 0.23 26.1 0.3 26.6 1.2 69.3 105.5 26.1 0.3 EP 017E 15C 3021 19189 0.8 22.1222 8.4 0.0253 8.7 0.0041 2.2 0.26 26.1 0.6 25.3 2.2 -44.7 204.7 26.1 0.6 EP 017E 16C 3051 16390 0.9 21.0663 6.7 0.0264 6.8 0.0040 1.1 0.16 26.0 0.3 26.5 1.8 72.9 158.8 26.0 0.3 EP 017E 17T 6012 36359 0.6 21.3112 3.9 0.0264 4.4 0.0041 1.9 0.43 26.2 0.5 26.4 1.1 45.4 93.7 26.2 0.5 EP 017E 18C 5967 38074 0.5 21.6152 2.7 0.0271 3.1 0.0042 1.6 0.51 27.3 0.4 27.1 0.8 11.4 63.9 27.3 0.4 EP 017E 19C 4058 42710 0.6 20.9604 4.8 0.0279 5.2 0.0042 2.0 0.39 27.3 0.5 27.9 1.4 84.8 114.5 27.3 0.5 EP 017E 20C 4788 49994 0.5 22.0775 4.2 0.0260 4.2 0.0042 0.4 0.09 26.8 0.1 26.0 1.1 -39.7 102.7 26.8 0.1 EP 017E 21C 5286 54458 0.7 21.0176 2.9 0.0273 3.2 0.0042 1.3 0.40 26.8 0.3 27.3 0.9 78.4 68.8 26.8 0.3 EP 017E 22C 3256 24681 1.1 21.1700 3.8 0.0265 4.0 0.0041 1.1 0.27 26.1 0.3 26.5 1.0 61.2 90.7 26.1 0.3 EP 017E 23C 3287 9898 0.8 21.3422 4.8 0.0265 5.1 0.0041 1.6 0.32 26.3 0.4 26.5 1.3 41.9 115.5 26.3 0.4 EP 017E 24C 6397 61217 0.5 20.8097 2.4 0.0299 5.3 0.0045 4.7 0.89 29.0 1.4 29.9 1.6 102.0 57.7 29.0 1.4 EP 038B-1C 192 752 1.2 31.7667 66.4 0.0179 67.4 0.0041 11.5 0.17 26.5 3.0 18.0 12.0 -1013.4 2194.1 26.5 3.0 EP 038B-2C 292 1389 0.9 25.7960 53.7 0.0223 54.8 0.0042 10.9 0.20 26.8 2.9 22.4 12.1 -432.5 1507.3 26.8 2.9 EP 038B-3C 238 3070 1.1 24.4464 122.4 0.0227 122.6 0.0040 7.0 0.06 25.9 1.8 22.8 27.7 -293.4 1510.8 25.9 1.8 EP 038B-4C 210 1540 0.9 21.5033 59.7 0.0233 61.7 0.0036 15.8 0.26 23.4 3.7 23.4 14.3 23.9 1567.9 23.4 3.7 EP 038B-5C 198 1152 1.0 -1.2738 3225.1 -z0.4492 3225.2 0.0042 9.3 0.00 26.7 2.5 -605.6 NA 0.0 870.9 26.7 2.5 EP 038B-8C 158 1308 1.4 21.0842 86.0 0.0264 87.4 0.0040 15.7 0.18 25.9 4.1 26.4 22.8 70.9 2672.4 25.9 4.1 EP 038B-9C 293 3464 1.1 17.5417 43.8 0.0315 44.5 0.0040 8.3 0.19 25.8 2.1 31.5 13.8 491.8 1011.2 25.8 2.1 EP 038B-10C 133 848 1.0 -1.2437 759.4 -0.4565 759.6 0.0041 17.5 0.02 26.5 4.6 -619.1 NA 0.0 992.3 26.5 4.6 EP 038B-11C 198 1257 0.9 6.2955 176.1 0.0858 176.4 0.0039 11.5 0.07 25.2 2.9 83.6 142.5 2443.4 256.1 25.2 2.9 EP 038B-13C 293 2458 0.8 33.6180 57.9 0.0160 59.3 0.0039 12.4 0.21 25.0 3.1 16.1 9.5 -1185.1 1928.8 25.0 3.1 86 EP 038B-15C 147 1399 0.9 18.9318 84.9 0.0314 87.1 0.0043 19.2 0.22 27.8 5.3 31.4 27.0 321.1 2511.4 27.8 5.3 EP 038B-16C 196 1410 1.0 13.6952 67.9 0.0425 68.7 0.0042 10.5 0.15 27.1 2.8 42.2 28.4 1014.4 1585.9 27.1 2.8 EP 038B-18C 398 2632 1.2 18.1560 86.7 0.0308 86.9 0.0041 6.3 0.07 26.1 1.6 30.8 26.3 415.4 2584.0 26.1 1.6 EP 038B-19C 310 2467 1.1 33.6761 54.3 0.0171 54.8 0.0042 7.6 0.14 26.9 2.0 17.3 9.4 -1190.4 1790.9 26.9 2.0 EP 038B-20C 640 12737 1.3 10.6677 1.6 0.4806 4.0 0.0372 3.6 0.92 235.4 8.4 398.5 13.1 1502.9 29.9 235.4 8.4 EP 038B-21C 195 1301 0.9 24.1574 37.8 0.0237 41.1 0.0042 16.2 0.40 26.7 4.3 23.8 9.7 -263.2 988.6 26.7 4.3 EP 038B-22C 418 4069 1.0 19.0175 34.6 0.0302 35.4 0.0042 7.6 0.21 26.8 2.0 30.2 10.5 310.9 809.6 26.8 2.0 EP 038B-23C 450 3858 0.6 31.6983 49.1 0.0180 49.8 0.0041 8.6 0.17 26.7 2.3 18.2 9.0 -1007.0 1534.4 26.7 2.3 EP 038B-24C 192 2199 0.9 9.8477 111.8 0.0590 112.4 0.0042 11.4 0.10 27.1 3.1 58.2 63.6 1652.6 48.4 27.1 3.1 87 1. 2. Analyses with >10% uncertainty (1-sigma) in 206Pb/238U age are not included. Analyses with >10% uncertainty (1-sigma) in 206Pb/207Pb age are not included, unless 206Pb/238U age is <500 Ma. 3. Best age is determined from 206Pb/238U age for analyses with 206Pb/238U age <900 Ma and from 206Pb/207Pb age for analyses with 206Pb/238Uage > 900 Ma. 4. All uncertainties are reported at the 1-sigma level, and include only measurement errors. 5. Systematic errors are as follows (at 2-sigma level): [sample 1: 2.5% (206Pb/238U) & 1.4% (206Pb/207Pb)] 6. Analyses conducted by LA-MC-ICPMS, as described by Gehrels et al. (2008). 7. U concentration and U/Th are calibrated relative to Sri Lanka zircon standard and are accurate to ~20%. 8. Common Pb correction is from measured 204Pb with common Pb composition interpreted from Stacey and Kramers (1975). 9. Common Pb composition assigned uncertainties of 1.5 for 206Pb/204Pb, 0.3 for 207Pb/204Pb, and 2.0 for 208Pb/204Pb. 10. U/Pb and 206Pb/207Pb fractionation is calibrated relative to fragments of a large Sri Lanka zircon of 563.5 ± 3.2 Ma (2-sigma). 11. U decay constants and composition as follows: 238U = 9.8485 x 10-10, 235U = 1.55125 x 10-10, 238U/235U = 137.88. 12. Weighted mean plots determined with Isoplot (Ludwig, 2008). 88 APPENDIX B: SODIC-(CALCIC) ALTERATION IN TWO ARIZONA PORPHYRY COPPER SYSTEMS: HYBRID HYDROTHERMAL SYSTEMS OF LARAMIDE AND MID-TERTIARY AGES Phillip A. Nickerson* Mark D. Barton Eric Seedorff Lowell Institute for Mineral Resources Department of Geosciences University of Arizona 1040 East Fourth Street Tucson, Arizona 85721-0077, USA To be submitted to Economic Geology 89 ABSTRACT The flanks and cores the Laramide Tea Cup and Oligocene Eagle Pass porphyry copper systems in Arizona are examined here using U-Pb geochronology, as well as field and petrographic studies, to better characterize sodic (-calcic) and iron oxide-rich alteration found in porphyry systems. New U-Pb ages of zircons from Tea Cup reveal that the porphyry system dates from between ~72 and 70 Ma. Sodic assemblages at Tea Cup and Eagle Pass contain quartz, albite, chlorite, and epidote, whereas sodic-calcic assemblages found only at Tea Cup contain actinolite, andesine, epidote and, in areas of leaching of quartz, local garnet. Feldspar-destructive, sulfide-poor, iron oxide-rich alteration intensely developed at Tea Cup is characterized by the assemblage quartz + chlorite + albite ± specular hematite. Previously documented occurrences of these alteration styles in the Yerington district, Nevada, at the Ann-Mason deposit and the Yerington mine, and at SierritaEsperanza in the Pima district, Arizona, provide a basis of comparison for the new work. Sodic (-calcic) alteration at the Tea Cup is developed 2 - 4 km outboard from the most intense potassic alteration at paleodepths ranging from ~6 - 8 km. Iron oxide-rich alteration developed structurally higher at paleodepths of ~2 - 4 km. Sodic (-calcic) alteration at Eagle Pass is most intense 3 - 6 km outboard from the most intense potassic alteration across 4 km of paleodepth, and a spatially and mineralogically distinct zone of sodic alteration occurs in the immediate footwall of the Eagle Pass fault. The diverse manifestations of distal hydrothermal alteration in porphyry systems can be rationalized if all porphyry systems are conceptually regarded as hybrid 90 hydrothermal systems: a magmatic-hydrothermal portion best developed in the proximal or core region, and a non-magmatic portion dominated by externally derived fluids of various compositions on the flanks. The non-magmatic portion may be weakly developed to intense, and the associated alteration patterns may range spatially from completely outboard of the magmatic-hydrothermal alteration products in certain systems to intimately interfingering with or overprinting the magmatic-hydrothermal products in other systems. When dilute meteoric external fluids, which are characteristic of temperate climates, are circulated, propylitic alteration develops on the periphery. When saline brines, which are characteristic of arid regions, are convected on the periphery of a porphyry system, sodic (-calcic) alteration forms as the fluid descends on the warming path. After the externally-derived fluids eventually turn toward the surface, iron oxiderich alteration (with or without metals other than Fe, such as Cu and Au) forms at shallow structural levels on the cooling path. Nonetheless, the sodic (-calcic) and iron oxide-rich alteration also can be developed without being associated with a magmatic-hydrothermal system as long as there is a thermal drive for fluid circulation, as likely occurred along the Eagle Pass fault and in many IOCG systems worldwide. INTRODUCTION Sodic (-calcic) and iron oxide-rich hydrothermal alteration are essential components of iron-oxide copper gold (IOCG) deposits (Barton and Johnson, 1996, 2000; Williams et al., 2005). Sodic (-calcic) and iron oxide-rich hydrothermal alteration, however, also have been documented in some porphyry copper deposits (e.g., Yerington, Nevada; Carten, 1986; Sierrita-Esperanza, Arizona; Stavast et al., 2008; Ridgeway; 91 Wilson et al., 2003). Where documented in porphyry copper systems, sodic (-calcic) alteration is commonly developed at deep and distal positions, whereas iron oxide-rich hydrothermal alteration generally is developed distally at shallow levels (Carten, 1986; Dilles and Einaudi, 1992; Dilles et al., 2000; Barton et al., 2005). Although some workers remain skeptical of the origin of sodic(-calcic) alteration in porphyry systems (e.g., Bouzari and Clark, 2006; Sillitoe, 2010), in the most extensively studied porphyry systems that exhibit sodic (-calcic) and iron oxide-rich alteration, geologic and isotopic evidence indicates that the fluids were externally-derived saline brines that were drawn towards, and circulated by, magmatic heat sources (Dilles et al., 1992, 1995; Battles and Barton, 1995). Thus, the overall hydrothermal system can be regarded as composite, with a core formed from magmatic-hydrothermal fluids and fringes formed from externally-derived fluids. Deciphering the source of the brine that led to sodic (-calcic) and iron oxide-rich alteration is useful to the exploration geologist as these styles of alteration can be used as vectors toward mineralization, especially in porphyry systems that were tilted by post-ore faults (Nickerson et al., 2010). Moreover, iron oxide-rich alteration, although not necessarily well mineralized, can contain significant copper-gold mineralization (e.g., Pumpkin Hollow, Yerington district, Nevada; Battles and Barton, 1995). This paper examines the Tea Cup and Eagle Pass porphyry copper systems in Arizona (Fig. 1), which have been significantly tilted by sets of rotated normal faults, exposing the roots and flanks of the systems. The original work at Tea Cup builds on early work by Cornwall (1982) and more recent studies by Barton et al. (2005) and 92 Nickerson et al. (2010). The work at Eagle Pass builds on earlier geologic mapping and structural interpretation by work by Blacet and Miller (1978), Davis and Hardy (1981), and Naruk (1986) but represents the first description of hydrothermal alteration in the area. Sodic (-calcic) and iron oxide-rich hydrothermal alteration are well exposed on the flanks of the Tea Cup and Eagle Pass porphyry systems, as well as along the footwall of one of the Tertiary normal faults. Geologic mapping, electron microprobe analyses, and U-Pb geochronology are combined with previous palinspastic reconstructions to characterize the hydrothermal mineral assemblages, their timing, and the spatial distribution of these alteration types over ~5 km of paleodepth in the systems. The observations are then compared and contrasted with other localities, and the synthesis reveals two distinct situations in which sodic (-calcic) and iron oxide-rich alteration can be spatially associated with porphyry systems. In the first, sodic (-calcic) and iron oxiderich alteration are broadly contemporaneous with porphyry-related magmatism and the other of which was serendipitously superimposed on a portion of a porphyry system during extension-related exhumation of the porphyry system. GEOLOGIC SETTING The porphyry copper deposits of Arizona include some of the best studied porphyry systems in the world and have been the focus of over a century of scientific study (Ransome, 1903; Titley and Hicks, 1966; Titley, 1982a; Pierce and Bolm, 1995). However, the new ages on porphyry copper systems in Arizona (Seedorff et al., 2005a; Stavast, 2006; Nickerson and Seedorff, Appendix A), as well as the recognition and 93 description of the flanks and roots of these complex hydrothermal systems (Seedorff et al., 2008; Stavast et al., 2008; Nickerson et al., 2010), continue to advance the understanding of these porphyry copper systems. The Tea Cup (Fig. 2) and Eagle Pass (Fig. 3) porphyry systems, which are the focus of this study, are located in southeastern Arizona in the heart of the porphyry copper belt of southwestern North America (Fig. 1). Nearby porphyry copper districts include Ray (Phillips et al., 1974), Globe-Miami (Peterson, 1962), Superior (Hammer and Peterson, 1968; Manske and Paul, 2002), Poston Butte (Nason et al., 1982), Christmas (Koski and Cook, 1982), Pima (Barter and Kelly, 1982; Jansen, 1982; Titley, 1982c; Aiken and Baugh, 2007), Safford (Robinson and Cook, 1966; Dunn, 1978; Langton and Williams, 1982), and Morenci (Moolick and Durek, 1966; Enders et al., 2006). Exploration for porphyry copper deposits in the region has ebbed and flowed in tandem with copper prices (Lowell, 1978; Paul and Manske, 2005), with times of intense exploration occurring mainly in the late 19th and middle 20th centuries. The discovery of the Resolution deposit near Superior in the mid-1990s has renewed the interest of both junior and major mining companies in the region. As opposed to the well documented occurrences of sodic (-calcic) alteration on the continental margin of North America where plutons intruded into the thick sequence of sedimentary and volcanic rocks (Dilles et al., 2000), the Laramide (~80-50 Ma) and younger magmatism in Arizona intruded a thin (~2 km) cratonal section of sedimentary rocks (Titley, 1982b). As summarized by Dickinson (1989), the metamorphic basement of southeastern Arizona consists of the Mesoproterozoic Pinal Schist (ca. 1.7 Ga). These 94 crystalline rocks were intruded at 1.6 Ga by arc plutons of the Madera Diorite and at 1.4 Ga by widespread anorogenic granitic plutons known at Tea Cup as the Ruin Granite (Cornwall and Krieger, 1975a, b) and at Eagle Pass as the Laurel Canyon Granodiorite (Simons, 1964). The 1.4 Ga anorogenic plutons are host to the largest volume of hydrothermal alteration observed in both localities. Before 1.1 Ga, the basement was beveled and unconformably overlain by approximately 1 km of dominantly siliciclastic sedimentary rocks of the Proterozoic Apache Group and Troy Quartzite. Near the time of deposition of the Troy Quartzite, the siliciclastic sedimentary sequence and the underlying crystalline rocks were intruded by diabase sheets, sills, and dikes that are dated at ~1.1 Ga (Shride, 1967; Wrucke, 1989). The diabase sheets are most abundant in sedimentary rocks of the Apache Group and in the upper one km of the underlying crystalline rocks (Howard, 1991). The Proterozoic strata of the Troy Quartzite and Apache Group are disconformably overlain by approximately 1.0-1.5 km of Paleozoic strata, mainly carbonate rocks. Where preserved, evaporite-bearing beds are present in the uppermost part of the Paleozoic section in Permian strata (Blakey and Knepp, 1989). During Laramide time, regional contraction produced basement-cored uplifts similar to those of the central Rocky Mountains (Davis, 1979), and a large magmatic arc was built on the western margin of the North American plate (Drewes, 1976; Dickinson and Snyder, 1978; Dickinson, 1989). The arc formed between about 84 and 61 Ma and shows an overall progression to more felsic compositions over time (Cornwall, 1982; Lang and Titley, 1998; Seedorff et al., 2005a). Contraction clearly postdates early (~8580 Ma) relatively mafic magmatism (Willden, 1964). Porphyry copper formation is 95 related to somewhat younger (~75-55 Ma) arc magmatism of intermediate to silicic composition (Titley, 1982b; Lang and Titley, 1998), which, in the cases of at least certain deposits, postdates reverse faulting (Seedorff et al., 2005a; Barton et al., 2005). A period of tectonic quiescence and erosion characterized the post-Laramide period until Oligocene or early Miocene time (Dickinson, 1991), when magmatism and extension took hold in much of the region formerly occupied by the Laramide arc (Coney and Reynolds, 1978). Magmatism produced the bimodal Galiuro Volcanics exposed in the Galiuro Mountains and the Eagle Pass porphyry dike swarm in the northern Pinaleño Mountains (Nickerson and Seedorff, Appendix A). Large-magnitude extension dismembered and tilted porphyry systems and formed the Catalina-Rincon and Pinaleño metamorphic core complexes (Davis, 1980). Extension and magmatism continued through the Miocene, but by 15 Ma was of lesser magnitude and was more silicic, respectively. In many cases sedimentation accompanied extension in the newly formed basins. Post-extension, Tertiary and Quaternary gravels were deposited to form widespread pediment surfaces on older rocks (Dickinson, 1991). Today, the landscape is undergoing incision as the pediment surfaces are exhumed by down-cutting along the Gila River (Richard and Spencer, 1997). GEOCHRONOLOGY In this study, U-Pb geochronology was utilized to test a hypothesis that the Red Hills dike swarm is part of the Laramide Tea Cup porphyry system (Barton et al., 2005; Seedorff et al., 2005a). U-Pb zircon geochronology by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was conducted on for 96 samples at the University of Arizona LaserChron Center (Fig. 8A-E). Methods are discussed in Appendix E. Tea Cup system Samples were collected in and around the Tea Cup porphyry system to further constrain the timing of magmatism. Previous work by Barton et al. (2005) and Seedorff et al. (2005a) demonstrated that the composite Tea Cup pluton intruded over a period of two m.y. between ~74-72 Ma. Samples from the previous work (GB 202, GB 203) were dated again in this study, as were additional samples of dikes that crop out west of the Tea Cup pluton near the Red Hills prospect (Fig 2). The source intrusion of the dikes has there been a topic of speculation (Richard and Spencer, 1997). Nickerson et al. (2010) proposed, on the basis of similar mineralogy and a palinspastic structural reconstruction, some of the dikes were sourced from the biotite granite phase of the Tea Cup pluton. Results corroborate (Fig 4) this hypothesis as the ages yielded from both the pluton (GB 202: 71.1 ± 1.9 Ma; GB 203: 70.53 ± 0.73) and the dikes near the Red Hills (SP 100: 71.94 ± 0.73 Ma) fall within the 2σ error of one another. It is important to note that the samples GB 202 and 203 previously dated by Seedorff et al. (2005a) yielded ages ~ 2 m.y. younger in this study. An explanation for this discrepancy has not been identified at this time. Sample SP 103 (70.1 ± 1.5 Ma) was collected from a muscovitebearing quartz latite dike intruding the biotite granite phase of the Tea Cup pluton, which is known to be sourced from the muscovite-biotite granite phase of the Tea Cup pluton. Sample SP 102 (67.5 ± 2.9 Ma) was collected from a 50-m wide granite porphyry dike 97 five km north of the Red Hills, and its age indicates it postdates the intrusion of the Tea Cup pluton. Eagle Pass system U-Pb geochronology was previously conducted on the Eagle Pass dike swarm (Nickerson and Seedorff, Appendix A), yielding intriguing results. Ages from three dikes of different composition fell within 2σ error of one another at 26.5 Ma. Sulfide-bearing potassic alteration is hosted in one of the dated porphyry dikes, indicating that the Eagle Pass represents the first porphyry system in Arizona with a well documented postLaramide age. Furthermore, the northeast-southwest strike of the porphyry dikes, which has been shown to be a hallmark of Laramide porphyry systems (Heidrick and Titley, 1982), is also prominently displayed in the Oligocene dike swarm (Fig. 5A-B). The observed preference in strike direction shown in Laramide porphyry dikes (e.g., Safford: Fig. 5C) in Arizona has been attributed to a strong regional northeast-southwest compressional stress field during the Laramide (Heidrick and Titley, 1982). The same preferential strike direction of the Oligocene dikes suggests that near Eagle Pass a Laramide regional stress patterns prevailed until the onset of extension in Arizona, which in this region began after 26.5 Ma (Nickerson and Seedorff, Appendix A). HYDROTHERMAL ALTERATION ASSEMBLAGES Field and petrographic studies were conducted to constrain the mineralogy, timing, and spatial relationships of hydrothermal alteration in the study areas. Alteration terminology follows that of Seedorff et al. (2005b, 2008). At both Tea Cup and Eagle Pass, two types of feldspar-stable alteration are prevalent (Table 1). The core of the 98 hydrothermal system is defined by porphyry copper-style potassic alteration, whereas, sodic (-calcic) is developed in a distal position. In addition, iron oxide-rich, feldspardestructive alteration is intensely developed in the Tea Cup porphyry system. Tea Cup system Hydrothermal alteration in the Tea Cup porphyry system is described in several previous studies (Barton et al., 2005; Nickerson et al., 2010) and is summarized in the following text and in Figures (6-8 and Tables 1-5. Potassic alteration, which is typified by secondary biotite and/or K-feldspar plus quartz veins, formed in three distinct centers, each focused on a different phase of the composite Tea Cup pluton, which evolved to more felsic compositions with time. The oldest and most intense potassic alteration exposed in the study area is located near the cupola of the hornblende-biotite granodiorite, immediately west of the Kelvin prospect (Figs. 2, 6), where steeply dipping, east-west striking, sulfide-poor veins (Fig 7B) of quartz-K-feldspar, biotite, quartz, and magnetite-quartz locally reach up to 5 vol% abundance in outcrop. A younger, distinct area of widespread potassic alteration is centered just east of Mount Grayback near the cupola of the biotite - muscovite ± garnet granodiorite (the youngest phase of the pluton), where it takes the form of steeply dipping east-west striking (Fig. 7C) quartz +K-feldspar + muscovite ± biotite ± sulfide veins associated with aplitic to pegmatitic phases of the two-mica granite. Locally, vein abundance reaches ~1-3 vol%. Finally, to the west, weak to moderate potassic alteration occurs at the Red Hills prospect, where secondary, shreddy textured biotite and steeply dipping east-west striking (Fig. 7D) quartz ± Kfeldspar ± pyrite ± chalcopyrite veins (Fig. 3) reach ~1 vol% in abundance. As noted 99 above, Nickerson et al. (2010) proposed, and new U-Pb age dates corroborate (Fig 4A), that the potassic alteration exposed in the Red Hills is associated with the intrusion of the intermediate aged biotite granite phase of the Tea Cup pluton. Greisen-style alteration, which by definition is characterized by the presence of coarse-grained muscovite, consists of muscovite ± pyrite ± quartz that is widely developed west of Mount Grayback in the biotite - muscovite ± garnet granodiorite and, rarely, in the hornblende-biotite granodiorite located 1-2 km west of the Tea Cup cupola (Figs. 2, 6). Greisen locally forms narrow muscovite-rich veinlets, whereas other zones have widths of tens of centimeters. The character of the greisen varies along strike from solely muscovite-rich alteration envelopes to quartz + sulfide–rich cores with muscoviterich envelopes; locally, both have outer envelopes of K-feldspar (Seedorff et al., 2008). In contrast to the K-silicate and greisen alteration that are centrally located in the hydrothermal systems, sodic, sodic-calcic, and rare calcic assemblages are locally present to the north and are widespread to the south of the zone of most intense potassic alteration near the cupola of the hornblende-biotite granodiorite (Figs. 2, 6). Sodic assemblages contain quartz, albite, chlorite, and epidote, whereas sodic-calcic assemblages contain actinolite, andesine, epidote and, in areas of leaching of quartz, local garnet (Fig. 8A; Barton et al., 2005; Seedorff et al., 2008). At the eastern margin of the most intense sodic (-calcic) alteration, a potassium feldspar-stable, quartz-destructive assemblage of chlorite, actinolite, epidote, titanite is developed locally. Feldspar-destructive, sulfide-poor, iron oxide-rich alteration is intensely developed in the Ruin Granite near the eastern margin of the Tea Cup pluton and east of 100 the Red Hills prospect (Figs. 2, 6). The sulfide-poor nature of this type of feldspardestructive alteration, like the aforementioned sodic-calcic alteration,is characteristic of IOCG systems (e.g., Barton and Johnson, 2000; Williams et al., 2005). Steeply-dipping east-west striking veins of specular hematite + chlorite + quartz ± magnetite ± pyrite (Figs. 8B-C) reach several vol% in abundance, and locally areas of quartz + specularite hematite completely destroy preexisting texture. Zones of chlorite ± quartz alteration surround the most intense areas of sulfide-poor sericite-bearing alteration. Eagle Pass system Original, reconnaissance-scale mapping of hydrothermal alteration in the Eagle Pass porphyry system reveals that hydrothermal alteration is zoned in a symmetric pattern centered on the Oligocene Eagle Pass dike swarm (Figs. 3, 9). Three types of porphyry dikes were identified during field mapping and are described below in order of decreasing abundance: 1) Granite porphyry dikes with an aphanitic light gray groundmass of quartz and K-feldspar, 10% 2-4 mm quartz phenocrysts, 10% 1-2mm plagioclase phenocrysts, 5% 1-3 mm K-feldspar phenocrysts, and 1% 1-2 mm biotite phenocrysts. 2) Quartz monzonite dikes with a gray fine-grained groundmass of plagioclase and K-feldspar, 10% 1-3 mm plagioclase phenocrysts, 10% 1-4 mm Kfeldspar phenocrysts, 5% 1 mm biotite phenocrysts, 1% 2 mm hornblende phenocrysts, and 1% 1-2 mm quartz phenocrysts. 3) Quartz diorite dikes with an aphanitic dark gray groundmass of biotite, plagioclase, and quartz, 30% 1-3 mm plagioclase phenocrysts, and 5% 1-2 mm biotite phenocrysts. 101 Potassic alteration is most intensely developed within meters of the porphyry dikes at the southwestern end of the dike swarm, where it is characterized by secondary biotite, the addition of magnetite, and local areas of 1 vol% quartz ± sulfide veins. The vast majority of the potassic hydrothermal alteration at Eagle Pass is hosted in the Proterozoic units; however, the Oligocene dikes are locally cut by quartz - pyrite ± chalcopyrite veins. The intensity of potassic alteration decreases to the northwest and to the southeast of the center of the dike swarm. Quartz ± sulfide veins are absent outside the dike swarm; however, secondary biotite and magnetite are present as far as 1 km from the dike swarm. Sodic (-calcic) alteration is developed ~2 km distal to potassic alteration and within a zone approximately ~1 km from and parallel to the Eagle Pass fault (Fig. 9). Near the fault zone, sodic (-calcic) alteration is characterized by the assemblage quartz + chlorite + albite ± specular hematite (Fig. 8D). This assemblage overprints potassic alteration (chlorite replaces biotite, albite replaces oligoclase) developed in Proterozoic units but is only locally developed in the finer grained and less permeable Oligocene porphyry dikes. Tertiary andesite lava flows in the hanging wall of the Eagle Pass fault are predominantly unaltered, with the exception of sporadic specular hematite veins. North and south of the Eagle Pass dike swarm, sodic (-calcic) alteration is characterized by the destruction of quartz and the assemblage albite + chlorite + actinolite + epidote ± titanite ± hematite (Figs. 8E, 8G). Sodic (-calcic) alteration is most intensely developed north of the dike swarm, west of the contact between the Pinal Schist and Laurel Canyon Granodiorite (Fig. 9). Porphyry dikes do not crop out in this area; however, some 102 northeast-southwest striking quartz + epidote veins are truncated by the porphyry dikes two kilometers to the south. Whether those veins are directly associated with the intense sodic (-calcic) alteration to the north is uncertain. West of the most intense sodic (-calcic) alteration, a potassium feldspar-stable, quartz-destructive assemblage of chlorite, actinolite, epidote, and titanite is locally developed (Fig. 8F). COMPOSITIONS OF HYDROTHERMAL MINERALS Electron microprobe analysis of compositions of feldspar, mica, chlorite, amphiboles, and epidote from the Tea Cup and Eagle Pass porphyry systems were conducted on the Cameca SX 50 and Cameca SX 100 instruments. The beam diameter for analysis of all minerals except plagioclase was five μm, whereas the diameter for plagioclase varied from five to fifteen μm. Tea Cup system Minerals formed during potassic, sodic (-calcic), iron oxide-rich, and greisen alteration, as well as compositions of minerals from fresh Ruin Granite, were analyzed with the electron microprobe. Results are shown in Tables 2-4. Plagioclase compositions from sodic (-calcic) alteration in the Ruin Granite vary from An19 to An01 and in the Tea Cup pluton vary from An17 to An01. Mg/(Mg+Fe) ratios for biotite and chlorite replacing biotite found in potassically altered rocks range from 0.49 to 0.55 in the Ruin Granite and from 0.55 to 0.60 in porphyry dikes. Compositions of white micas from iron oxide-rich alteration at the Red Hills prospect range from 46 to 48 wt% SiO2. White micas in greisen alteration contain 0.0 to 0.37 wt% F, and SiO2 contents vary from 45-49 wt%. When compositions of minerals in the same alteration type are examined as a function of 103 paleodepth or distance from the center of the hydrothermal systems, no systematic patterns in composition are revealed for plagioclase, biotite, chlorite, or white mica. Eagle Pass system The composition of igneous minerals in the Laurel Canyon Granodiorite, as well as, minerals from sodic (-calcic) and potassic assemblages from Eagle Pass were analyzed with the electron microprobe. Plagioclase compositions from sodic (-calcic) alteration hosted in the Laurel Canyon Granodiorite north of the Eagle Pass dike swarm range from An23 to An01. Plagioclase from sodic (-calcic) alteration near the Eagle Pass fault are albitic, with compositions ranging from An04 to An00. Feldspar compositions from the potassium feldspar-stable, quartz-destructive assemblage of chlorite + epidote + titanite average An01 and Or95, respectively. Amphiboles present in sodic (-calcic) alteration are actinolitic in composition (Leake, 1997). Compositions of biotite and chlorite replacing biotite hosted in potassically altered Laurel Canyon Granodiorite showed elevated Mg/(Mg+Fe) ratios (0.50-0.59) compared to chlorite present in sodic (-calcic) alteration (0.24-0.48). Figure 10 illustrates this distinction by comparing Mg/(Mg+Fe) versus lateral distance from the center of the dike swarm. A clear pattern is discernible, where higher Mg/(Mg+Fe) ratios in mafic alteration minerals occur closer to the center of the dike swarm in potassic alteration and lower ratios were measured in sodic (-calcic) alteration on the periphery of the dike swarm. 104 Gains and losses in sodic alteration The combination of electron microprobe analysis and modal mineralogy of fresh and sodicly-altered assemblages at Tea Cup and Eagle Pass allows for the estimation of gains and losses of chemical constituents in sodic alteration. Table 5 compares the SiO2, CaO, Na2O, K2O, Fe2O3, and FeO contents ofr fresh and sodicly-altered samples. Majorelement compositions (in oxide wt%) of quartz, titanite, magnetite, ilmenite, and hematite were calculated from idealized mineral formulas, as these phases were not analyzed by electron microprobe in this study. The densities of idealized mineral phases (Nesse, 2000) were used to covert modal mineralogy (vol%) into masses (wt%). Thus, the results shown here should be considered estimates of the major-element contents of samples but not a substitute for whole-rock analyses. All sodicly-altered samples show increases in Na2O and CaO contents and decreases in K2O contents when compared to their fresh equivalents. In addition, samples MW Spec Hem and TC 010’ show significant decreases in SiO2 contents, and sample MW Spec Hem shows a significant increase in Fe2O3 content. COMPARISON OF SODIC (-CALCIC) AND GREISEN HYDROTHERMAL ALTERATION ASSEMBLAGES AT TEA CUP AND EAGLE PASS WITH OTHER LOCALITIES The Tea Cup and Eagle Pass localities are compared to well documented examples of sodic -(calcic) and iron oxide-rich hydrothermal alteration in Tables 6 and 7 and Figure 11. Previous workers showed that examples of sodic (-calcic) alteration in the western North America were predominantly Jurassic events (Battles and Barton, 1995; 105 Dilles et al., 1995), with a few younger exceptions. However, results of this study and related work by Seedorff et al. (2008) indicate that less voluminous sodic (-calcic) alteration may be a widespread feature of many Laramide porphyry districts in Arizona in which deep levels are exposed. This study extends that observation to the mid-Tertiary, as it is now clear that Eagle Pass is an Oligocene porphyry system, and it, too, exhibits sodic (-calcic) alteration. In addition, the tectonic setting of the porphyry systems does not appear to be a limiting factor in the formation of sodic (-calcic) alteration, as the Oligocene Eagle Pass porphyry system developed during a period of slab rollback as opposed to an arc setting (Table 7). Sodic (-calcic) mineral assemblages in the various porphyry systems exhibit some differences. For instance, plagioclase compositions in the Arizona systems are more albitic, and the mineral assemblages at Eagle Pass and Sierrita-Esperanza contain fewer calcium-rich minerals (Fig. 11) than the sodic (-calcic) occurrences at Ann-Mason and Yerington. Furthermore, the potassium feldspar-stable, quartz-destructive chlorite + epidote + titanite assemblage documented at Tea Cup and Eagle Pass does not appear to have a close counterpart in the other systems. The vertical distribution of alteration varies among the systems is shown in Table 6. At Ann-Mason and the Yerington mine, there is a progression from more calcic assemblages at depth to more sodic assemblages at shallower levels, which is interpreted to represent the evolution of hydrothermal fluid compositions with time (e.g., Dilles et al., 2000). A change in assemblages with depth is not as pronounced in the Arizona systems (Table 6), particularly at Tea Cup where the most calcic (andradite-bearing) 106 assemblage is located structurally higher than garnet-absent assemblages. Despite spatial complexities that may be the result of the superposition of multiple episodes of sodic(calcic) alteration forming events, Figure 11 illustrates that deeper alteration assemblages typically were stable at higher activity ratios of Ca2+/(H+)2 than shallower assemblages. If hydrothermal fluids are assumed to flow upwards, this suggests that hydrothermal fluids at each locality follow a similar geochemical path from higher to lower activity ratios of Ca2+/(H+)2 with time. Evidence for vertical zoning from sodic (-calcic) alteration at depth to shallow iron oxide-rich alteration is clearly discernible in the Tea Cup porphyry system, where sodic (-calcic) alteration forms at paleodepths of 6 - 8 km and iron-oxide rich alteration forms at 2 - 4 km (Table 7). At Ann-Mason and the Yerington mine, however, the iron oxide-rich alteration is absent in the Singatse Range, where sodic (-calcic) alteration is well developed, but iron oxide-rich alteration is well developed in structurally higher positions exposed to the west in the neighboring Buckskin Range (Dilles et al., 2000). At Eagle Pass, hematite veins are superimposed directly upon sodic (-calcic) assemblages north of the Eagle Pass dike swarm and crosscut sodic (-calcic) alteration in the immediate footwall of the Eagle Pass fault. Documented examples of greisen style alteration in porphyry copper systems are sparse (Seedorff et al., 2005b, 2008); however, electron microprobe analyses of white micas (Stavast, 2006) from the Ruby Star Granodiorite (Pima district) and Schultze Granite (Globe-Miami district) provide a basis for comparison of white mica mineral compositions at Tea Cup (Table 8). White micas from all three greisen localities are 107 muscovite and have less that 0.10 wt% F. The samples vary by several weight percent SiO2 and FeO but display no other major compositional heterogeneities. ORIGIN OF SODIC (-CALCIC) AND IRON OXIDE-RICH ALTERATION Using observations from Tea Cup and Eagle Pass and the results of the comparison to other well studied occurrences of sodic (-calcic) and iron oxide-rich alteration in porphyry systems, hypotheses are put forward to explain the occurrences of sodic (-calcic) and iron-oxide alteration found in the study areas (Figs. 12-13). The results are then generalized to yield two models (14 A,B) for the formation of sodic (calcic) and iron oxide-rich alteration in porphyry and extensional settings Key components of the models are the source of the fluids and transition from sodic (-calcic) to iron oxide-rich alteration. Source of fluids Based on stable isotopic and geologic evidence, Dilles and Einaudi (1992) and Dilles et al. (1992, 1995, 2000) argued that the source of fluids that caused sodic (-calcic) alteration in the Yerington batholith was hypersaline formation water. Although stable isotopic data are not available for Tea Cup, previous workers at Tea Cup (Barton et al, 2005; Nickerson et al., 2010) also argue for a non-magmatic fluid source for sodic (calcic) and iron oxide-rich alteration. In addition, spatial and temporal evidence at Eagle Pass argues against a magmatic source, as sodic (-calcic) alteration near the Eagle Pass fault postdates the Eagle Pass dike swarm (the only plausible nearby magmatic source), and the most widespread sodic (-calcic) alteration increases in intensity several kilometers distant from the Eagle Pass dike swarm. 108 The interpretation of the formation of sodic (-calcic) alteration in the Yerington district (Dilles and Einaudi, 1992; Dilles et al., 1992, 1995, 2000) predicts that sodic (calcic) alteration should occur wherever granitic heat sources are emplaced into sedimentary-volcanic sections containing trapped saline or hyper-saline fluids, provided that sufficient fracture permeability is available. Geologic observations confirm that such conditions are met in the Yerington district, Nevada, and at Sierrita-Esperanza in the Pima district, Arizona (Stavast, 2006). However, evaporite-bearing sedimentary units due not crop out near the Tea Cup and Eagle Pass localities. Unconformities between Tertiary and Proterozoic rocks at Tea Cup (Nickerson et al., 2010) and between Cretaceous and Proterozoic rocks at Eagle Pass (Simons, 1964) demonstrate that Permian evaporatebearing sedimentary rocks that are regionally observed in southeastern Arizona are presently absent at Eagle Pass. The denudation is most likely the result of erosion during or following Laramide contraction, which created basement-cored uplifts (Davis, 1979) prior to the onset of Laramide magmatism (Drewes, 1976). At Tea Cup, however, the Permian evaporite-bearing sedimentary rocks may still have been present during the intrusion of the Tea Cup pluton at 71 Ma, preserved in a footwall syncline east of the reverse faults documented at Tea Cup (Fig. 12A-B). The nature of Laramide reverse faulting in the vicinity of Eagle Pass is poorly understood, but a geologic setting similar to Tea Cup also is plausible at Eagle Pass prior to large-magnitude Oligo-Miocene extension (Fig. 13A), given the stratigraphic evidence for reverse faulting (i.e., Cretaceous strata deposited unconformably on Proterozoic rocks, with omission of ages of rocks of intervening ages, which are present regionally). Hence, evaporites may have 109 been present in nearby country rocks during formation of the porphyry systems at all of the above localities in question. As noted above, there are two distinct areas of sodic (-calcic) alteration at Eagle Pass, and the occurrence that is spatially associated with the Eagle Pass fault is shown by crosscutting relationships to be younger than they Eagle Pass dike swarm (Fig. 13A-D), and (U-Th)/He dates indicate that it formed at 18.95 ± 0.12 Ma (Appendix F). The lack of a observable relationship to any exposed magmatism and the close spatial relationship shared with the Eagle Pass fault suggests that this occurrence of sodic (-calcic) alteration is genetically related to the Eagle Pass fault and fluid flow accompanying crustal extension. Broadly similar occurrences of syn- or post-slip chlorite- and iron oxide-rich hydrothermal alteration associated with normal faults previously was documented in the Colorado River Extensional Corridor (e.g., Spencer and Welty, 1986). There, saline fluids are hypothesized to be derived from evaporite basins that formed contemporaneously with normal faulting in an arid environment (Beane et al., 1986; Wilkins et al., 1986; Roddy et al., 1988), consistent with association of saline fluid inclusions with these deposits and formation of widespread halite deposits at about this time in many parts of Arizona (Scarborough, 1989). A syn-extensional volcanic fanglomerate nearly 4500 m thick rests in the hanging wall of the Eagle Pass fault (Davis and Hardy, 1981). Although evaporite beds are not a primary feature in the fanglomerate section exposed at the surface, it is likely that evaporite beds could have formed in the geologic environment in which the fanglomerate was deposited (Fig.13 C). Alternatively, saline formation waters could have been derived from circulation through late Paleozoic 110 evaporite beds, i.e., possibly the same source as the older sodic (-calcic) alteration on the periphery of the Eagle Pass dike swarm (Fig. 13B). Relationship of sodic-(calcic) alteration to iron oxide-rich alteration Large volumes of sodic (-calcic) alteration are commonly spatially associated with iron oxide-rich alteration in IOCG systems; however, a genetic relationship between the two styles of hydrothermal alteration is controversial (Williams et al., 2005). Proponents of a magmatic model for the formation of IOCG deposits suggest that both styles of alteration have a magmatic source (e.g., Perring et al., 2000). The general independence of different types of IOCG systems from specific magmatic compositions, akin to what is observed in other magmatic-hydrothermal ore deposits (e.g., porphyry deposits; Seedorff et al., 2005b), as well as, paleoclimate correlations, geochemical arguments based on solubilities, and correlation with known evaporites led Barton and Johnson (1996) to suggest an evaporitic source model for IOCG deposits. In the evaporitic source model, sodic (-calcic) alteration results from warming of saline fluids as they are drawn towards an igneous heat source. Along the warming path, Na and Ca are precipitated and Fe, Si, K, Cu, and Au are removed. IOCG mineralization is suggested to result from the cooling of these fluids at shallower structural levels along a cooling path were Fe, Si, H+, ±K, ±S, ±Cu, and ±Au are precipitated (Barton and Johnson, 1996, 2000). As previously described, an evaporitic source for sodic (-calcic) and iron oxiderich alteration is suggested by spatial and temporal geologic evidence at Tea Cup and Eagle Pass. When the predicted flow paths of warming and cooling fluids of the 111 evaporitic source model (Barton and Johnson, 1996) are compared to the palinspastic reconstruction of sodic (-calcic) and iron oxide-rich alteration at Tea Cup, the predicted patterns of element transport are observed. At the other localities considered in Table 7 iron oxide-rich alteration is not observed. However, iron oxide-rich alteration and mineralization is abundant at shallower structural levels in other parts of the Yerington district (e.g., Buckskin mine, Gibson, 1988; Dilles et al., 2000). DISCUSSION Hybrid hydrothermal systems There is a long history of debate between the Plutonists and the Neptunists about the origin of fluids in hydrothermal systems, including in porphyry deposits (e.g., Seedorff et al., 2005b, p. 287). In many cases, the sources of fluids and metals in porphyry systems have been viewed as virtually entirely magmatic (e.g., Sales, 1954; Westra and Keith, 1981; Sillitoe, 1995b), whereas another end-member was that plutons served mainly as thermal drives for circulation of external fluids (e.g., Norton, 1978, 1982). In the last three or four decades, the prevailing view has called for an essential role for magmatism with a variable, generally subordinate role for external fluids (e.g., Gustafson and Hunt, 1975; Gustafson, 1978), a consensus that has edged even closer to the magmatist end member in more recent years (e.g., Hedenquist and Lowenstern, 1994).As a result, all porphyry systems can be regarded conceptually as hybrid hydrothermal systems (Fig. 15 A-C): a magmatic-hydrothermal portion best developed in the proximal or core region, and a non-magmatic portion dominated by externally derived fluids on the flanks. The magmatic-hydrothermal portion is always well developed; it is 112 an essential and defining characteristic of the porphyry deposit type. The non-magmatic portion is variably developed and has more diverse expressions because the characteristics of the non-magmatic portion are subject to more variables. The products of magmatic-hydrothermal fluid are more regular and predictable because the magmatic-hydrothermal fluid tends to overwhelm other influences in and near a mineralizing intrusion, and all of the components necessary for making a deposit are derived from the same, magmatic source: (1) the aqueous fluid involved in all aspects of alteration-mineralization; (2) ligands, such as Cl, S, and O, necessary to complex the metals, and (3) the elements necessary to precipitate the metals, such as S. The components that will be transported by the fluid will largely be governed by such factors as temperature and the total chlorinity and total sulfur content of the fluid (e.g., Fig. 15 of Barton, 1996; Reed, 1997). The fact that the magmatic-hydrothermal fluid is initially in equilibrium with the igneous rocks, however, causes a first-order relationship between magma composition and metal content (Seedorff et al., 2005b). The diversity of products of magmatic-hydrothermal fluid results from differences in factors of second-order importance, such as the level of emplacement of the system and the chemical and physical characteristics of the wall rocks. External fluids, in contrast, generally produce hydrothermal products that are much less regular and predictable because at least two and commonly all three of the above components that are necessary for making a deposit originate from different sources (Barton, 1996). Furthermore, a magma body, if present, may serve as a thermal drive for fluid circulation yet may not contribute any of the three necessary components, 113 as in many IOCG deposits (e.g., Barton and Johnson, 1996, 2000). As in the magmatichydrothermal case, the components that will be transported by the fluid will largely be governed by such factors as temperature and the total chlorinity and total sulfur content of the fluid, but the composition of potential external fluids is more diverse. The external fluid could be a fluid at the surface (e.g., dilute, oxygenated groundwater, a moderately saline, moderately reduced lake water, a brine in a salar or playa, or seawater; Barton and Johnson, 2000, plot these compositions); in many of these cases, the composition of the fluid is at least indirectly controlled by climate, which in turn is a function of factors such as latitude and orographic features (Barton and Johnson, 1996). Alternatively, the external fluid could be a basinal fluid or formation water. Finally, it could be a surface or basinal fluid whose composition was significantly shifted by interaction with wall rocks (e.g., evaporite beds) along the flow path of the external fluid, i.e., a dilute meteoric fluid could become a saline brine. As emphasized by Barton (1996), these differences will impact (1) the expected alteration-mineralization patterns and (2) the ligands available to transport metals. Because reduced sulfur necessary to precipitate sulfide minerals is not necessarily present in the external fluid, the availability of (3) reduced sulfur or some other type of chemical trap at the site of ore deposition may be required for formation of an orebody. In spite of the inherent geochemical elegance of surficial and basinal fluid systems, these systems are conceptually less straightforward than magmatichydrothermal systems because the factors that govern metal transport and deposition are largely independent variables, as opposed to being inextricably linked, as they are for magmatic-hydrothermal systems. Therefore, the hydrothermal products of external, non- 114 magmatic fluid flow in and around porphyry systems should consist of diverse types of mineral assemblages and of variable intensity. One type of mineral assemblage that can form on the periphery due to circulation of external fluids is propylitic alteration. Propylitic alteration develops when dilute meteoric or formation waters are circulated (Fig. 15A), as at Bingham (Bowman et al., 1987) and Bajo de la Alumbrera (Proffett, 2003). In contrast, when saline brines are convected on the periphery of a porphyry system (Fig. 15B-C), sodic (-calcic) alteration develops at depth on the warming path, and iron oxide-rich alteration develops at shallow structural levels on the cooling path of the externally derived fluids. When this type of peripheral alteration is developed on the fringe of a porphyry system, an IOCG deposit can develop on the flanks of or considerably distal to a porphyry system (Dilles et al., 2000), as is weakly to moderately developed at Tea Cup (this study) and intensely developed at Pumpkin Hollow in the Yerington district (Ohlin, 2010). If other compositions of external fluids are involved, then additional variations on the theme of porphyry deposits as variably hybrid systems are possible (e.g., Seedorff and Barton, 2004, p. 16). Although other factors can also be significant, to a first approximation dilute meteoric waters at the surface typify temperate climates, and saline waters typify arid climates (e.g., Barton and Johnson, 1996). The non-magmatic portion of a porphyry system may be weakly developed (e.g., Robinson: Maher, 1996), moderately developed (Tea Cup: this study), to intensely developed (e.g., Yerington mine: Carten, 1986); and the associated alteration patterns may range spatially from largely outboard of the magmatic-hydrothermal alteration 115 products in certain systems (e.g., Bajo de la Alumbrera: Proffett, 2003) to intimately interfingering with or overprinting the magmatic-hydrothermal products in other systems (e.g., Ann-Mason: Dilles and Einaudi, 1992). Even in known porphyry districts, not all of the sodic-calcic alteration necessarily formed contemporaneously with the magmatic-hydrothermal portion of the hydrothermal system; indeed, some of the sodic-calcic alteration at Eagle Pass formed on the flanks of the porphyry system, but the sodic (-calcic) alteration along Eagle Pass fault is demonstrated by superposition to be younger than the dike swarm and synchronous with post-ore extensional dismemberment. Thus, the sodic-calcic alteration along the Eagle Pass fault is genetically unrelated to, yet partially superimposed on, the porphyry system. This relationship also has analogs in other porphyry systems: the Ajo porphyry copper system in western Arizona, which formed during the Laramide at ~63 Ma, is adjacent to a large zone of intense sodic-calcic alteration that affected the Cardigan Peak pluton in the early Miocene (20-23 Ma) and contains abundant saline fluid inclusions (Cox and Ohta, 1984; Hagstrum et al., 1987; Cox et al., 2006). Thus, the origin of distal alteration types present at each porphyry system must be judged on the geologic and geochemical merits of its individual characteristics, and each system should be explored accordingly. Implications for exploration The use of observed patterns in hydrothermal alteration as a vector towards porphyry mineralization has yielded exploration success for economic geologists in the past (e.g., San Manuel-Kalamazoo, Lowell, 1968). However, most discoveries have resulted from a top-down or side-in exploration approach, and use of vectors from the 116 bottom-up to ore bodies is a relatively recent advance (e.g., Maher et al., 2005; Maher, 2008; Seedorff et al., 2008), which has the possibility to yield significant finds in tilted terrains such as southwestern North America (Maher, 2008; Nickerson et al., 2010). Further study is required to hone this new approach to exploration in tilted terrains (e.g., Seedorff et al., 2008); however, results here indicate the composition of external fluids play a primary role in the manifestation of distal hydrothermal alteration in porphyry copper systems. Thus, the presence of intense sodic (-calcic) alteration should not be considered more prospective for porphyry copper formation than the presence of propylitic alteration. However, sodic-calcic and iron oxide-rich hydrothermal alteration are distinctive, and an understanding of their genetic implications (i.e., deep and shallow levels, respectively, on the periphery of a porphyry copper system) could prove useful when exploring in tilted terrains. Mineralization directly associated with iron oxide-rich alteration is another possible exploration target in composite porphyry systems. The best example of such a deposit is Pumpkin Hollow in the Yerington district (measured and indicated resource of 531 M tons containing 0.55% Cu, 0.003 oz/t Au opt, and 0.079 oz/t Ag; TetraTech, 2010). In the Red Hills prospect at Tea Cup, mineralized iron oxide-rich alteration is superimposed upon mineralized potassic alteration. The combination of the two styles of mineralization produced a low-grade large-tonnage resource (450 million tonnes of 0.1% Cu; Williams and Forrester, 1995). However, in IOCG systems there are many occurrences of sodic (-calcic) and iron oxide-rich hydrothermal alteration but few economic deposits. This may result from the systems having an effective mechanism of 117 metal transport (i.e., the circulation of heated brines) but commonly an ineffective mechanism for metal precipitation mechanism (Barton and Johnson, 2000). A similarly high ratio of occurrences to deposits should be expected in the composite porphyry system environment. However, where a source of sulfur and an effective mechanism for metal precipitation is present (i.e., carbonate rocks at Pumpkin Hollow), the resulting mineralization can be economically significant. SUMMARY AND CONCLUSIONS Results of U-Pb geochronology, geologic mapping, petrographic study, and electron microprobe analyses, constrain the possible origins of sodic (-calcic) alteration in two Arizona porphyry copper systems. Spatial and temporal constraints, combined with previous isotopic studies that indicate that the sodic (-calcic) and iron oxide-rich alteration formed from externally derived saline fluids, suggest that these porphyry systems are hybrid hydrothermal systems, in which magmatic fluids dominated the center of the system and external fluids circulated peripherally. Conceptually, all porphyry systems may be regarded as hybrid hydrothermal systems with an essential, usually overwhelmingly dominant magmatic-hydrothermal contribution. The composition of external fluids and wall rocks are proposed to control the manifestation of distal alteration styles, which, to a first approximation, correlate with climate—propylitic alteration forming from dilute meteoric fluids that characterize temperate climates, and sodic (-calcic) alteration forming from saline brines that are most available in arid climates. Sodic (-calcic) and iron oxide-rich alteration are genetically related to one another, with the former forming on the warming path, and the latter forming on the 118 cooling path of saline hydrothermal fluids. Extension in arid climates, without the requisite need for coeval plutons as the drive for fluid circulation, is another means of producing sodic (-calcic) and iron oxide-rich alteration. Saline fluids derived from highly saline surface waters in evaporite basins developed in half-grabens were warmed by an elevated geothermal gradient and convected up highly porous and permeable normal faults. ACKNOWLEDGMENTS We would like to thank K. Dominick for assistance at the Michael J. Drake Electron Microprobe Laboratory (University of Arizona). Financial support for this project came from two awards from the Society of Economic Geologists student research fund, NSF Grant EAR08-38157 to Mark D. Barton, Science Foundation Arizona and the industry sponsorship of the Lowel Institute for Mineral Resources, and Bronco Creek Exploration. Some of the samples used in this study were collected and initially examined by Tyler Vandruff, Eric Flesch, and Bill Stavast. 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Titley, S.R., 1982c, Some features of tectonic history and ore genesis in the Pima mining district, Pima County, Arizona, in Titley, S.R., ed., Advances in geology of the porphyry copper deposits, southwestern North America: Tucson, University of 132 Arizona Press, p. 387-406. Titley, S.R., and Hicks, C.L., eds., 1966, Geology of the porphyry copper deposits, southwestern North America: Tucson, University of Arizona Press, 287 p. Westra, G., and Keith, S. B., 1981, Classification and genesis of stockwork molybdenum deposits: Economic Geology, v. 76, p. 844-873. Wilkins, J., Jr., Beane, R.E., and Heidrick, T.L., 1986, Mineralization related to detachment faults: A model: Arizona Geological Society Digest 16, p. 108-117. Willden, R., 1964, Geology of the Christmas quadrangle, Gila and Pinal Counties, Arizona: U. S. Geological Survey Bulletin 1161-E, 64 p. Williams, P.J., Barton, M.D., Johnson, D.A., Fontboté, L., de Haller, A., Mark, G., Oliver, N.H.S., and Marschik, R., 2005, Iron oxide copper-gold deposits: Geology, space-time distribution, and possible modes of origin: Economic Geology 100th Anniversary Volume, p. 371-405. Williams, S.A., and Forrester, J.D., 1995, Characteristics of porphyry copper deposits: Arizona Geological Society Digest 20, p. 21-34. Wilson, A.J., Cooke, E.R., and Harper, B.L., 2003,The Ridgeway gold-copper deposit: A high-grade alkalic porphyry deposit in the Lachlan fold belt, New South Wales, Australia: Economic Geology, v.98, p. 1637-1666. Wrucke, C.T., 1989, The Middle Proterozoic Apache Group, Troy Quartzite, and associated diabase of Arizona: Arizona Geological Society Digest 17, p. 239-258. 133 TABLE 1. Hydrothermal alteration assemblages Alteration type Potassic Location Tea Cup Added and recrystallized minerals1 Quartz + k-feldspar + biotite(Phg# 49-55) + magnetite + muscovite ± pyrite ± chalcopyrite ± molybdenite Greisen Tea Cup Muscovite ± pyrite ± quartz ± molybdenite Quartz ± orthoclase Sodic Tea Cup Albite(An# 0-4) + chlorite + epidote ± titanite ± Quartz ± magnetite ± orthoclase Sodiccalcic Tea Cup Albite/oligoclase(An# 1-19) + epidote + actinolite + titanite ± andradite ± Oligoclase FeOx rich Tea Cup Specular hematite + chlorite + quartz ± muscovite/alumino-celadonite ± magnetite ± pyrite Quartz ± orthoclase Potassic Eagle Pass Quartz + k-feldspar + biotite(Phg# 50-59) + magnetite ± pyrite ± chalcopyrite Quartz ± orthoclase ± biotite ± magnetite Sodic (+qtz) Eagle Pass Quartz + albite(An# 0-4) + chlorite + epidote Quartz ± magnetite Sodic (-qtz) Eagle Pass Albite/oligoclase(An# 1-23) + epidote ± clinochlore ± actinolite ± specular hematite ± muscovite/alumino-celadonite ± Quartz ± orthoclase Relict Minerals2 Quartz ± orthoclase ± biotite ± magnetite An# = anorthite component in plagioclase; Phg# = phlogopite component in biotite 1 Minerals listed in order of abundance 2 Minerals occurring in trace amounts not considered 134 TABLE 2. Representative feldspar compositions. Sample SP SP SP 123 TC number 035 035 kspar1 011 plg1 plg2 kspar2 TV08 07 plg2 EP 086 kspar3 EP 086 plg1 EP 038c kspar2 MW NACA2 plg1 Location Tea Cup Tea Cup Tea Cup Tea Cup Tea Cup Eagle Pass Eagle Pass Eagle Pass Eagle Pass Alteration assemblage fresh fresh potassic sodic calcic fresh fresh potassic sodic plag plag plag plag kspar Replacing Host rock Yg Yg Yg Yg Yg Yg Yg Yg Yg SiO2 64.54 64.54 64.35 64.54 62.76 63.34 65.30 64.72 67.61 TiO2 0.01 0.01 0.00 0.02 0.00 18.64 22.89 18.87 20.62 Al2O3 22.25 22.25 18.80 18.81 23.41 0.00 0.00 0.03 0.06 Cr2O3 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.05 Fe2O3 0.00 0.00 0.05 0.11 0.19 0.08 0.00 0.39 0.00 FeO 0.03 0.03 0.00 0.00 0.00 0.00 0.03 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MnO 0.04 0.04 0.00 0.01 0.00 0.00 0.00 0.01 0.00 CaO 3.47 3.47 0.03 0.02 4.32 0.00 3.65 0.00 0.85 Na2O 9.70 9.70 1.33 0.89 9.27 0.77 10.21 0.72 11.60 K2O 0.17 0.17 14.65 15.05 0.20 15.20 0.13 15.43 0.10 F 0.00 0.00 0.00 0.08 0.00 0.30 0.00 0.25 0.00 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 100.21 100.21 99.23 99.48 100.15 98.20 102.22 100.32 100.90 Or# 0.01 0.94 0.96 0.00 0.00 0.93 0.01 0.93 0.01 An# 0.16 0.00 0.03 0.00 0.06 0.00 0.16 0.00 0.04 0.07 0.96 Total End Member Ab# 0.83 0.06 0.01 0.99 0.94 0.07 0.83 Yg = Ruin granite at Teac Cup and the Laurel Canyon granodiorite at Eagle Pass. 135 TABLE 3. Representative mica and chlorite compositions. Sample EP EP 022b bt1 EP 034 TC 008 number 024 chl2 bt1 bt1 SP 123 bt2 TC 011 chl1 SP 079 ser2 Location Eagle Pass Eagle Pass Eagle Pass Tea Cup Tea Cup Tea Cup Tea Cup Alteration Assemblage fresh potassic sodic after potassic fresh potassic sodic sericitic Mineral name annite phlogopite clinochlore phlogopite phlogopite clinochlore aluminoceladonite biotite shreddy biotite biotite biotite vein Yg Yg Yg Yg Yg Yg Yg SiO2 35.50 37.31 26.15 35.71 35.56 29.98 46.64 TiO2 3.41 1.98 0.10 2.81 3.00 0.00 0.28 Al2O3 14.55 17.03 18.73 17.37 14.69 19.03 28.64 Cr2O3 0.01 0.00 0.04 0.00 0.01 0.00 0.01 Fe2O3 5.36 3.81 4.55 4.19 4.28 2.04 1.16 FeO 19.28 13.70 23.19 15.10 15.42 10.39 4.16 MgO 7.73 11.56 13.71 9.66 11.75 23.87 2.54 Replacing Host Rock MnO 0.46 0.35 0.56 0.61 0.34 1.89 0.03 CaO 0.00 0.00 0.02 0.00 0.00 0.08 0.00 Na2O 0.21 0.03 0.01 0.05 0.10 0.01 0.20 K2O 9.39 9.74 0.00 9.52 9.44 0.07 10.49 H2O 3.48 3.62 11.18 3.38 3.53 12.07 4.12 F 0.55 0.64 0.00 0.99 0.57 0.13 0.44 Cl 0.09 0.03 0.01 0.04 0.08 0.01 0.01 Subtotal 100.02 99.80 98.23 99.44 98.80 99.56 98.72 O=F+Cl -0.25 -0.28 0.00 -0.43 -0.26 Total 99.77 99.52 98.23 99.01 98.54 Yg = Ruin granite at Tea Cup and the Laurel Canyon granodiorite at Eagle Pass. -0.06 -0.19 99.50 98.53 136 TABLE 4. Representative epidote and amphibole compositions. Sample MW MW MW TV07 08 TC 010' number SPECHEM NACA3 NACA3 ep2 ep2 ep1 ep1 act1 TC 006 amph2 Location Eagle Pass Eagle Pass Eagle Pass Tea Cup Tea Cup Tea Cup sodic sodic sodic calcic sodic sodic epidote epidote actinolite epidote epidote actinolite Replacing kspar vein biotite kspar quartz biotite Host rock Yg Yg Yg Yg Yg Yg SiO2 38.26 37.25 51.37 37.08 38.40 50.44 TiO2 0.03 0.02 0.05 0.08 0.01 0.64 Al2O3 23.18 22.00 4.11 22.88 25.28 4.87 Cr2O3 0.00 0.00 0.00 0.03 0.00 0.01 Fe2O3 13.06 15.42 2.54 14.04 9.96 4.90 FeO 0.20 0.00 11.79 0.52 0.60 8.47 MgO 0.00 0.00 14.21 0.00 0.00 14.79 MnO 0.20 0.07 0.34 0.51 0.59 0.81 CaO 23.11 23.15 12.59 22.82 23.28 11.72 Na2O 0.00 0.00 0.48 0.05 0.00 0.96 K2O 0.00 0.00 0.15 0.00 0.00 0.37 H2O 1.88 1.87 1.86 1.80 1.90 2.08 F 0.00 0.00 0.41 0.15 0.01 0.00 Cl 0.01 0.01 0.04 0.00 0.01 0.00 Subtotal 99.94 99.78 99.92 99.95 100.04 100.07 O=F+Cl 0.00 0.00 -0.18 -0.06 0.00 0.00 Total 99.94 99.78 99.74 99.89 100.03 100.07 Alteration assemblage Mineral Name Yg = Ruin granite at Tea Cup and the Laurel Canyon granodiorite at Eagle Pass. 137 TABLE 5. Modal mineralogy and oxide weight% of alteration types. Sample EP 024 MW MW Spec TC 008 number NaCa2 Hem Location TC 010' Eagle Pass Eagle Pass Eagle Pass Tea Cup Tea Cup fresh sodic sodic fresh sodic Quartz 40 39 0 38 3 Oligoclase 30 0 0 30 0 Albite 0 48 70 0 65 Orthoclase 21 0 0 23 0 Biotite 7 0 0 7 0 Muscovite 0 0 3 0 3 Chlorite Epidote 0 0 4 8 0 4 0 0 17 11 Actinolite 0 0 0 0 0 Titanite 0 1 1 0 1 Magnetite 1 0 0 1 0 Ilmenite 1 0 0 1 0 Hematite 0 0 22 0 0 100 100 100 100 100 Alteration assemblage Total Sample weight% oxide SiO2 75 76 51 75 59 CaO 1.0 2.3 1.1 1.0 2.9 Na2O 3.1 5.6 8.0 3.1 7.7 K2O 3.9 0.0 0.2 4.3 0.3 Fe2O3 1.1 3.3 23 1.0 1.5 FeO 2.1 1.0 0.4 1.8 2.0 138 TABLE 6. Compilation of sodic (-calcic) mineral assemblages versus depth from localities in the western United States. Tea Cup porphyry system, Kelvin-Riverside district, central Arizona4 Eagle Pass porphyry system, Klondyke district, southeastern Arizona5,6 Paleodepth (km) Ann-Mason deposit, Yerington district, western Nevada1 Yerington mine, Yerington district, western Nevada2 Sierrita-Esperanza deposit, Pima district, southern Arizona3 1 Olg/Ab+Chl+Verm+Rt±Tnt±Py±Qtz ; Ab+Chl+Ser+Rt+Py(±Tm±Verm); Ab+Tm+Rt+Py±Chl±Ser Not exposed Not exposed Not exposed Not exposed 2 Olg/Ab+Chl+Verm+Rt±Tnt±Py±Qtz ; Ab+Chl+Ser+Rt+Py(±Tm±Verm); Ab+Tm+Rt+Py±Chl±Ser Qtz+Olg/And+Tnt+Rt+Apt±Ep ; Qtz+Olg+Tnt+Apt+Act±Ep Not exposed Hem+Qtz+Chl+Ser±Mt± Py Not exposed 3 Ep+Tnt±Olg/Ab±Qtz±Act±Bi±Ser± Py(±Chl±Rt) Qtz+Olg/And+Tnt+Rt+Apt±Ep ; Qtz+Olg+Tnt+Apt+Act±Ep; Qtz+Ab+Rt+Apt+Chl+Ep+Py+ Ser+Cal; Qtz+Alb+Tnt+Apt+Chl+Act+E p±Py+Ser Not exposed Hem+Qtz+Chl+Ser±Mt± Py; Mt+Qtz+Chl+Ser±Hem± Py Not exposed 4 Olg/And+Tnt+Qtz±Rt; Olg/Ab+Act+Qtz+Tnt+Ep(±Py); Olg/Ab+Qtz+Tnt+Ep+Act(±Chl); Ep+Tnt±Olg/Ab±Qtz±Act±Bi±Ser± Py(±Chl±Rt) Qtz+Ab+Rt+Apt+Chl+Ep+Py+ Ser+Cal; Qtz+Alb+Tnt+Apt+Chl+Act+E p±Py+Ser Ab+Chl+Act+Ep (Qtz destroyed) Not exposed Chl+Ep+Tnt (Qtz destroyed Kspar stable) 5 Olg/And+Tnt+Qtz±Rt; Olg/Ab+Act+Qtz+Tnt+Ep(±Py); Olg/Ab+Qtz+Tnt+Ep+Act(±Chl) Not exposed Ab+Chl+Act+Ep (Qtz destroyed) Not exposed Ab+Chl+Act+Ep± Tnt (±Qtz destroyed) 6 Olg/And+Tnt+Qtz±Rt; Olg/Ab+Act+Qtz+Tnt+Ep(±Py); Olg/Ab+Qtz+Tnt+Ep+Act(±Chl) Not exposed Ab+Chl+Act+Ep (Qtz destroyed) Chl+Ep+Tnt (Qtz destroyed Kspar stable); Alb+Chl+Ep+Anr±Act Ab+Chl+Act+Ep± Tnt±Hem (±Qtz destroyed) 139 1 7 Not exposed Not exposed Ab+Chl+Act+Ep (Qtz destroyed) Ab+Chl+Act+Ep±Sph (Qtz destroyed) Ab+Chl+Act+Ep±S ph±Hem (Qtz destroyed) 8 Not exposed Not exposed Ab+Chl+Act+Ep (Qtz destroyed) Ab+Chl+Act+Ep±Sph (Qtz destroyed) Ab+Chl+Act+Ep±S ph±Hem (Qtz destroyed) From Dilles and Eunaudi (1992). 2From Carten (1986). 3From Stavast (2006). 4From this study. 5From this study. 6Absolute paleodepth not constrained; Mineral abbreviations: Act = actinolite, Alb = albite, And = andesine plagioclase, Anr = andradite, Apt, apatite, Bt = biotite, Cal = calcite, Chl = chlorite, Ep = epidote, Hb = hornblende, Hem = hematite, Mt = magnetite, Olg = oligoclase, Py = pyrite, Rt = rutile, Ser = sericite, Tnt = titanite, Tm = tourmaline, Verm = vermiculite, Qtz = quartz. 140 TABLE 7. Geologic setting of sodic (-calcic) alteration occurrences in the western United States Location Ann-Mason, Yerington district, Nevada1 Age of alteration Jurassic Intrusive rocks Granite, granite porphyry dikes Wall rocks Quartz monzodiorite Tectonic environment Recently emergent arc Source of salinity Jurassic evaporites Yerington mine, Yerington District, Nevada2 Jurassic Granite, granite porphyry dikes Quartz monzodiorite Recently emergent arc Jurassic evaporites Sierrita-Esperanza, Pima district, Arizona3 Laramide Granodiorite Granite, carbonates Continental arc Permian evaporites Tea Cup porphyry system, KelvinRiverside district, southeastern Arizona4 Laramide Biotite hornblende granodiorite and biotite granite Granite Continental arc Permian evaporites? Eagle Pass porphyry system, Klondyke district, southeastern Arizona5 Oligocene Granite, quartz Granite, Slab rollback Permian monzonite, and granitic magmatism evaporites? quartz diorite gneiss porphyry dikes, composite pluton? 1 From Dilles and Eunaudi (1992). 2From Carten (1986). 3From Stavast (2006). 4From this study. 5From this study. 141 TABLE 8. Representative vein muscovite compositions from greisen alteration Sample number DM04 670 Schultze1 TV125 Ruby Star2 SP 114 Tea Cup3 Mineral Name Muscovite Muscovite Muscovite SiO2 50.40 47.99 46.20 TiO2 .25 0.26 0.46 Al2O3 29.02 28.21 29.97 Cr2O3 0.02 Fe2O3 1.08 FeO 3.19 5.59 3.88 MnO 0 0.15 0.11 MgO 2.23 2.11 1.82 CaO .10 0.11 0.02 BaO 0 0.08 Na2O .16 0.24 0.25 K2O 10.23 10.32 10.51 SO3 0.00 0.02 P 2O 5 0.00 0.00 F 0.01 0.03 0.08 Cl 0.00 0.00 0.00 H2O 4.38 4.20 4.31 Subtotal 100.01 99.32 98.70 O=F+Cl -0.01 -0.01 -0.03 Total 100.00 99.31 98.67 2 3 1From Stavast (2006). From Stavast (2006). From this study. 142 Fig. 1. Geologic map of south-central Arizona showing the study area, nearby porphyry copper deposits, the Catalina core complex, the Pinaleño core complex, and the Tortilla Mountains (geology from Reynolds, 1988). Fig. 2. Geologic map of the Tea Cup area. The map is based on new mapping and previous work by Schmidt (1971), Cornwall and Krieger (1975a and 1975b), Bradfish (1979), Richard and Spencer (1997), and Barton et al. (2005a). Fig. 3. Geologic map of the Eagle Pass area. A. Geologic map of the northern portion of the Pinaleño metamorphic core complex including endpoints of cross section A-A’ through the dike swarm. EPF = Eagle Pass fault; PDF=Pinaleño detachment fault. B. Location of cross section B-B’ in Fig. 12D. Dashed box is area shown in Fig. 1A. C. Cross section oriented perpendicular the Eagle Pass dike swarm. A-A’ located in Fig. 1A. Fig 4. U-Pb geochronology. The 206Pb/238U zircon ages for rock samples collected from the Tea Cup pluton and Red Hills dike swarm. Sample location located in Appendix E (Table 1). A. SP 100 Red Hills dike collected near the Red Hills prospect. B. SP 102 granite porphyry dike located 5 km north of the Red Hills prospect. C. SP 103 muscovitebearing quartz latite dike intruding the Tea Cup pluton. D. Collected from the muscovitebiotite granite phase of the Tea Cup pluton. E. GB 202 collected from the hornblendebiotite granodiorite phase of the Tea Cup pluton. Fig 5. Stereonets for Eagle Pass dikes and Safford veins. A. Orientation of dikes in the Pinaleño MCC. Dashed line = plane to beta axis. B. Orientation of dikes in the Pinaleño MCC with beta axis rotated to vertical, i.e., the proposed orientation of the dikes 143 prior to tilting. C. Mineralized veins found in dike rocks in the Kennecott area of the Laramide aged Safford district; after Dunn (1978). Fig. 6. Map illustrating the distribution of hydrothermal alteration in the Tea Cup area. Fig. 7. Equal area plot stereonets of Laramide hydrothermal features in the study area. A. Compilation all strike and dip measurements of veins and porphyry dikes from the Tea Cup porphyry system. B. Orientations of veins and porphyry dikes from the oldest hydrothermal system sourced from the biotite-hornblende granodiorite. C. Orientations of veins and porphyry dikes from the middle-aged hydrothermal system sourced from biotite granite. Alteration crops out in and around the Red Hills prospect. D. Orientations of veins and porphyry dikes from the youngest hydrothermal system sourced from the biotite-muscovite±garnet granite near Mount Grayback. Fig. 8. Photographs of rock slabs showing hydrothermal alteration at Tea Cup (AC) and Eagle Pass (D-G). A. Albite-epidote-chlorite±garnet sodic (-calcic) alteration of the Ruin Granite on the southeastern flank of the Tea Cup pluton B. Quartz vein surrounded by coarse-grained muscovite in the biotite-muscovite±garnet granodiorite west of Mount Grayback. C. Specular hematite-quartz vein in the Red Hills prospect. D. Quartz-chlorite-albite±specular hematite alteration hosted in the Laurel Canyon granodiorite. Sample located ~100 m from the Eagle Pass Fault. Alteration is interpreted to be considerably younger than the porphyry system (see text) and to be associated with the normal faulting. E. Albite+chlorite +epidote ±actinolite±titanite alteration hosted in the Laurel Canyon granodiorite. Sample located north of the Eagle Pass dike swarm. 144 Alteration is interpreted to be associated with the intrusion of the dike swarm. F. Chlorite+epidote+titanite, quartz destructive, K-feldspar stable alteration hosted in the Laurel Canyon granodiorite. G. Specular hematite+quartz alteration hosted in the Laurel Canyon granodiorite; K-feldspar is altered to albite. Fig 9. Mapped pattern of hydrothermal alteration near the Eagle Pass dike swarm of Oligocene age. Fig 10. Zoning pattern observed in Mg/(Mg+Fe) ratio in biotite and chlorite from Eagle Pass. Fig 11. Log(aCa2+/a2H+) versus log(aMg2+/a2H+) for 400° C, 500 bars, for the system CaO-MgO-Al2O3-SiO2-HCl-H2O, showing boundaries of stability fields of plagioclase compositions An5, An23, An35; epidote solid solution (SS) given by mole fraction Fe-endmember component X(Ca2Fe3Si3O12(OH)), grossular-andradite (grandite) garnet solid solution, and K-feldspar (after Dilles et al., 1995). Mineral assemblages from AnnMason, Yerington, Tea Cup, Eagle Pass, and Sierrita-Esperanza are plotted on the diagram. The dashed arrow indicates how fluids are interpreted to have evolved from more calcic to less calcic with time. Fig 12. Two models depicting the generation of sodic-calcic alteration. A. Sodiccalcic alteration generated on the periphery of a porphyry system. Fluids are derived from evaporite deposits and circulated by a magmatic heat source. B. Sodic-calcic alteration generated along a normal fault. Fluids are derived from evaporite deposits and circulate up the porous and permeable fault zone. Fluids are heated by the warm upper crust commonly observed in extension tectonic settings. 145 Fig 13. Reconstructed cross section for Tea Cup system. A. Hypothetical Laramide geologic cross section (after Nickerson et al., 2010) depicting the composite Tea Cup pluton intruding a basement-cored uplift. Thick black lines represent the modern surface. Maroon lines mark the paleosurface at 73 Ma and 25 Ma. Q = Undifferentiated Quaternary deposits; Tc = Tertiary conglomerate; Ts= Oligo-Miocene sedimentary rocks; Kmbg = biotite-muscovite±garnet granodiorite; Kbg = biotite granite; K = hornblendebiotite granodiorite; Khbg = biotite-hornblende quartz monzodiorite; P = Paleozoic sedimentary rocks; Ya = Proterozoic Apache Group; Yr = Proterozoic Ruin Granite. B. Reconstruction of hydrothermal alteration. Yellow arrows illustrate a proposed fluid flow path for the external saline fluids that produced sodic (-calcic) and iron-oxide rich alteration at Tea Cup. No vertical exaggeration. Fig 14. Sequential time panels depicting possible origin of the two sodic (-calcic) alteration events at Eagle Pass. One has a magmatic heat source, and one is related to extension. Qu = undifferentiated Quaternary rocks; Tv = Tertiary volcanic rocks; Tep = Oligocene Eagle Pass pluton (inferred; the pluton is not exposed at the surface); Kc = Cretaceous conglomerate; Plz = Paleozoic rocks including dolomite and evaporite bearing units; Yag; Proterozoic Apache Group; Ylc = Proterozoic Laurel Canyon granodiorite. A. Sodic (-calcic) alteration formed forms during the intrusion and cooling of the Eagle Pass pluton (the magmatic source of the Eagle Pass dike swarm). B. Generation of fault related sodic (-calcic) alteration option 1. Slip on the Eagle Pass fault dismembers the Eagle Pass pluton. Sodic (-calcic) alteration forms as saline formation waters derived from Paleozoic dolomite and evaporite bearing units (Plz) are circulated 146 up the fault. C. Generation of fault related sodic (-calcic) alteration option 2. Slip on the Eagle Pass fault dismembers the Eagle Pass pluton. Sodic (-calcic) alteration forms as saline formation waters derived from Tertiary evaporite bearing units (Tc) are circulated up the fault. D. Modern cross section B to B’. Cross section endpoints shown on Fig. 1B. Fig 15. Diagram depicting variation in peripheral styles of alteration in composite porphyry systems created by variation in external fluid compositions. A. Propylitic alteration is generated by circulating fresh external fluids. B. Sodic (-calcic) and ironoxide rich alteration is created by circulating saline fluids derived from ancient evaporitebearing sedimentary rocks. C. Sodic (-calcic) and iron-oxide rich alteration is created by circulating saline fluids derived from modern evaporite-bearing sedimentary rocks. 147 Figure 1. 148 Figure 2. 149 Figure 3. 150 Figure 4. 151 Figure 5. 152 Figure 6. 153 Figure 7. 154 Figure 8. 155 Figure 9. 156 Figure 10. 157 Figure 11. 158 Figure 12. 159 Figure 13. 160 Figure 14. 161 Figure 15. 162 APPENDIX C: DISMEMBERED PORPHYRY SYSTEMS NEAR WICKENBURG, ARIZONA: DISTRICT-SCALE RECONSTRUCTION WITH AN ARC-SCALE CONTEXT Phillip A. Nickerson* Eric Seedorff Lowell Institute for Mineral Resources Department of Geosciences University of Arizona 1040 East Fourth Street Tucson, Arizona 85721-0077, USA To be submitted to Economic Geology 163 ABSTRACT This study combines results from reconnaissance-scale mapping of hydrothermal alteration, rock types, and structures to provide a district-scale cross section and associated palinspastic reconstruction of an area near Wickenburg, Arizona, that contains previously undescribed Laramide (~70 Ma) porphyry systems. Extension at the district scale in this poorly understood segment of the Laramide porphyry belt is placed in an arcscale context by using a compilation of tilt measurements on Tertiary sedimentary and volcanic rocks to make a new estimate of the geometry of the Laramide porphyry belt of southwestern North America prior to extension. Crosscutting relationships between normal faults and tilting of hanging wall and footwall rocks indicate that the study area contains five sets of nearly planar normal faults superimposed upon one another. Geologic relationships demonstrate that the normal faults initiated at angles between 60 and 70° and rotated to angles as gentle as 20° during slip. The amount of displacement on the largest faults is no greater than 4 - 6 km. A faultby-fault palinspastic reconstruction of displacement reveals a total of ~160% northeastsouthwest extension across the study area and implies the presence of two, spatially distinct hydrothermal systems sourced from different cupolas of a Late Cretaceous pluton. Hydrothermal alteration is zoned from greisen to potassic to transitional greisenpotassic assemblages from deep to shallow structural levels. The reconstruction is used to identify two exploration targets centered on potassic alteration in two porphyry systems that are now covered by younger Tertiary and Quaternary rocks. Igneous source rock compositions and styles of alteration suggest that the prospects may be porphyry 164 molybdenum systems of the Mo-Cu subclass, similar to previously identified nearby porphyry resources. A compilation of strikes and dips of Tertiary units in various extensional domains astride the Laramide porphyry belt of southwestern North America is utilized create a reconstruction of the porphyry belt. The resulting interpretation of the pre-extension geometry of the Laramide porphyry belt displays a variably well defined axis, approximately 100 km wide prior to extension with gaps and clusters of deposits along the 700-km strike length of the arc, with the majority of porphyry deposits along the axis but with others in fore-arc or rear-arc settings. The interpreted pre-extensional geometrylosely resembles that of other porphyry belts and magmatic arcs formed at convergent oceanic-continental plate boundaries. INTRODUCTION In southwestern North America, the Cenozoic Basin and Range extensional province is superimposed upon many types of ore deposits (Fig. 1), including the numerous porphyry systems of the Laramide (80-50 Ma) magmatic arc. The Laramide magmatic arc contains some of the best studied porphyry systems in the world (e.g., Titley and Hicks, 1966; Titley, 1982a; Pierce and Bolm, 1995) (Fig. 2). However, few previous studies consider the effect that post-mineralization normal faulting has had on spatial relationships at the deposit scale (e.g., Lowell, 1968; Wilkins and Heidrick, 1995; Stavast et al., 2008) or the scale of the magmatic arc (Richard, 1994). The superposition of normal faults and porphyry systems creates challenges and benefits for the study of both extensional and hydrothermal processes. For example, challenges can arise where 165 hydrothermal alteration destroys critical structural markers and where key parts of ore bodies are dismembered by normal faults. Benefits of this juxtaposition arise when products of one of the geologic processes help constrain aspects of the other process. For example, predictable patterns in hydrothermal alteration zoning can be used as structural markers (Nickerson et al., 2010), which may better constrain structural reconstructions and, in turn, aid in better discriminating between different styles of extension. In addition, deep levels of ore forming systems can be exhumed in the footwall of normal faults and examined at the surface to better constrain ore forming processes (Carten, 1986; Dilles and Einaudi, 1992; Seedorff et al., 2008). Regional-scale reconstructions commonly subdivide regions into extensional domains and then restore extension in each of the extended domains. At the arc-scale, such reconstructions can aid in understanding tectonic processes (e.g., McQuarrie and Wernicke, 2005) or, as attempted here and earlier by Richard (1994) using an alternative method, the original distribution of porphyry deposits along a magmatic arc. This study focuses on a poorly understood segment of the Laramide porphyry copper belt near the town of Wickenburg in central Arizona (Fig. 3) and provides the first public documentation of porphyry systems in the area, i.e., notwithstanding company reports. Previous detailed mapping of rocks types and structural geology (Peterson, 1985; Capps et al., 1986, Stimac et al., 1987; Powers, unpublished map) is combined with original, reconnaissance-scale mapping of hydrothermal alteration and examination of areas critical to a structural interpretation of the area, which were made possible by helicopter-assisted access. The data for rock types, structure, and alteration are used to 166 make a structural analysis of the area, including a palinspastic reconstruction of the Oligo-Miocene extension. The reconstruction demonstrates that extension was produced by five super-imposed sets of normal faults, and the district-scale reconstruction is used to identify two new porphyry exploration targets centered on potassic alteration. The results from the Wickenburg area are placed in an arc-scale context by using the equations of Jackson and McKenzie (1983) to generate a new estimate of the original, pre-extensional distribution of porphyry deposits along the Laramide arc. LOCATION AND GEOLOGIC SETTING Location The study area is located ~70 km northwest Phoenix, Arizona, and ~10 km east of Wickenburg Arizona (Fig. 3). The study area, ~250 km2 in size, includes portions of the Wickenburg, Buckhorn, Hieroglyphic, and Bradshaw Mountains, as well as Sheep Mountain. Mining districts in the study area include the White Picacho and Sheep Mountain districts. Four-wheel drive roads provide access to the Wickenburg, Buckhorn, and Hieroglyphic Mountains. Access to steep and rugged terrain of Sheep Mountain and the Bradshaw Mountains is limited, where helicopter support greatly facilitated geologic mapping. Laramide porphyry copper province Porphyry deposits in Arizona are some of the best studied deposits in the world (e.g., Seedorff et al., 2005a), and many have been productive mines for over a century (e.g., Miami, Inspiration, Ray, and Morenci; Parsons; 1933) (Fig. 2). Nearly all porphyry deposits in Arizona formed during Laramide time (~80-50 Ma) when northeast-directed 167 subduction of the Farallon plate beneath the North American plate produced a northwestsoutheast striking magmatic arc (Titley, 1982b; Lang and Titley, 1998). The district-scale portion of this study examines a segment of the Laramide arc located between the GlobeMiami district and the Bagdad deposit, within which an economic deposit has yet to be identified (Fig. 2). Extension in western Arizona The study area lies between the highly extended Harcuvar and Harquahala metamorphic core complexes to the west and the Bradshaw Mountains to the east (Fig. 3), which lie within the Basin and Range extensional province. Three competing models have emerged to explain the relationships between low-angle mylonitic fabrics that are observed in mid-crustal metamorphic core complexes and the brittle normal faults that are exposed in the upper crust of western Arizona and throughout the Basin and Range province. The first model proposes that the low-angle features are normal faults that initiated at low angles, have tens of km of displacement (Wernicke, 1981, 1985; John, 1987), and eventually expose mylonitic rocks at the surface as extension proceeds (Fig. 4A). A second model and its variations, known as the rolling hinge model, suggests that strongly listric normal faults with tens of km of displacement can be folded by isostatic uplift during extension to expose mylonitic fabrics at the surface (Spencer, 1984; Buck, 1988; Wernicke and Axen, 1988) (Fig. 4B). The first two models contend that a master fault in extensional systems serves as a detachment into which smaller scale faults sole, thereby transferring their displacement. 168 The final model (Fig. 4C) puts forth that a set of “domino–style” faults breaks at high angles (60°-70°) and rotates to low angles during extension (Proffett, 1977; Davis, 1983). When the faults rotate to low angles (~20-30°), slip on the faults becomes kinematically unfavorable (Anderson, 1951), and a new set of faults forms at high angles. Mylonitic rocks in the down-dip toes of abandoned faults, now tilted to low anlges, can be brought to the surface (Davis 1983, 1987), especially if the process is repeated by movement on multiple, crosscutting sets of faults. Previous workers in the Vulture Mountains, ~10 km west of the study area (Fig. 3) proposed that southwest dipping, listric normal faults were responsible for the observed repetition of steeply dipping (up to ~85°) Tertiary sedimentary and volcanic rocks exposed in the Vulture Mountains, as well as for the slightly less tilted (up to ~65°) Tertiary sedimentary and volcanic rocks exposed in the study area (Rehrig et al., 1980) . However, subsequent detailed geologic mapping in the study area (Capps et al., 1986; Stimac et al., 1987) at 1:24,000 scale revealed that normal fault geometries are nearly planar and that higher angle faults cut lower angle faults. Determining the style of extension in the district-scale study area is essential to creating the district-scale reconstruction. Thus, predictions of the two competing models for extension regarding the geometries of the normal faults, and deformation in the hanging walls and footwalls of the normal faults are tested below. Constraints include the amounts of tilting and amount of offset observed of structural markers and structure contour maps illustrating the shapes of the fault planes. 169 Rock types Previous geologic maps are heavily utilized in this study for the distribution of rock types, although new mapping and field checking influenced the interpretation of the nature of various contacts (e.g., unconformity, fault, intrusive, stratigraphic), and the structural interpretations and distribution of alteration products are entirely the product of this study. Geologic maps at 1:24,000 scale of the Wickenburg, southern Buckhorn, and northwestern Hieroglyphic Mountains (Stimac et al., 1987), the western Hieroglyphic Mountains (Capps et al., 1986), the Buckhorn Creek area (Peterson, 1985), and the vicinity near Sheep Mountain (Powers, unpublished map) were compiled and generalized to produce Figure 5. Rocks in the study area consist of Proterozoic amphibolite, gneiss, schist, granite, and pegmatite, intruded by Late Cretaceous granite, and overlain by late Oligocene and Miocene volcanic rocks (Fig 5.) (Stimac et al., 1987). Proterozoic, Paleozoic, and Mesozoic sedimentary rocks, which are locally important ore hosts in some Laramide porphyry deposits (e.g., Resolution, Manske and Paul, 2002), have been denuded in the study area. Most likely the denudation occurred during Laramide or Sevier uplift in the Late Cretaceous (Flowers et al., 2008). The metamorphic Proterozoic rocks exposed in the study area belong to the Yavapai Supergroup (DeWitt et al., 2008). In the Bradshaw Mountains (Fig. 3), the Yavapai Supergroup displays a consistent north-south striking moderate to steeply dipping lineation. Variations in the lineation are used later in this study to constrain Tertiary deformation in the metamorphic rocks. Late Cretaceous granite, dated at 68.4 170 Ma (K/Ar) 10 km west of the study area in the Vulture Mountains (Rehrig et al., 1980), crops out predominantly in the western half of the study area (Fig. 5). The granite is porphyritic to equigranular in texture containing 30-40% orthoclase, 20-30% plagioclase, 20-30% quartz, 3-5% biotite, 1-2% magnetite, and up to 5% sphene, zircon, and other accessory minerals (Stimac et al., 1987). The crystalline Proterozoic and Cretaceous rocks are overlain by Tertiary units, which include siliciclastic sedimentary rocks, volcanic rocks, debris flows, and conglomerates. The oldest Tertiary unit is a red to brown conglomerate containing pebble- to boulder-sized clasts of older crystalline rocks and some volcanic rocks. The conglomerate is similar in appearance to the synextensional red-bed conglomerates of the Whitetail and Cloudburst Formations in southeastern Arizona (Dickinson, 1991). The conglomerate unit varies in thickness from 1 m to 10’s of m and consistently has steep dips of ~55° - 75° to the northeast. Approximately one to two kilometers of Tertiary volcanic and sedimentary rocks overlie the basal Tertiary conglomerate. The geologic map and cross section in Figure 6 depicts a portion of this sequence. Tertiary volcanic and sedimentary rocks have not been dated in the study area. However, volcanism in the nearby Vulture Mountains (Fig. 3) is known to have occurred between ~25-15 Ma. The oldest volcanic unit is a basaltic lava flow that in some places is interbedded with the basal conglomerate (Fig. 6). Above the basalt, rhyolite lava flows and tuffs of the San Domingo Volcanics occur in the western half of the study area. The Morgan City Rhyolite, Spring Valley Rhyolite, and Castle Creek Volcanics occupy a similar stratigraphic position in the eastern half of the study 171 area (Capps et al., 1986; Stimac et al., 1987). Dacite to rhyodacite lava flows and tuffs make up the structurally higher Hells Gate Volcanics. Resting unconformably above the Hells Gate Volcanics are interbedded basalts, tuffs, volcanic megabreccias, and debris flow deposits with nearly horizontal bedding attitudes. Northwest striking and steeply dipping felsic and mafic dikes locally intrude the crystalline basement and the Tertiary volcanic rocks. The youngest Tertiary unit is a brown colored, consolidated to semiconsolidated conglomerate. A thin layer of Quaternary-Tertiary gravels locally covers the conglomerate. ECONOMIC GEOLOGY The study area contains mineralization that is related to several genetic types of deposits and formed at distinctly different times (DeWitt et al., 2008; this study). Gold and copper associated with volcanogenic massive sulfide systems are hosted in metamorphosed Proterozoic rocks. Pegmatite dikes of Proterozoic age have been investigated for their beryllium and lithium potential (Jahns, 1952; London and Burt, 1978). Epithermal style mineralization is locally hosted in Tertiary volcanic rocks. Many of the washes in the study area produced and continue to produce gold in placer deposits hosted in Tertiary and Quaternary gravels. Just west of the study area in the Vulture Mountains, the Vulture mine produced 340,000 ounces of gold and 260,000 ounces of silver between 1863 and 1942 (White, 1989). Mineralization consists of native gold and electrum hosted in Proterozoic and Cretaceous crystalline rocks and is interpreted to be genetically related to a Cretaceous dike (Spencer et al., 2004). 172 Several porphyry systems near the study area of Laramide age have yielded identified resources but no significant past or current production. The largest resource is the Copper Basin prospect, which is located 20 km north of the study area in the Silver Mountain mining district of the southern Bradshaw Mountains (Fig. 3). This prospect, which is distinct from the Copper Basin district described by Johnston and Lowell (1961) that is located farther north near Prescott (Fig. 2), takes its name from the amphitheatershaped basin in which it lies, which was named by soldiers stationed nearby at Fort Misery at the end of the 19th century (Tognoni, 1969). Chalcopyrite and molybdenite are exposed at the surface in Copper Basin, as well as spectacular Cu-oxide seeps in the drainages. Drilling conducted in the late 1960’s and early 1970’s produced a resource estimate of one billion tons of 0.16% Cu and 0.031% MoS2 based on eight drill holes (unpublished Asarco report, 1974). Near Sheep Mountain (Fig. 5), two porphyry prospects have been identified. On the eastern flank of Sheep Mountain, a resource containing 40 million tons of 1.6% Cu and 0.04% MoS2 have been defined at the Sheep Mountain East prospect (Ullmer, 2007). The mineralization lies underneath ~700 m of Tertiary volcanic and sedimentary rocks. Molybdenite from drill core at the prospect has been dating the Re-Os technique at 70.34 ± 0.36 Ma (R. Powers, written comm., 2012). Approximately 5 km to the west of Sheep Mountain East is the Sheep Mountain West prospect, where several outcrops of intensely altered Proterozoic granite are exposed in tilted fault blocks (Fig 5.). The altered Proterozoic rocks are unconformably overlain by Tertiary volcanic and sedimentary rocks. Several drill holes have been drilled 173 in the last decade exploring for supergene mineralization, but a significant resource has not been identified. HYDROTHERMAL ALTERATION Hydrothermal alteration was mapped at reconnaissance scale across the study area (Fig. 7). Three important styles of alteration have been identified: greisen, potassic, and transitional greisen-potassic. The term greisen is used here to describe hydrothermal alteration assemblages where coarse-grained (> 0.5 mm) white mica is an important constituent (e.g., Shaver, 1991; Seedorff et al., 2005a). Where greisen occurs in porphyry copper systems, it occurs at deep levels of the system, generally beneath the level of the orebodies and beneath the most intense potassic alteration and well below the level where sericitic alteration develops (Seedorff et al., 2005a, 2008); in contrast, greisen can occur in porphyry molybdenum deposits of the Mo-Cu subclass in and above orebodies and the most intense potassic alteration, in a position that would be analogous for the position of sericitic alteration in many porphyry copper systems (Shaver, 1991; Seedorff et al., 2005a). Greisen Hosted within the Cretaceous granite (Fig. 8A), northeast-striking veins of quartz + muscovite + pyrite ± chalcopyrite ± K-feldspar (Fig. 8B) commonly compose 1-5% of outcrops in the central Wickenburg Mountains (Fig. 7). Locally, greisen veins + envelopes are so intense that they constitute up to 20 vol% of outcrops. Vein fillings range from 1 - 50 mm wide and have envelopes 5 - 50 mm wide. White mica grains ranges in size from 0.5 - 5 mm and are found in both the vein filling and alteration halo. 174 Quartz in the vein filling is commonly milky white in color. Sulfides are found predominantly in the vein filling but also in the alteration halo. They range in size from 1-15 mm and have a pyrite to chalcopyrite ratio of approximately 10:1. K-feldspar is rarely found in the greisen veins, where it comprises <1% of the vein filling. Potassic In Buckhorn Creek west of Sheep Mountain (Fig. 7), northeast-striking veins of quartz + K-felsdspar ± white mica ± pyrite ± chalcopyrite with biotite envelopes cut Yavapai Schist (Fig. 8C). Veins vary in size from 1-15 mm wide with alteration halos <10 mm wide. Quartz is the dominant mineral in the vein filling (~65%), accompanied by K-feldspar (~20%), white mica (~10%), and sulfides (~5%; pyrite >> chalcopyrite). White mica ranges in size from 0.1-2 mm. The veins increase in abundance to the northeast until they reach an abundance of 5 vol% before they are unconformably covered by Tertiary volcanic rocks. Transitional greisen-potassic This classification is used here with the meaning of Shaver (1991), who first described this coarse-grained white mica-bearing style of alteration at the Hall (Nevada Moly) deposit, Nevada, where it overlies potassic alteration and is regarded as a coarsegrained analogue of sericitic alteration (Shaver, 1991). At Sheep Mountain (Fig. 7), veins of quartz + K-feldspar ± white mica ± sulfide (1-5 mm wide) are cut by quartz + Kfeldspar + white mica + sulfide veins (1-5 mm wide) with white mica halos (<5 mm wide; Fig 8D). The vein density is intense in several areas, where it comprises 5-10 vol% of outcrops. White mica varies in size from 0.1-1 mm. Envelopes surrounding the quartz 175 in the vein filling of both vein types conspicuously change between white mica and Kfeldspar along strike. STRUCTURAL GEOLOGY The repetition of structural markers in the study area (i.e., Tertiary sedimentary and volcanic units, the Tertiary-Proterozoic unconformity, contacts between Proterozoic units, and styles of hydrothermal alteration), was determined by previous studies to be the result of movement on Tertariy (~25-15 Ma) normal faults (Rerhig et al., 1980; Peterson, 1985; Capps et al., 1986; Stimac et al., 1987). By scrutinizing crosscutting relationships between the normal faults exposed in the study area, relative ages can be determined, which is critical to constraining the style of deformation and is necessary for subsequently grouping faults into sets or generations. Examination of the normal faults in map view reveals that five distinct sets of Tertiary normal faults are present in the study area (Fig. 9). Faults within each set have similar strikes and dips and exhibit common crosscutting relationships. Unless they significantly influence the map pattern, faults determined to have less than 500 m of offset are not shown on the geologic map (Fig. 5) and were not assigned to a set of faults (Fig. 9). Many dozens of such small-offset normal faults were identified in previous work across the study area (e.g., Stimac et al., 1987; Fig. 6). Set 1: Two faults from this set crop out at the surface in the Wickenburg Mountains (Fig. 9.), the Wickenburg Mountains fault and the Mount Vernon Fault. These faults have sinuous expressions at the modern surface produced by the intersections of their presentday gentle dips with the modern topography in the study area. A structure contour map 176 (Fig. 10) reveals that the Wickenburg Mountains fault and the Mount Vernon fault have azimuths of ~125 and dip ~4° to the southwest. Across 4 km of down-dip exposure on the Wickenburg Mountains fault (Fig. 10B), the fault dip decreases only slightly from 5.1° to 3.3° (curvature of 0.5°/km). The structure contour map also reveals a northeast-southwest striking trough in the plane of the Mount Vernon fault. Such “mullion” features are commonly observed in low-angle normal faults (e.g., John, 1987; Wong and Gans, 2008). Set 2: The northeast-southwest striking faults in this set strike nearly perpendicular to faults in all other sets. One fault from this set is exposed in the central portion of the study area, where it has a measured dip in outcrop of 45° to the southeast (Fig. 9). This fault places Tertiary volcanic and sedimentary rocks on Proterozoic rocks. To date we have not identified a structural marker that tightly constrains displacement on this fault. Set 3: Faults from this set crop out across the study area. They strike with an azimuth of ~150 and have dips measured in outcrop that range from ~40-50° to the southwest. Ten faults from this set are shown in the map. Typical offsets on faults from this set are approximately one km. The Castle Creek fault (Fig. 9), which bounds the west side of Sheep Mountain, and the Trilby Wash fault belong to this set. Set 4: Members of the second youngest set of faults have an azimuth of ~150 and dip steeply to the southwest at ~60-70°. Dozens of faults from this set crop out across the study area (Stimac et al., 1987); however, few have significant amounts of offset and only four are shown on Figure 9. The fault with the largest offset is the Buckhorn Creek fault (Fig. 9), which has 1.5 km of slip in the central portion of the study area. 177 Set 5: Faults belonging to the youngest set have azimuths of ~330 and dip steeply to the northeast at ~70°. Faults from this set are more common in the eastern half of the study area, and only two are depicted on Figure 9. An example is the Evans Butte fault (Fig. 9), which bounds the western side of the valley west of Sheep Mountain and exhibits ~500 m of offset. STRUCTURAL INTERPRETATION AND PALINSPASTIC RECONSTRUCTION OF NORMAL FAULTS As previously mentioned, earlier work (Stimac et al., 1987) in a portion of the study area concluded that there is no kinematic linkage between the different sets of normal faults described above and that individual normal faults are nearly planar in geometry (Fig. 6)). Original observation and compilation of crosscutting relationships between normal faults across the entire study area (Fig. 9) and structure contour maps of normal faults (Fig. 10) are combined with an analysis of Tertiary tilting shown below to interpret the style of extension in the study area. The interpretation provides the means to palinspastically reconstruct Tertiary extension in a 20-km long cross section through the study area. Tertiary tilting The consistent ~65° northeasterly dip of the oldest Tertiary rocks and of the Tertiary-Proterozoic unconformity (Fig. 5) is consistent with slip on and concurrent tilting of the southwest dipping normal faults. Orientations of foliation in the Proterozoic Yavapai Schist can constrain the magnitude of Tertiary tilting of crystalline rocks in the study area. The orientation of foliation in the Yavapai Schist regionally is commonly 178 consistent over distances of 10’s of km (e.g., DeWitt et al., 2008). Thus any changes observed in the orientation of foliation are likely the result of deformation subsequent to the Proterozoic foliation-forming event. The most probable candidate for reorienting foliation is Tertiary extension. Foliation measurements of the Yavapai Schist in the Wickenburg Mountains, which have been highly extended (Stimac et al., 1987), are compared to foliation measurements of the Yavapai Schist 20 km to the north in the Bradshaw Mountains (Fig. 3). An area for which there is no evidence for significant Tertiary extension and tilting (Rehrig et al., 1980; DeWitt et al., 2008). Measurements of foliation in the two areas are compared in contoured equal area stereographic projection in Figures 11A and 11B, and the average foliation varies significantly between the two areas. To further test the hypothesis that the rigid body rotation was caused by tilting associated with Tertiary extension, the foliation data from the Wickenburg Mountains are rotated 65° clockwise about a horizontal axis trending 150° (Fig. 11C). This rotation would restore the amount of Tertiary tilting recorded by the attitude of the Tertiary-Proterozoic unconformity and by dips on Tertiary volcanic and sedimentary rocks across the study area. The mean plane of the rotated Wickenburg Mountain foliation data (Fig. 11C) plots very close to the mean plane of the foliation data from the unextended Bradshaw Mountains, strongly suggesting that the Yavapai Schist and other Proterozoic rocks record the same magnitude of Tertiary tilting observed in the Tertiary-Proterozoic unconformity and Tertiary volcanic and sedimentary rocks across the study area. 179 Style of extension As mentioned above, debate surrounds the style of extension in the study area (i.e., listric versus more planar, “domino-style” normal faults). Predictions of the competing models are outlined here and tested against observations in the study area. Listric normal faults produce different amounts of hanging-wall and footwall tilting during fault slip as rocks in the hanging wall are transported down a curved fault plane. Where multiple listric normal faults are active, the dip of beds in the hanging walls of successive fault blocks in the transport direction should show progressively steeper dips (e.g., Ramsay and Huber, 1987, p. 520). Observations in map view (Fig. 3) and stereographic analysis (Fig. 11A-C) are not consistent with prediction listric fault geometry. The Yavapai Schist, Tertiary-Proterozoic unconformity, and the oldest Tertiary volcanic and sedimentary rocks in the study area are all tilted ~65° to the northeast during Tertiary extension. This observation requires curvature on fault planes in the study area to be minimal. Furthermore, where significant down-dip exposure of fault planes allows for the determination of fault curvature at the surface (Fig. 10), it is indeed calculated to be quite low (0.3°/km). Taken together, evidence in the study area controverts the involvement of listric normal faults in extension and suggests that extension was accommodated by superimposed sets of nearly planar, “domino-style” faults. Interpretation of the normal faults The grouping of the Tertiary normal faults into fault sets, each with a distinct relative age, suggests that each set can be viewed as sequential generations of faults. Hence, each generation is defined as a set of similarly oriented faults that moved more or 180 less contemporaneously during specific time windows, as evidenced by their consistent crosscutting. As the normal faults within a given set cut and extended the crystalline and supracrustal rocks in the study area, the dip of the active fault planes rotated to lower angles. Once the fault planes of a fault set rotated to angles that were kinematically unfavorable for slippage (less than ~30°; Anderson, 1951), a new fault set with new fault planes formed, and faults of the new set cut and progressively rotated the older fault sets and any contained geologic elements, including porphyry systems. This repeated sequence of events produced a cumulative northeastward tilting of ~65° as evidenced by the present-day dips of the oldest Tertiary volcanic and sedimentary rocks, the dips of Proterozoic-Tertiary unconformity, and change in foliation observed in the Yavapai Schist between local extended and unextended terrains. Approach to restoring movement on normal faults Figures 12 and 13 show palinspastic reconstruction of the 20-km long cross section in the study area and an interpretation of that reconstruction. Displacement along the normal faults was removed in sequential order, from the youngest to the oldest generation of normal faults (panels A through F in Fig. 12), as determined by dip measurements and relative ages. The magnitude of slip on individual faults was constrained using structural markers, including the Proterozoic-Tertiary unconformity, contacts between various lithologies of Proterozoic metamorphic rocks, Tertiary volcanic stratigraphy, and hydrothermal alteration assemblages. Tertiary sedimentary and volcanic rocks were rotated to horizontal in the time slice of the reconstruction when they were deposited. 181 Due to the significant percentage of crystalline rocks in the study area, and thus the paucity of structural markers in certain areas, a number of uncertainties remain in the restoration. The three-dimensional shape of the igneous bodies is unknown; thus the form chosen here is based on relationships that are plausible considering constraints imposed by restoration of hydrothermal alteration patterns (Fig. 13B). As previously mentioned, dips measurements are not available on some faults, either from this study or previous work, due to lack of exposure. In these cases, crosscutting relationships were used to assess the generation to which such faults belonged, and then dips measured from other faults of the same fault set were used. Examination of the district-scale reconstruction The palinspastic reconstruction reveals a total of ~160% northeast-southwest extension across the study area (Fig. 13A). The magnitude of northwest-southeast directed extension is not constrained. The reconstruction implies the presence of two, spatially distinct hydrothermal systems sourced from different cupolas of a Late Cretaceous pluton (Fig. 13A). The Cretaceous pluton intrudes metasedimentary and metavolcanic rocks in the west and metaplutonic rocks in the east. Potassic and transitional potassic-greisen hydrothermal alteration exposed at Buckhorn Creek and Sheep Mountain appear to be sourced from the easternmost cupola of the pluton, whereas the greisen alteration hosted in Late Cretaceous granite in the Wickenburg Mountains is part of a separate hydrothermal system centered on the western cupola of the pluton (Fig 13B). Hydrothermal alteration is zoned upward from greisen to potassic to transitional greisen-potassic assemblages (Fig. 13B). 182 Exploration targets Leading up to and subsequent to the discovery of the Kalamazoo orebody (Lowell, 1968), knowledge and understanding of post-mineralization Tertiary extension in the Laramide porphyry province began to change exploration strategies. Tilted and dismembered orebodies were eventually recognized to be common features in the Basin and Range province (e.g., Proffett, 1977; Shaver and McWilliams, 1987; Seedorff, 1991; Seedorff et al., 1996), and Wilkins and Heidrick (1995) suggested that orebodies in the Basin and Range province should be assumed to be faulted and tilted until proven otherwise. During the past decade, the importance of tilting of orebodies across the Basin and Range province has continued to be emphasized by numerous workers (e.g., p. 276277 of Seedorff et al., 2005a; Maher, 2008; Stavast et al., 2008; Nickerson et al., 2010) and is again demonstrated here. Despite at least two drilling campaigns in the 1960’s and 2000’s, economic mineralization has not yet been located at the Sheep Mountain West prospect. The palinspastic reconstruction demonstrates that sulfide-bearing transitional greisen-potassic alteration at Sheep Mountain and potassic alteration at Buckhorn Creek are both pieces of a larger dismembered porphyry system. Potassically altered pieces of the same porphyry system are shown to be “structurally covered” (Corn an Ahern, 1994) by Tertiary volcanic and sedimentary rocks west of Sheep Mountain in the modern cross section (Fig. 12A). To our knowledge, this target has not been tested with a drill hole but significant mineralization could be associated with potassic alteration. 183 Additionally, it is likely that intense greisen alteration exposed in the Wickenburg Mountains is the expression of a porphyry system (Maher, 2008; Seedorff et al., 2008; Stavast et al., 2008). Whether the intensity of greisen alteration has any correlation to the development of structurally higher levels of potassic and sericitic alteration, including sulfide mineralization, remains uncertain. However, outcrops in the Wickenburg Mountains demonstrate that significant magmatic fluids were released at least locally from that portion of the Late Cretaceous pluton. Structurally higher levels that may contain porphyry mineralization are not located in the line of section but may lie underneath Quaternary and Tertiary cover southwest of the study area. The targets generated by the district-scale palinspastic reconstruction provide an example of a geologically based method for exploring beneath post-mineralization cover rocks. In the Laramide porphyry province, geologically driven exploration underneath post-mineralization cover has yielded several discoveries (e.g., Kalamazoo, Lowell, 1968; Resolution, Paul and Manske, 2005). Continued exploration in the province should incorporate structural interpretations when designing exploration programs that may also involve geophysical and geochemical techniques. CLASSIFICATION OF PORPHYRY SYSTEMS NEAR WICKENBURG Because an orebody has not been located in the study area, it is speculative to classify the two indentified porphyry systems based on an economically dominant metal. However, deposit classes are at least partially constrained by compositions of igneous source rocks and may display some distinctive styles of hydrothermal alteration (Seedorff et al., 2005a). For example, porphyry Au deposits are normally associated with dioritic 184 host rocks, whereas porphyry W and Sn deposits are associated with rhyolitic and rhyodacitic source rocks, respectively. The granitic composition of the inferred Late Cretaceous source rocks for the porphyry systems in the study area (Figs. 13A-B) may be indicative of porphyry molybdenum deposits of the quartz monzonitic-granitic porphyry Mo-Cu or granitic porphyry Mo subclasses (Seedorff et al., 2005a). Nonetheless, porphyry Cu-(Mo) deposits in the Globe-Miami district (Fig. 2) are sourced from the Schultze Granite, which is compositionally similar (Stavast, 2006; Maher, 2008) to the Late Cretaceous granite in the study area. The conspicuous absence of large numbers of porphyry dikes in the study area is also commonly observed in porphyry Mo-Cu systems (e.g., Hall (Nevada Moly), Shaver, 1991; Buckingham, Loucks and Johnson, 1992). The transitional greisen-potassic style of alteration documented on Sheep Mountain is perhaps suggestive of a porphyry Mo-Cu system as well, because the only other well documented instance of this distinctive style of high-level alteration is the Hall (Nevada Moly) porphyry Mo-Cu system (Shaver, 1991). The high Mo contents observed in the nearby porphyry resources at Sheep Mountain East (0.04 % MoS2; Fig, 3) and Copper Basin (0.031% MoS2; Fig. 3) also are suggestive of porphyry Mo-Cu affinities. Together, this evidence suggests that the porphyry systems identified here are perhaps part of a cluster of porphyry Mo-Cu systems located in the middle of what was previously thought to be a large gap in the Laramide porphyry belt (Titley, 1982b). 185 ARC-SCALE RECONSTRUCTION OF TERTIARY EXTENSION IN THE LARAMIDE PORPHYRY COPPER BELT To better understand spatial relationships of porphyry deposits in the Laramide porphyry copper belt, a preliminary regional scale reconstruction of Cenozoic extension has been undertaken (Figs. 14-17), revisiting a topic addressed earlier by Richard (1994) but using a different approach. The approach taken here is first described, and then, compared to the previous work. Methodology A compilation of strikes and dips of the oldest pre- and syn-extension Oligocene and Miocene sedimentary and volcanic strata across the porphyry belt serves as the data for the reconstruction (Fig. 14). The tilting information recorded by the bedding attitudes provides a basis for grouping regions where the magnitude of extension was similar. These data are then adapted to estimate a β factor utilizing the equations of Jackson and McKenzie (1983). The β factor is calculated using the following equation: β= sin 𝜃 sin 𝜃′ where θ is the dip of a normal fault at its inceptions, and θ’ is the dip of the normal fault after fault motion ceases. Several assumptions are made in the calculations: (1) the dips of syn- and post-extension Tertiary rocks record only the effects of Cenozoic extension; (2) normal faults were tilted to lower angles by the same amount that Tertiary beds were tilted to steeper dips; (3) single sets of faults accommodated a maximum of 30° of tilting; (4) all extension was northeast-southwest directed; (5) tilting was unidirectional; and (6) any post-Laramide strike-slip faulting did not significantly alter deposit locations. It is 186 unlikely that these conditions are met across the entire region considered here; however, the generalization of Cenozoic extension in this manner allows for a palinspastic reconstruction of the porphyry systems of the Laramide porphyry copper belt that is more representative of its original form than the current, post-extension distribution. Using geometric considerations, Jackson and McKenzie (1983) demonstrated that a normal fault which is back-tilted from 60° to 30° produces a β factor of 1.73, equivalent to 73% extension. In the strike and dip compilation used here, dips of 0° to 30°, 30° to 60°, and 60° to 90° are grouped together. An average amount of extension was assigned for each domain (Fig. 15), and a regional contour map of the magnitude extension was created. Locations of porphyry deposits were restored to the northeast by removing the cumulative amount of extension between the modern location of a deposit and the unextended terrain outside the Basin and Range (either the Colorado Plateau or the southern Rocky Mountains). In addition to the uncertainties introduced from the assumptions made in its construction, further uncertainties about the distribution of porphyry deposits arise from their degree of preservation and the limited modern exposure of the porphyry copper belt. Denudation prior to or during Tertiary extension in Arizona could have completely eroded porphyry systems in the arc. Furthermore, Quaternary and Tertiary sedimentary and volcanic rocks cover greater than 50 percent of the surface in the Basin and Range province of Arizona (Reynolds, 1988). These younger rocks likely conceal additional Laramide porphyry systems. Thus, the geometry of the exposed porphyry deposits of the 187 Laramide magmatic arc in the reconstruction should be considered representative but not absolute. As previously mentioned, this study follows in the path of a previous arc-scale reconstruction by Richard (1994). Central to both approaches were the process of delineating extensional domains using tilting information recorded in Tertiary rocks and restoring extension using the equations of Jackson and McKenzie (1983). However, the two reconstructions differ in one important way. The earlier work averaged the dips of Tertiary rocks to determine tilting within domains, as opposed to estimating tilting using the dips of only the oldest pre- or syn-extension Tertiary rocks. By averaging the dips of all Tertiary rocks, calculations of extension are influenced by rocks which only record a portion of the extension with a domain. Thus, the earlier calculations significantly underestimated the amount of extension. Examination of the arc-scale reconstruction of the Laramide porphyry beltThe Laramide porphyry copper belt is a manifestation of the Laramide magmatic arc of southwestern North America (Titley, 1982b). Hence, when discussing the geometry of the porphyry copper belt it is appropriate to call on terminology used to describe magmatic features in continental arcs. It is important to consider, however, that the ages of Laramide porphyry deposits span ~75-55 Ma (Titley, 1982b; Seedorff et al, 2005b). Thus, the reconstruction of the porphyry belt shown here is a time-integrated product, not a snapshot of arc magmatism. The reconstructed distribution of porphyry deposits of the Laramide arc (Fig. 16, 17A) yields a variably well defined zone, with gaps and clusters of deposits along the 700 188 km of strike length parallel to the Laramide plate margin. The apparent axis of the porphyry copper belt (dashed in Figure 17A) extends from Mineral Park to Red Mountain. Along-axis deposits lie between Mineral Park and Red Mountain. Forearc deposits include Ajo, Cananea, and La Caridad, and rear-arc deposits include the Safford district, Morenci, Tyrone, Chino, and Hillsboro. Along-axis spacing between the deposits is variable. Deposits in the Globe-Miami, Safford. and Pima districts are separated by only a few kilometers, whereas Sheep Mountain and Ajo are separated by an apparent gap of more than 100 km along the axis of the magmatic arc. Across-axis spacing of deposits is also highly variable. Resolution lies 20 km from the deposits of the Globe-Miami district, but La Caridad is separated from Hillsboro by 240 km. Casa Grande and Vekol, as well as deposits within the Globe-Miami and Pima districts, are separated by less than 10 km across axis. In the Globe-Miami and Pima districts, studies have shown that the clustering of deposits reflects in part the dismemberment by Tertiary normal faults (Stavast, 2006; Maher, 2008; Stavast et al., 2008). That is, the named deposits identified today were once parts of larger porphyry systems, as is the case in the classic example of San Manuel-Kalamazoo (Lowell, 1968). This reconstruction, using dips of Tertiary beds to make estimates of the amount of extension, is a basis for comparison for future arc-scale structural reconstructions of the porphyry belt. For example, a more precise and time-consuming approach would be to perform fault-by-fault restorations, of the type employed here only in the Wickenburg area, across the arc at numerous locations up and down the arc. 189 DISCUSSION Style of extension in western Arizona As introduced above, debate surrounds the style of extension in western Arizona, and three competing models have been put forward (Fig. 4). Previous work in the Vulture Mountains concluded that extension was accommodated on strongly listric normal faults (Rerhig et al., 1980). Results shown here indicate that extension in the study area was accommodated via normal faulting similar to the “domino-style” model of extension. Whereas similar relationships observed in map pattern between faults, hanging wall rocks, and footwall rocks do indicate a similar style of extension in the study area and the Vulture Mountains, evidence within the study area precludes normal faults from having a strongly listric geometry. The principal difference observed between extended rocks in the Vulture Mountains and the study area, is that rocks in the Vulture Mountains are more tilted (~85° northeast). An increase in the amount of tilting in the Vulture Mountains can be explained using the style of extension demonstrated in the study area if an additional set of southwest dipping normal faults had been active there. Evidence for such a fault set has been documented at the Vulture mine, where a normal fault has been back-tilted through horizontal to a dip of 15° northeast overturned (Grubensky and Shipman, 2004). This fault set has been tilted approximately an additional 20° to the southwest compared to the low-angle faults exposed in the Wickenburg Mountains (Fig. 10), consistent with the ~20° increase in tilting observed in the supracrustal rocks in the Vulture Mountains. Thus, it is proposed here that both the Vulture Mountains and the study area were part of 190 a regional system of superimposed sets of rotating planar normal faults that accommodated significant southwest-northeast extension between ~25 and 15 Ma. The Harcuvar and Harquahala metamorphic core complexes are located approximately 30 km west of the Vulture Mountains. The timing of extension in these core complexes and in the study area was similar (~25-15 Ma, Rehig et al., 1980; Carter et al., 2004). However, in the Harcuvar and Harquahala Mountains upper plate rocks were transported to the northeast, opposite the transport direction observed in the study area and in the Vulture Mountains (Spencer and Reynolds, 1990). Mylonitic rocks in the core complexes are interpreted by Reynolds and Spencer (1985) to have formed during slip on the Bullard detachment fault. According to Reynolds and Spencer (1985), the Bullard fault initiated slip at a low angle (10°-20°), accommodated as much as 50 km of slip, and captured the displacement of higher-angle faults that are interpreted to sole into the detachment fault (Carter et al., 2004). This style of extension varies significantly from was is observed in the study area, but has also been proposed to explain the formation of the metamorphic core complexes further west in the Colorado River extensional corridor in western Arizona and southeastern California (Howard and John, 1987; Lister and Davis, 1989). Metamorphic core complexes are known to be mid-crustal expressions of extension (Davis, 1980). The lack of mylonitic fabrics exposed in the study area and the Vulture Mountains suggests that normal faulting has only exposed the upper-crustal expressions of extension in these areas. Currently, it is difficult to reconcile the different styles of extension proposed here for upper-crustal rocks with models proposed for mid- 191 crustal extension in the nearby Harcuvar and Harquahala metamorphic core complexes (Fig. 3). Further study is required to determine what factors control the different style of extension in each area, or whether the proposed style of extension in the metamorphic core complexes should be reconsidered. Comparison of the scale and geometry of the Laramide magmatic arc to other arcs Whereas exploration in the Laramide porphyry copper belt has evolved to consider deposit-scale (e.g., Lowell, 1968; Wilkins and Heidrick, 1995), district-scale (e.g., Stavast et al., 2008), and sometimes regional-scale extension (e.g., Maher, 2008), little attention has been given to the effects of extension at the scale of the Laramide porphyry belt (Richard, 1994), and a comparison of the pre-extension geometry of the Laramide porphyry copper belt to magmatic features in other well studied arcs is lacking. The length, breath, and spacing between porphyry centers in the reconstructed Laramide porphyry copper belt is compared to other magmatic features in the prolific central Chilean porphyry copper sub-belt in the Miocene-early Pliocene magmatic arc (Sillitoe and Perelló, 2005) and the Quaternary Cascade volcanic arc of northwestern North America (Hildreth, 2007) in Figure 17A-C. The magmatic features in each of the arcs are distinctive. For example, as previously mentioned, the Laramide porphyry belt spans about 20 million years of activity (~75-55 Ma, Lang and Titley, 1998; Seedorff et al., 2005b) and was not necessarily stationary during that interval. The central Chilean sub-belt—somewhat arbitrarily constrained in length—was active for about 12 million years (16-4 Ma, Sillitoe and Perelló, 2005). The Quaternary portion of the Cascade arc includes only its last two million years of activity (Hildreth, 2007), and this portion is not 192 yet sufficiently eroded to reveal much about its potential for porphyry mineralization (e.g., John et al., 2005). The length of the Laramide porphyry copper belt, at 700 km, is greater than the 400-km long Miocene-early Pliocene porphyry copper sub-belt of central Chile, but shorter than the 1,250 km long chain of volcanic fields Quaternary Cascade arc. Spacing between deposits (and volcanic fields) along strike is similar, with all three arcs having area of clustered magmatic activity, as well as apparent gaps in magmatic activity greater than 100 km. One clear difference is the breadth of the Laramide porphyry copper belt south of Red Mountain, where it reaches a maximum width of 240 km. The maximum across axis width between magmatic features in the other arcs is less than 150 km. Clearly, there is no blueprint for magmatic features in convergent oceaniccontinental plate margin arc. Differences in the interaction between down-going slabs, mantle wedges, and continental crust will make each arc distinctive. However, when compared at the entire arc scale, differences in geometry between the reconstructed Laramide magmatic arc (as revealed by the porphyry copper belt) and other arcs appear to be minimal. CONCLUSIONS The effects of Tertiary extension on the geometry of Laramide porphyry systems has been demonstrated at the district and porphyry belt scale. Original reconnaissance mapping was combined with previous detailed mapping to serve as data for a 20 km long palinspastic reconstruction. The reconstruction revealed that two porphyry-style hydrothermal systems emanate from a Laramide aged pluton exposed in the study area. 193 Hydrothermal alteration is zoned from greisen at deeper levels, to potassic and transitional greisen-potassic at higher levels. Five superimposed sets of normal faults, which initially developed and high angles and then rotated to lower angles during extension, dismembered the porphyry systems and buried potentially well-mineralized fault blocks underneath Tertiary volcanic and sedimentary rocks. This upper-crustal style of extension differs from mid-crustal models for extension in the nearby Harcuvar and Harquahala metamorphic core complexes which formed contemporaneously. Further study will be required to rectify the apparent inconsistency in the style of extension in the region. Extension at the scale of the Laramide porphyry belt was quantified using a compilation strikes and dips documented in pre- and syn-extension rocks across the porphyry belt. The tilting information recorded by the attitudes provides a basis to group regions where the magnitude of extension was similar, and then is adapted to estimate β factor . Tertiary extension was then restored quantitatively to reveal the pre-extension geometry of the arc, where the majority of porphyry deposits clearly define a 100 km wide axis, and others lie in fore-arc or rear-arc settings. 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Wong, M.S., and Gans, P.B., 2008, Geologic, structural, and thermochronologic constraints on the tectonic evolution of the Sierra Mazatán core complex, Sonora, Mexico: New insights into metamorphic core complex formation: Tectonics, v. 27, no. 4, TC4013. FIGURE CAPTIONS Figure 1. Location map depicting selected ore deposits which lie in the Basin and Range province of western North America. MCC = metamorphic core complex. Dashed box indicates location of Figure 3. Figure 2. Index map of porphyry deposits in the Laramide porphyry copper belt. Modified from Titley, (1982b). Figure 3. Genearalized geologic map of western Arizona showing location of the districtscale study area (dashed box) and nearby mountain ranges discussed in the text. MCC = metamorphic core complex (geology from Reynolds, 1988). Figure 4. Three models proposed to explain the link between upper-crustal and midcrustal extension in the Basin and Range province. A. Extension accommodated along a “detachment” fault which initiates slip at a dip angle < 30° (after Wernicke, 1985). B. Extension accommodated along a strongly listric “detachment” fault which is up-warped by isostacy during extension (after Spencer, 1984). C. Extension accommodated along two sets of planar normal faults which rotate to lower dips during extension (after Dickinson, 1991). 204 Figure 5. Generalized geologic map across the study area depicting rock units, faults, selected bedding orientations, and localities discussed in the text. Tertiary volcanic rocks in the Hells Gate Formation and older units are grouped in the Tertiary lower volcanic unit. Tertiary volcanic rocks younger than the Hells Gate Formation are grouped in the Tertiary upper volcanic unit. Geology from Peterson (1985),_Capps et al. (1986), Stimac et al. (1987) and Powers (unpublished map). Figure 7. Geologic map and cross section D-D’, digitized from Stimac et al. (1987) Figure illustrates the detailed pre-existing mapping of rock type and structural geology in the district-scale study area. Location of map shown in Figure 6. Figure 7. Reconnaissance map of hydrothermal alteration in the study area. Key for rock units faded in the background is found in Figure 5. Figure 8. Photographs of styles of veins and associated alteration in the study area. A. Unaltered Cretaceous granite. B. Quartz-muscovite-pyrite±chalcopyrite±K-feldspar vein hosted in Cretaceous granite; an example of greisen style alteration. B. Quartz+Kfeldsspar+white mica+pyrite±chalcopyrite vein with a biotite envelope cutting Yavapai Schist at Buckhorn Creek; an example of potassic alteration. C. Quartz+K-feldspar±white mica±sulfide veins cut by quartz+K-feldspar+white mica+sulfide veins with white mica halos hosted in Proterozoic gneiss at Sheep Mountain West prospect. The crosscutting vein is an example of the transitional greisen-potassic style of alteration. Figure 9. Normal faults in the study area grouped into five sets, numbered from oldest to youngest. Faults within each set have similar strikes and dips, as well as, common cross cutting relationships. 205 Figure 10. Structure contour map of two faults from set one in the exposed in the Wickenburg Mountains. A. Structure contour map with topography as a base layer. B. Structure contour map with the hanging wall and footwall of each fault shaded. Dips are calculated across two intervals on the southwestern low-angle fault, illustrating that the dip of the faults changes only slightly over 6 km of nearly continuous down dip exposure. The calculated curvature is 0.5°/km. Figure 11. Contoured poles to planes of foliation measurements in the Yavapai Schist depicted on stereonets using equal area lower hemisphere projections. A. Foliation measurements in the Yavapai Schist from the unextended southern Bradshaw Mountains 20 km north of Sheep Mountain. Data from DeWitt et al. (2008). B. Foliation measurements in the Yavapai Schist from the Wickenburg Mountains. Data from Stimac et al. (1987). C. Rotation of the data in panel B 65° clockwise about a horizontal axis striking 150°. The rotation restores Tertiary tilting in the study area. The rotated data from the Wickenburg Mountains very closely match the data from the Bradshaw Mountains, indicating that congruent amounts of tilting are recorded in the Yavapai Schist, the Proterozoic-Tertiary unconformity, and Tertiary sedimentary and volcanic rocks. Figure 12. Panels depicting the palinspastic reconstruction of cross section A to A’. Locations of endpoints and key to rock units are located on Figure 5. A. Modern cross section. B. Restoration of the 5th set of normal faults. C. Restoration of the 4th set of normal faults. D. Restoration of the 3rd set of normal faults. E. Restoration of the 2nd set of normal faults. The fault in this set strikes nearly perpendicular to the line of section. 206 The true orientation of this fault prior to slip was 110°, 60° SW. F. Restoration of the 1st set of normal faults. Figure 13. An interpretive cross section constrained by the palinspastic reconstruction. Unit legend the same as Figure 5. A. The interpretation is faded in the background, and pieces of the reconstruction are shown in the foreground. Geographic locations discussed in the text are indicated with thin lines. Two exploration targets are indentified which are located directly above the two cupolas of the Cretaceous pluton. B. Interpretation of the zoning patterns in hydrothermal alteration in the two hydrothermal systems identified in the study area. Figure 14. Compilation of strikes and dips of Tertiary sedimentary and volcanic rocks. (rock units from Reynolds, 1988) Figure 15. Domains of Cenozoic extension constrained by dip measurements in Tertiary sedimentary and volcanic rocks (Fig. 14). Locations of porphyry deposits shown in the background. Figure 16. Index map of porphyry deposits in their present and restored location. Figure 17. Comparison of porphyry systems of the reconstructed Laramide porphyry copper belt to features in other magmatic arcs. A. The reconstructed location of porphyry systems of the Laramide magmatic arc. B. Porphyry copper systems of Miocene-Early Pliocene magmatic arc of central Chile (after Sillitoe and Perelló, 2005). C. The Quaternary Cascade magmatic arc of northwestern North America (after Hildreth, 2007), showing major volcanic centers. Note the change in scale from panels A and B to panel C. 207 Figure 1. 208 Figure 2. 209 Figure 3. 210 Figure 4. 211 Figure 5. 212 Figure 6. Figure 6 continued. 213 214 Figure 7. 215 Figure 8. 216 Figure 9. 217 Figure 10. 218 Figure 11. 219 Figure 12. 220 Figure 13. 221 Figure 14. 222 Figure 15. 223 Figure 16. 224 Figure 17. 225 APPENDIX D: ELECTRON MICROPROBE ANALYSIS OF FELDSPAR, SHEET SILICATES, EPIDOTE, AND AMPHIBOLES FROM TEA CUP AND EAGLE PASS, ARIZONA Figure 1. Location map of samples from the Tea Cup porphyry system, Pinal County, Arizona Figure 2. Location map of samples from the Eagle Pass porphyry system, Graham County, Arizona 226 Figure 1. 227 Figure 2. 228 Table 1. Location of Tea Cup eletron microprobe samples Position Sample # (Lat/Lon hddd mm.mmm') on Fig. 1 Sample Name TV07 08 0 N33 04.165 W111 03.203 TC 004 1 N33 04.098 W111 03.798 TC 011 2 N33 04.029 W111 03.923 TC 010 3 N33 04.211 W111 03.974 TC 008 4 N33 04.001 W111 03.212 TC 009 5 N33 04.020 W111 03.164 TC 007 6 N33 04.015 W111 03.146 TC 001 7 N33 03.945 W111 03.600 TC 002 8 N33 04.071 W111 03.235 SP 004 9 N33 04.463 W111 03.879 SP 007 10 N33 04.423 W111 03.820 SP 009 11 N33 05.877 W111 01.109 SP 014 12 N33 06.024 W111 02.008 SP 017 13 N33 02.783 W111 11.522 SP 019 14 N33 02.350 W111 13.547 SP 020 15 N33 02.352 W111 13.504 SP 023 16 N33 02.335 W111 13.412 SP 025 17 N33 02.725 W111 13.199 SP 029 18 N33 01.880 W111 11.456 SP 032 19 N33 02.535 W111 11.493 SP 034 20 N33 02.929 W111 11.876 SP 035 21 N33 03.263 W111 12.121 SP 043 22 N33 05.041 W111 12.816 SP 048 23 N33 03.426 W111 12.948 SP 073b 24 N33 02.281 W111 11.059 SP 075 25 N33 02.773 W111 13.098 SP 079 26 N33 02.716 W111 13.075 SP 081 27 N33 02.670 W111 12.925 SP 092 28 N33 02.562 W111 13.162 SP 097 29 N33 02.391 W111 13.089 SP 114 30 N33 05.114 W111 04.773 SP 115 31 N33 05.128 W111 04.819 SP 123 32 N33 05.506 W111 02.282 229 Table 2. Location of Eagle Pass eletron microprobe samples Location Sample # (Lat/Lon hddd mm.mmm') on Fig. 2 Sample name MW SPCHEM 0 N32 48.840 W110 07.354 MW 001 1 N32 48.392 W110 06.688 MW NACA2 2 N32 48.452 W110 06.804 MW NACA3 3 N32 48.612 W110 07.113 MW ALT5 4 N32 49.235 W110 07.808 FRS ORCLE 5 N32 47.738 W110 06.599 EP 005 6 N32 46.678 W110 07.598 EP 007 7 N32 46.448 W110 07.362 EP 006 8 N32 46.207 W110 07.336 EP 016 9 N32 45.198 W110 08.139 EP 017 10 N32 45.304 W110 08.153 EP 021 11 N32 45.531 W110 07.973 EP 022 12 N32 45.576 W110 07.934 EP 024 13 N32 48.212 W110 07.275 EP 033 14 N32 44.951 W110 07.830 EP 034 15 N32 44.968 W110 07.776 EP 035 16 N32 44.974 W110 07.751 EP 037 17 N32 44.994 W110 07.452 EP 038 18 N32 45.336 W110 07.361 EP 040 19 N32 43.295 W110 05.820 EP 042 20 N32 44.224 W110 05.923 EP 046 21 N32 43.114 W110 07.389 EP 070 22 N32 48.144 W110 10.096 EP 086 23 N32 46.466 W110 07.674 230 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 004 SP 007 SP 009 Sample number kspar1 SP 004 plg1 plag2 SP 007 plg3 kspar2 Replacing kspar kspar plag Host rock Yg Yg Yg Yg Kpd SiO2 64.90 68.95 68.95 68.70 93.36 TiO2 0.00 0.00 0.00 0.00 0.04 Al2O3 18.02 19.42 19.63 19.46 3.01 Cr2O3 0.00 0.00 0.00 0.00 0.00 Fe2O3 0.07 0.00 0.00 0.00 0.00 FeO 0.00 0.00 0.03 0.00 0.13 MgO 0.00 0.00 0.00 0.00 0.00 MnO 0.00 0.00 0.01 0.00 0.00 CaO 0.00 0.12 0.42 0.34 0.07 Na2O 0.33 12.23 11.74 11.61 0.09 K2O 15.88 0.02 0.06 0.06 1.88 F 0.00 0.07 0.00 0.00 0.43 Cl 0.00 0.01 0.00 0.00 0.00 Total 99.20 100.79 100.85 100.18 98.83 Based on IV=4 Si (T) 3.01 3.00 2.99 3.00 3.85 Al (T) 0.99 1.00 1.01 1.00 0.15 Fe3+ (T) 0.00 0.00 0.00 0.00 0.00 Na (A) 0.03 1.03 0.99 0.98 0.01 K (A) 0.94 0.00 0.00 0.00 0.10 Ca (A) 0.00 0.01 0.02 0.02 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) 0.00 0.00 0.00 0.00 0.00 Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.01 0.00 0.00 0.06 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 7.99 8.00 8.00 7.94 End Member Or# An# Ab# 0.95 0.01 0.04 0.97 0.00 0.03 0.00 0.01 0.99 0.00 0.02 0.98 0.91 0.03 0.06 SP 014 kspar2 Yg 65.18 0.02 17.92 0.00 0.00 0.00 0.00 0.00 0.00 0.88 15.23 0.00 0.04 99.27 3.02 0.98 0.00 0.08 0.90 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.92 0.00 0.08 231 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 020 Sample number SP 014 plg1 SP 017 plg1 SP 017 ser1 SP 019 plg1 kspar1 Replacing plag plag plag Host rock Yg Kpd Kpd Yg Yg SiO2 68.71 67.12 68.03 64.69 63.95 TiO2 0.00 0.04 0.04 0.00 0.03 Al2O3 19.37 20.02 20.04 19.24 18.12 Cr2O3 0.02 0.00 0.00 0.01 0.02 Fe2O3 0.00 0.00 0.00 0.00 0.03 FeO 0.02 0.00 0.04 0.12 0.00 MgO 0.00 0.02 0.00 0.00 0.00 MnO 0.02 0.03 0.00 0.02 0.00 CaO 0.32 0.17 0.28 2.74 0.00 Na2O 11.59 11.79 12.22 11.17 0.33 K2O 0.16 0.02 0.07 0.04 15.87 F 0.04 0.00 0.00 0.00 0.00 Cl 0.06 0.00 0.01 0.00 0.00 Total 100.28 99.21 100.74 98.03 98.35 Based on IV=4 3.00 2.96 2.97 2.96 3.00 Si (T) 1.00 1.04 1.03 1.04 1.00 Al (T) 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.98 1.01 1.03 0.99 0.03 Na (A) 0.01 0.00 0.00 0.00 0.95 K (A) 0.02 0.01 0.01 0.13 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.01 0.00 0.00 0.00 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 7.99 8.00 8.00 8.00 8.00 End Member Or# An# Ab# 0.01 0.02 0.98 0.00 0.01 0.99 0.00 0.01 0.98 0.00 0.12 0.88 0.97 0.00 0.03 SP 020 kspar2 Yg 64.26 0.00 18.18 0.01 0.00 0.00 0.00 0.01 0.00 1.09 15.02 0.00 0.01 98.58 3.00 1.00 0.00 0.10 0.89 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.90 0.00 0.10 232 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 020 SP 023 SP 023 SP 025 SP 025 Sample number kspar3 kspar1 kspar2 kspar1 kspar2 Replacing Host rock Yg Yg Yg Yg Yg SiO2 64.80 65.46 64.81 64.54 65.00 TiO2 0.00 0.07 0.00 0.01 0.00 Al2O3 18.43 18.52 18.43 18.42 18.32 Cr2O3 0.00 0.01 0.00 0.00 0.05 Fe2O3 0.12 0.13 0.00 0.04 0.00 FeO 0.00 0.00 0.02 0.00 0.00 MgO 0.00 0.01 0.00 0.00 0.00 MnO 0.00 0.00 0.00 0.00 0.00 CaO 0.00 0.00 0.00 0.00 0.00 Na2O 0.40 0.51 0.55 0.49 0.58 K2O 16.10 15.79 16.27 15.55 15.78 F 0.00 0.19 0.33 0.00 0.17 Cl 0.01 0.02 0.01 0.00 0.00 Total 99.87 100.62 100.28 99.05 99.83 Based on IV=4 2.99 2.99 3.00 2.99 3.00 Si (T) 1.00 1.00 1.00 1.01 1.00 Al (T) 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.04 0.05 0.05 0.04 0.05 Na (A) 0.95 0.92 0.96 0.92 0.93 K (A) 0.00 0.00 0.00 0.00 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.03 0.05 0.00 0.03 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 7.97 7.95 8.00 7.97 End Member Or# An# Ab# 0.96 0.00 0.04 0.95 0.00 0.05 0.95 0.00 0.05 0.95 0.00 0.05 0.95 0.00 0.05 SP 025 plg1 Yg 67.91 0.01 20.14 0.00 0.06 0.00 0.00 0.01 0.53 11.10 0.20 0.00 0.00 99.96 2.96 1.04 0.00 0.94 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.01 0.03 0.96 233 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 029 SP 032 Sample number kspar1 SP 029 plg1 kspar1 SP 032 plg1 SP 032 plg2 Replacing plag plag Host rock Kpd Kpd Kpd Kpd Kpd SiO2 63.98 99.51 64.05 67.60 59.68 TiO2 0.00 0.01 0.00 0.03 0.00 Al2O3 18.42 0.24 18.79 20.49 24.57 Cr2O3 0.02 0.02 0.00 0.00 0.03 Fe2O3 0.04 0.11 0.03 0.00 0.02 FeO 0.00 0.00 0.00 0.00 0.16 MgO 0.00 0.00 0.00 0.00 0.00 MnO 0.01 0.00 0.00 0.00 0.00 CaO 0.00 0.01 0.01 0.78 6.43 Na2O 0.28 0.02 0.54 11.29 7.51 K2O 15.83 0.01 15.69 0.23 0.70 F 0.00 0.06 0.00 0.05 0.00 Cl 0.01 0.01 0.00 0.00 0.00 Total 98.58 99.98 99.13 100.46 99.11 Based on IV=4 2.99 3.98 2.97 2.95 2.69 Si (T) 1.01 0.01 1.03 1.05 1.31 Al (T) 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.02 0.00 0.05 0.95 0.66 Na (A) 0.94 0.00 0.93 0.01 0.04 K (A) 0.00 0.00 0.00 0.04 0.31 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.01 0.00 0.01 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 7.99 8.00 7.99 8.00 End Member Or# An# Ab# 0.97 0.00 0.03 0.96 0.02 0.02 0.95 0.00 0.05 0.01 0.04 0.95 0.04 0.31 0.65 SP 035 plag3 Yg 64.83 0.00 18.02 0.02 0.00 0.05 0.01 0.00 0.00 0.64 15.73 0.13 0.00 99.38 3.01 0.99 0.00 0.06 0.93 0.00 0.00 0.00 0.00 0.00 0.02 0.00 7.98 0.94 0.00 0.06 234 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 043 Sample number SP 035 plg2 kspar1 SP 043 plg1 SP 043 plg2 SP 048 plg1 SP 048 plg2 Replacing kspar plag plag plag Host rock Yg Yg Yg Yg Yg Yg SiO2 64.54 65.03 69.18 67.70 68.63 68.00 TiO2 0.01 0.00 0.00 0.00 0.00 0.00 Al2O3 22.25 18.00 19.21 18.76 19.59 19.78 Cr2O3 0.00 0.00 0.00 0.00 0.01 0.00 Fe2O3 0.00 0.00 0.00 0.00 0.00 0.00 FeO 0.03 0.05 0.08 0.02 0.01 0.04 MgO 0.00 0.00 0.00 0.00 0.01 0.00 MnO 0.04 0.00 0.00 0.00 0.01 0.00 CaO 3.47 0.00 0.23 0.04 0.02 0.24 Na2O 9.70 0.67 11.64 11.72 11.80 12.10 K2O 0.17 15.74 0.13 0.09 0.03 0.09 F 0.00 0.01 0.00 0.00 0.30 0.07 Cl 0.00 0.00 0.01 0.00 0.00 0.00 Total 100.21 99.50 100.48 98.33 100.27 100.30 Based on IV=4 2.84 3.01 3.01 3.01 2.99 2.98 Si (T) 1.16 0.99 0.99 0.99 1.01 1.02 Al (T) 0.00 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.83 0.06 0.98 1.01 1.00 1.03 Na (A) 0.01 0.93 0.01 0.01 0.00 0.00 K (A) 0.16 0.00 0.01 0.00 0.00 0.01 Ca (A) 0.00 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.00 0.00 0.00 0.04 0.01 Cl (X) 0.00 0.00 0.00 0.00 0.00 0.00 O 8.00 8.00 8.00 8.00 7.96 7.99 End Member Or# An# Ab# 0.01 0.16 0.83 0.94 0.00 0.06 0.01 0.01 0.98 0.01 0.00 0.99 0.00 0.00 1.00 0.00 0.01 0.98 235 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 073b SP 081 SP 081 Sample number kspar1 kspar2 SP 081 plg1 SP 081 plg2 kspar1 Replacing plag plag plag Host rock Yg Yg Yg Yg Yg SiO2 64.28 64.49 64.29 68.16 68.56 TiO2 0.01 0.00 0.11 0.05 0.05 Al2O3 18.65 18.64 18.61 19.96 19.86 Cr2O3 0.00 0.00 0.02 0.00 0.02 Fe2O3 0.06 0.14 0.02 0.00 0.00 FeO 0.00 0.00 0.00 0.01 0.00 MgO 0.01 0.00 0.00 0.01 0.00 MnO 0.00 0.00 0.00 0.00 0.00 CaO 0.00 0.02 0.00 0.23 0.37 Na2O 0.97 1.08 0.78 11.81 11.55 K2O 15.08 15.39 15.45 0.15 0.09 F 0.08 0.00 0.00 0.14 0.00 Cl 0.00 0.00 0.00 0.00 0.00 Total 99.10 99.77 99.27 100.46 100.51 Based on IV=4 2.98 2.98 2.98 2.97 2.98 Si (T) 1.02 1.02 1.02 1.03 1.02 Al (T) 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.09 0.10 0.07 1.00 0.97 Na (A) 0.89 0.91 0.91 0.01 0.01 K (A) 0.00 0.00 0.00 0.01 0.02 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.01 0.00 0.00 0.02 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 7.99 8.00 8.00 7.98 8.00 End Member Or# An# Ab# 0.91 0.00 0.09 0.90 0.00 0.10 0.93 0.00 0.07 0.01 0.01 0.98 0.01 0.02 0.98 SP 097 kspar1 plag Yg 63.58 0.01 18.30 0.00 0.11 0.00 0.01 0.00 0.00 0.64 15.41 0.00 0.01 98.06 2.98 1.01 0.00 0.06 0.92 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.94 0.00 0.06 236 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 114 SP 123 Sample number kspar2 SP 114 plg1 SP 114 plg2 SP 115 plg1 kspar1 Replacing plag plag Host rock Yg Yg Yg Yg Yg SiO2 64.93 66.59 69.11 66.46 64.35 TiO2 0.00 0.07 0.03 0.00 0.00 Al2O3 18.56 19.21 20.17 19.71 18.80 Cr2O3 0.00 0.02 0.00 0.01 0.01 Fe2O3 0.08 0.00 0.01 0.00 0.05 FeO 0.00 0.17 0.00 0.06 0.00 MgO 0.02 0.02 0.00 0.00 0.00 MnO 0.04 0.01 0.01 0.01 0.00 CaO 0.01 0.19 0.32 0.65 0.03 Na2O 0.76 11.48 11.59 11.29 1.33 K2O 15.34 0.09 0.10 0.10 14.65 F 0.00 0.23 0.00 0.06 0.00 Cl 0.01 0.01 0.00 0.05 0.00 Total 99.74 97.97 101.34 98.36 99.23 Based on IV=4 2.99 2.98 2.98 2.96 2.97 Si (T) 1.01 1.02 1.02 1.04 1.02 Al (T) 0.00 0.00 0.00 0.00 0.00 Fe3+ (T) 0.07 1.00 0.97 0.98 0.12 Na (A) 0.90 0.01 0.01 0.01 0.86 K (A) 0.00 0.01 0.01 0.03 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.03 0.00 0.01 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 7.97 8.00 7.99 8.00 End Member Or# An# Ab# 0.93 0.00 0.07 0.01 0.01 0.99 0.98 0.00 0.02 0.96 0.03 0.01 0.12 0.00 0.88 SP 123 plag1 kspar Yg 62.47 0.00 23.98 0.00 0.00 0.18 0.00 0.03 5.11 8.99 0.26 0.10 0.00 101.08 2.75 1.25 0.00 0.77 0.01 0.24 0.00 0.00 0.00 0.00 0.01 0.00 7.99 0.01 0.24 0.75 237 Table 3. Normalized microprobe data: feldspars from Tea Cup SP 123 SP 123 TC 001 TC 001 TC 004 Sample number plg1 plg2 kspar1 plag2 plag3 Replacing vein vein plag Host rock Yg Yg Khbg Kpd Kpd SiO2 66.66 66.85 62.84 62.11 64.29 TiO2 0.00 0.01 0.01 0.04 0.03 Al2O3 21.02 21.15 24.16 24.20 18.77 Cr2O3 0.03 0.02 0.00 0.00 0.00 Fe2O3 0.04 0.19 0.02 0.00 0.00 FeO 0.00 0.00 0.00 0.06 0.07 MgO 0.00 0.01 0.00 0.00 0.00 MnO 0.03 0.02 0.01 0.02 0.02 CaO 1.48 1.39 5.26 5.38 0.01 Na2O 10.97 11.18 8.19 8.17 0.80 K2O 0.15 0.14 0.43 0.53 14.95 F 0.00 0.05 0.00 0.30 0.53 Cl 0.00 0.00 0.00 0.00 0.01 Total 100.39 100.98 100.91 100.68 99.26 Based on IV=4 2.91 2.91 2.75 2.74 2.97 Si (T) 1.08 1.09 1.25 1.26 1.03 Al (T) 0.00 0.01 0.00 0.00 0.00 Fe3+ (T) 0.93 0.94 0.70 0.70 0.07 Na (A) 0.01 0.01 0.02 0.03 0.88 K (A) 0.07 0.06 0.25 0.25 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.01 0.00 0.04 0.08 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 7.99 8.00 7.96 7.92 End Member Or# An# Ab# 0.01 0.07 0.92 0.01 0.06 0.93 0.02 0.26 0.72 0.00 0.16 0.83 0.92 0.00 0.08 TC 004 plag1 Khbg 57.58 0.00 26.95 0.00 0.15 0.00 0.00 0.00 8.69 6.35 0.18 0.13 0.00 99.97 2.57 1.42 0.00 0.55 0.01 0.42 0.00 0.00 0.00 0.00 0.02 0.00 7.98 0.01 0.43 0.56 238 Table 3. Normalized microprobe data: feldspars from Tea Cup TC 006 TC 006 TC 008 TC 009 TC 009 Sample number kspar1 plg1 kspar1 kspar1 kspar2 Replacing Host rock Khbg Khbg Yg Yg Yg SiO2 65.16 64.21 64.98 64.52 64.60 TiO2 0.03 0.00 0.03 0.01 0.01 Al2O3 18.62 22.95 18.77 18.64 18.78 Cr2O3 0.00 0.00 0.00 0.00 0.01 Fe2O3 0.00 0.15 0.00 0.24 0.06 FeO 0.08 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.02 0.01 0.01 MnO 0.00 0.02 0.00 0.01 0.00 CaO 0.00 3.55 0.00 0.00 0.07 Na2O 0.98 9.03 0.94 0.33 0.78 K2O 15.40 0.23 15.44 15.81 14.50 F 0.25 0.42 0.38 0.05 0.00 Cl 0.00 0.00 0.00 0.00 0.00 Total 100.41 100.40 100.40 99.60 98.82 Based on IV=4 2.99 2.81 2.98 2.98 2.98 Si (T) 1.01 1.18 1.02 1.01 1.02 Al (T) 0.00 0.01 0.00 0.01 0.00 Fe3+ (T) 0.09 0.77 0.08 0.03 0.07 Na (A) 0.90 0.01 0.90 0.93 0.85 K (A) 0.00 0.17 0.00 0.00 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.04 0.06 0.06 0.01 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 7.96 7.94 7.94 7.99 8.00 End Member Or# An# Ab# 0.91 0.00 0.09 0.01 0.18 0.81 0.91 0.00 0.09 0.97 0.00 0.03 0.92 0.00 0.08 TC 009 kspar3 Yg 64.42 0.00 18.54 0.00 0.05 0.00 0.00 0.01 0.00 0.25 16.03 0.00 0.01 99.31 2.99 1.01 0.00 0.02 0.95 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.98 0.00 0.02 239 Table 3. Normalized microprobe data: feldspars from Tea Cup TC 009 TC 009 TC 010' TC 011 TC 011 Sample number plg1 plg2 plg1 kspar1 plg1 Replacing kspar plag plag Host rock Yg Yg Yg Yg Yg SiO2 67.55 67.61 69.19 64.54 64.18 TiO2 0.00 0.00 0.04 0.02 0.05 Al2O3 20.53 20.14 19.92 18.81 23.27 Cr2O3 0.00 0.00 0.00 0.00 0.01 Fe2O3 0.41 0.04 0.00 0.11 0.00 FeO 0.00 0.00 0.06 0.00 0.14 MgO 0.00 0.00 0.01 0.00 0.00 MnO 0.01 0.00 0.00 0.01 0.02 CaO 1.15 0.62 0.07 0.02 4.07 Na2O 11.32 11.48 11.90 0.89 9.78 K2O 0.03 0.06 0.04 15.05 0.13 F 0.00 0.00 0.22 0.08 0.00 Cl 0.00 0.00 0.00 0.00 0.01 Total 101.00 99.96 101.36 99.48 101.65 Based on IV=4 2.94 2.96 2.98 2.97 2.80 Si (T) 1.05 1.04 1.02 1.02 1.20 Al (T) 0.01 0.00 0.00 0.00 0.00 Fe3+ (T) 0.95 0.97 1.00 0.08 0.83 Na (A) 0.00 0.00 0.00 0.88 0.01 K (A) 0.05 0.03 0.00 0.00 0.19 Ca (A) 0.00 0.00 0.00 0.00 0.00 Mg (A) 0.00 0.00 0.00 0.00 0.00 Ti (A) Cr (A) 0.00 0.00 0.00 0.00 0.00 Mn (A) 0.00 0.00 0.00 0.00 0.00 F (X) 0.00 0.00 0.03 0.01 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 O 8.00 8.00 7.97 7.99 8.00 End Member Or# An# Ab# 0.00 0.05 0.95 0.00 0.03 0.97 0.00 0.00 0.99 0.92 0.00 0.08 0.01 0.19 0.81 TV08 07 plg1 Yg 66.83 0.00 21.32 0.00 0.00 0.03 0.00 0.00 1.25 11.25 0.03 0.59 0.00 101.05 2.91 1.09 0.00 0.95 0.00 0.06 0.00 0.00 0.00 0.00 0.08 0.00 7.92 0.00 0.06 0.94 240 Table 3. Normalized microprobe data: feldspars from Tea Cup TV08 07 Sample number plg2 Replacing plag Host rock Yg SiO2 62.76 TiO2 0.00 Al2O3 23.41 Cr2O3 0.00 Fe2O3 0.19 FeO 0.00 MgO 0.00 MnO 0.00 CaO 4.32 Na2O 9.27 K2O 0.20 F 0.00 Cl 0.00 Total 100.15 Based on IV=4 2.77 Si (T) 1.22 Al (T) 0.01 Fe3+ (T) 0.79 Na (A) 0.01 K (A) 0.20 Ca (A) 0.00 Mg (A) 0.00 Ti (A) Cr (A) 0.00 0.00 Mn (A) F (X) 0.00 Cl (X) 0.00 O 8.00 End Member Or# An# Ab# 241 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 004 SP 004 ser1 SP 004 ser2 SP 009 ser1 chl1 clinochlore alumino-celadonite alumino-celadonite muscovite biotite vein vein biotite Yg Yg Yg Kpd 33.60 50.41 45.63 50.80 0.01 0.00 0.01 0.45 18.73 25.37 24.46 28.87 0.02 0.01 0.01 0.02 2.41 1.23 1.71 0.67 12.27 4.42 6.14 2.42 16.13 2.16 6.27 1.95 0.38 0.10 0.12 0.01 0.86 1.10 1.03 0.31 0.11 0.44 0.01 0.06 0.47 4.67 2.82 9.27 11.72 4.27 4.14 4.42 0.34 0.00 0.00 0.16 0.01 0.10 0.08 0.01 97.07 94.29 92.43 99.40 -0.15 -0.02 -0.02 -0.07 96.92 94.26 92.41 99.33 3.39 3.52 3.29 3.39 0.61 0.48 0.71 0.61 1.62 1.60 1.36 1.66 2.43 0.22 0.67 0.19 1.04 0.26 0.37 0.13 0.18 0.06 0.09 0.03 0.03 0.01 0.01 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.70 0.85 0.49 0.95 0.02 0.06 0.00 0.01 0.06 0.42 0.26 0.79 0.09 0.08 0.08 0.02 0.82 0.44 0.66 0.18 0.11 0.00 0.00 0.03 0.00 0.01 0.01 0.00 7.89 1.99 1.99 1.97 242 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 009 ser2 SP 014 SP 014 SP 014 SP 017 bt1 chl1 chl2 kspr1 muscovite annite clinochlore muscovite alumino-celadonite biotite biotite biotite Kpd Yg Yg Yg Kpd 48.05 35.90 26.97 47.17 47.98 0.13 2.81 0.07 0.14 0.21 31.64 15.19 18.70 32.90 29.60 0.00 0.01 0.02 0.01 0.00 0.78 4.85 4.18 0.47 1.10 2.80 17.46 21.29 1.70 3.97 1.02 8.96 15.60 0.88 2.31 0.00 0.26 0.63 0.03 0.08 0.17 0.00 0.04 0.00 0.24 0.15 0.02 0.00 0.28 0.09 10.05 9.42 0.00 10.29 9.25 4.40 3.62 11.31 4.43 4.28 0.08 0.24 0.16 0.00 0.30 0.02 0.21 0.02 0.01 0.00 99.28 98.94 98.97 98.31 99.40 -0.04 -0.15 -0.07 0.00 -0.13 99.24 98.79 98.90 98.31 99.27 3.24 2.84 2.84 3.19 3.26 0.76 1.16 1.16 0.81 0.74 1.75 0.26 1.16 1.82 1.62 0.10 1.06 2.45 0.09 0.23 0.16 1.16 1.88 0.10 0.23 0.04 0.29 0.33 0.02 0.06 0.00 0.02 0.06 0.00 0.00 0.01 0.17 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.94 0.05 0.12 0.96 0.85 0.02 0.00 0.00 0.04 0.01 0.86 0.95 0.00 0.89 0.80 0.01 0.00 0.00 0.00 0.02 0.10 0.05 1.00 0.07 0.17 0.02 0.06 0.05 0.00 0.06 0.00 0.03 0.00 0.00 0.00 1.98 1.91 7.94 2.00 1.94 243 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 017 bt2 SP 017 ser2 SP 019 ser1 SP 019 ser2 SP 019 ser4 alumino-celadonite clinochlore muscovite clinochlore muscovite biotite biotite biotite biotite Kpd Kpd Yg Yg Yg 45.72 33.91 47.13 31.02 49.03 0.15 0.72 0.24 0.13 0.05 30.02 22.00 34.16 21.39 31.25 0.00 0.02 0.00 0.01 0.00 1.07 3.02 0.52 3.19 0.52 3.85 15.42 1.87 16.27 1.89 2.69 10.58 1.03 14.96 1.40 0.10 0.48 0.03 0.45 0.00 0.12 0.39 0.04 0.11 0.27 0.08 0.10 0.59 0.04 0.11 8.82 1.89 9.42 0.89 9.53 4.31 12.10 4.21 11.78 4.32 0.00 0.07 0.61 0.49 0.30 0.01 0.01 0.00 0.00 0.02 96.93 100.71 99.85 100.75 98.68 0.00 -0.03 -0.26 -0.21 -0.13 96.93 100.68 99.60 100.54 98.55 3.18 3.35 3.14 3.10 3.29 0.82 0.65 0.86 0.90 0.71 1.64 1.91 1.83 1.61 1.77 0.28 1.56 0.10 2.22 0.14 0.22 1.27 0.10 1.36 0.11 0.06 0.22 0.03 0.24 0.03 0.01 0.04 0.00 0.04 0.00 0.01 0.05 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.79 0.93 0.93 0.52 0.96 0.01 0.02 0.08 0.01 0.01 0.78 0.24 0.80 0.11 0.82 0.01 0.04 0.00 0.01 0.02 0.20 0.70 0.12 0.87 0.15 0.00 0.02 0.13 0.15 0.06 0.00 0.00 0.00 0.00 0.00 2.00 7.98 1.87 7.85 1.93 244 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 020 bt1 SP 020 bt2 SP 020 bt3 SP 023 bt2 SP 023 ser1 muscovite vein Yg 46.26 0.32 30.67 0.00 0.80 2.90 1.62 0.05 0.03 0.21 9.68 4.29 0.08 0.00 96.91 -0.03 96.88 3.20 0.80 1.71 0.17 0.17 0.04 0.00 0.02 0.00 0.90 0.03 0.86 0.00 0.11 0.02 0.00 1.98 alumino-celadonite biotite Yg 45.13 0.42 30.37 0.02 1.28 4.61 1.79 0.03 0.00 0.12 10.27 4.28 0.07 0.01 98.40 -0.03 98.36 3.14 0.86 1.62 0.18 0.27 0.07 0.00 0.02 0.00 0.83 0.02 0.91 0.00 0.07 0.02 0.00 1.98 muscovite biotite Yg 47.47 0.01 31.06 0.00 0.79 2.83 2.13 0.06 0.01 0.11 10.22 4.39 0.06 0.01 99.14 -0.03 99.11 3.22 0.78 1.70 0.21 0.16 0.04 0.00 0.00 0.00 0.89 0.01 0.88 0.00 0.10 0.01 0.00 1.99 muscovite biotite Yg 45.60 0.20 32.86 0.00 0.75 2.70 1.00 0.00 0.00 0.32 11.00 4.35 0.07 0.02 98.87 -0.03 98.83 3.12 0.88 1.76 0.10 0.15 0.04 0.00 0.01 0.00 0.93 0.04 0.96 0.00 0.00 0.02 0.00 1.98 muscovite biotite Yg 47.64 0.42 31.25 0.01 0.81 2.90 1.67 0.06 0.00 0.30 10.75 4.46 0.00 0.00 100.27 0.00 100.27 3.20 0.80 1.68 0.17 0.16 0.04 0.00 0.02 0.00 0.92 0.04 0.92 0.00 0.04 0.00 0.00 2.00 245 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea CTable 4. Nor SP 025 bt1 SP 029 SP 029 SP 032 SP 032 SP 034 ser1 chl1 chl1 chl1 chl2 muscovite clinochlore clinochlore clinochlore clinochlore muscovite biotite biotite biotite biotite biotite plag Yg Kpd Kpd Kpd Kpd Yg 45.97 28.29 27.62 27.49 27.51 47.73 0.08 0.01 0.04 0.03 0.17 0.12 29.21 19.26 21.29 19.59 19.49 31.43 0.01 0.01 0.00 0.00 0.01 0.00 1.18 3.00 3.04 3.42 3.30 0.93 4.24 15.32 15.51 17.46 16.81 3.36 1.62 19.76 20.02 19.23 18.98 0.83 0.02 0.77 0.65 0.43 0.36 0.04 0.03 0.06 0.06 0.06 0.06 0.00 0.21 0.02 0.02 0.05 0.03 0.16 10.43 0.07 0.00 0.06 0.15 10.50 3.96 11.48 11.71 11.60 11.64 4.34 0.66 0.48 0.48 0.25 0.00 0.18 0.03 0.01 0.02 0.02 0.00 0.01 97.64 98.54 100.46 99.69 98.51 99.65 -0.28 -0.20 -0.21 -0.11 0.00 -0.08 97.36 98.34 100.25 99.58 98.51 99.57 3.22 2.90 2.77 2.81 2.83 3.23 0.78 1.10 1.23 1.19 1.17 0.77 1.63 1.22 1.29 1.17 1.20 1.74 0.17 3.02 3.00 2.93 2.91 0.08 0.25 1.31 1.30 1.49 1.45 0.19 0.06 0.23 0.23 0.26 0.26 0.05 0.00 0.07 0.06 0.04 0.03 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.88 0.15 0.12 0.10 0.14 0.93 0.03 0.00 0.00 0.01 0.01 0.02 0.93 0.01 0.00 0.01 0.02 0.91 0.00 0.01 0.01 0.01 0.01 0.00 0.04 0.98 0.99 0.98 0.97 0.07 0.15 0.15 0.15 0.08 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 1.85 7.84 7.85 7.92 8.00 1.96 246 rmalized microprobe data: sheet silicates from Tea Cup. Sample number SP 034 ser2 SP 034 ser3 SP 035 bt2 SP 035 chl1 Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) muscovite plag Yg 45.54 0.41 30.74 0.01 1.07 3.84 1.58 0.07 0.00 0.30 10.83 4.14 0.43 0.00 98.95 -0.18 98.76 3.15 0.85 1.65 0.16 0.22 0.06 0.00 0.02 0.00 0.89 0.04 0.95 0.00 0.01 0.09 0.00 1.91 muscovite phlogopite plag Yg Yg 46.87 36.63 0.10 3.14 30.10 15.74 0.00 0.02 1.21 3.93 4.36 14.15 0.93 10.64 0.04 0.60 0.00 0.01 0.13 0.05 10.28 9.46 4.25 3.16 0.19 1.46 0.00 0.00 98.48 98.98 -0.08 -0.62 98.40 98.36 3.24 2.85 0.76 1.15 1.69 0.29 0.10 1.23 0.25 0.92 0.06 0.23 0.00 0.04 0.01 0.18 0.00 0.00 0.90 0.11 0.02 0.01 0.91 0.94 0.00 0.00 0.08 0.05 0.04 0.36 0.00 0.00 1.96 1.64 alumino-celadonite biotite Yg 46.65 0.33 24.53 0.01 1.74 6.28 5.17 0.15 0.04 0.05 7.56 3.88 0.78 0.01 97.17 -0.33 96.84 3.29 0.71 1.33 0.54 0.37 0.09 0.01 0.02 0.00 0.63 0.01 0.68 0.00 0.31 0.17 0.00 1.83 247 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 035 ser1 SP 043 SP 043 SP 043 ser1 SP 048 bt1 chl1 chl2 alumino-celadonite clinochlore clinochlore muscovite muscovite plag biotite biotite vein biotite Yg Yg Yg Yg Yg 52.68 27.93 26.14 46.65 49.47 0.08 0.21 0.06 0.07 0.16 25.43 18.18 18.32 34.65 28.78 0.01 0.01 0.01 0.00 0.06 1.04 4.10 4.00 0.32 0.66 3.73 20.91 20.42 1.16 2.36 2.45 15.17 15.74 0.30 1.93 0.00 0.54 0.52 0.07 0.05 0.40 0.13 0.09 0.00 0.12 0.06 0.04 0.00 0.36 0.11 8.41 0.13 0.06 10.68 9.12 4.20 11.30 10.91 4.42 4.23 0.53 0.25 0.47 0.06 0.33 0.01 0.00 0.00 0.00 0.03 99.01 98.90 96.73 98.75 97.41 -0.22 -0.10 -0.20 -0.03 -0.15 98.79 98.80 96.53 98.72 97.27 3.55 2.93 2.82 3.14 3.37 0.45 1.07 1.18 0.86 0.63 1.56 1.19 1.14 1.89 1.69 0.25 2.38 2.53 0.03 0.20 0.21 1.84 1.84 0.07 0.13 0.05 0.32 0.32 0.02 0.03 0.00 0.05 0.05 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.93 0.21 0.11 0.99 0.94 0.01 0.01 0.00 0.05 0.01 0.72 0.02 0.01 0.92 0.79 0.03 0.01 0.01 0.00 0.01 0.24 0.96 0.98 0.04 0.18 0.11 0.08 0.16 0.01 0.07 0.00 0.00 0.00 0.00 0.00 1.89 7.92 7.84 1.99 1.93 248 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 048 SP 048 SP 073b SP 073b SP 073b SP 073b chl1 chl2 chl3 chl4 chl1 chl2 clinochlore clinochlore chamosite chamosite chamosite chamosite biotite biotite vein vein vein vein Yg Yg Yg Yg Yg Yg 26.43 26.09 24.74 24.41 26.21 23.30 0.10 0.00 0.03 0.01 0.02 0.02 19.47 20.20 19.69 19.07 17.13 20.71 0.02 0.03 0.01 0.00 0.00 0.01 3.68 3.71 5.15 5.05 4.57 5.56 18.77 18.92 26.26 25.74 23.28 28.36 14.32 14.85 8.19 8.54 6.52 8.15 1.13 1.20 0.99 1.02 1.52 1.13 0.09 0.05 0.09 0.11 0.31 0.03 0.00 0.00 0.03 0.08 0.09 0.05 0.00 0.05 0.32 0.11 0.92 0.07 10.79 11.03 10.69 10.45 10.13 10.73 0.59 0.35 0.00 0.18 0.09 0.08 0.00 0.01 0.01 0.01 0.02 0.04 95.39 96.48 96.20 94.76 90.80 98.24 -0.25 -0.15 0.00 -0.08 -0.04 -0.04 95.14 96.33 96.20 94.68 90.76 98.20 2.86 2.79 2.77 2.78 3.09 2.59 1.14 1.21 1.23 1.22 0.91 1.41 1.35 1.34 1.38 1.34 1.47 1.31 2.31 2.37 1.37 1.45 1.15 1.35 1.70 1.69 2.46 2.45 2.29 2.64 0.30 0.30 0.43 0.43 0.40 0.47 0.10 0.11 0.09 0.10 0.15 0.11 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.22 0.18 0.26 0.23 0.53 0.12 0.00 0.00 0.01 0.02 0.02 0.01 0.00 0.01 0.05 0.02 0.14 0.01 0.01 0.01 0.01 0.01 0.04 0.00 0.99 0.99 0.94 0.95 0.80 0.98 0.20 0.12 0.00 0.06 0.03 0.03 0.00 0.00 0.00 0.00 0.00 0.01 7.80 7.88 8.00 7.93 7.96 7.97 249 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 073b SP 073b SP 075 ser1 SP 075 ser2 SP 075 ser3 SP 075 ser4 ser1 ser2 muscovite muscovite muscovite muscovite muscovite muscovite biotite biotite biotite plag plag plag Yg Yg Yg Yg Yg Yg 48.96 45.21 45.32 48.28 48.45 47.69 0.04 0.66 0.66 0.04 0.12 0.09 29.75 30.86 30.26 31.76 30.75 32.18 0.00 0.01 0.02 0.00 0.01 0.00 1.30 0.97 1.12 0.83 0.88 0.85 4.67 3.49 4.05 2.97 3.17 3.06 0.40 1.38 1.62 0.59 0.71 0.55 0.12 0.02 0.05 0.01 0.07 0.02 0.05 0.00 0.00 0.13 0.03 0.05 0.19 0.30 0.22 0.22 0.17 0.18 10.15 10.60 10.78 9.99 9.69 10.03 4.29 4.22 4.03 4.36 4.32 4.30 0.28 0.20 0.61 0.19 0.19 0.29 0.00 0.01 0.00 0.01 0.00 0.00 100.19 97.92 98.74 99.37 98.57 99.29 -0.12 -0.09 -0.26 -0.08 -0.08 -0.12 100.07 97.83 98.48 99.29 98.49 99.17 3.32 3.14 3.14 3.25 3.29 3.22 0.68 0.86 0.86 0.75 0.71 0.78 1.69 1.67 1.62 1.78 1.75 1.79 0.04 0.14 0.17 0.06 0.07 0.05 0.26 0.20 0.23 0.17 0.18 0.17 0.07 0.05 0.06 0.04 0.04 0.04 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.03 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.93 0.90 0.88 0.95 0.94 0.94 0.03 0.04 0.03 0.03 0.02 0.02 0.88 0.94 0.95 0.86 0.84 0.86 0.00 0.00 0.00 0.01 0.00 0.00 0.09 0.02 0.02 0.10 0.14 0.11 0.06 0.04 0.13 0.04 0.04 0.06 0.00 0.00 0.00 0.00 0.00 0.00 1.94 1.95 1.87 1.96 1.96 1.94 250 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 076 ser1 SP 076 ser2 SP 076 ser3 SP 076 ser4 SP 076 ser6 muscovite plag Yg 48.76 0.02 29.88 0.00 0.91 3.28 1.55 0.00 0.00 0.22 10.16 4.29 0.29 0.00 99.37 -0.12 99.25 3.30 0.70 1.69 0.16 0.19 0.05 0.00 0.00 0.00 0.92 0.03 0.88 0.00 0.09 0.06 0.00 1.94 muscovite plag Yg 48.96 0.02 29.98 0.00 0.84 3.01 1.32 0.01 0.00 0.22 10.34 4.43 0.00 0.00 99.13 0.00 99.13 3.31 0.69 1.70 0.13 0.17 0.04 0.00 0.00 0.00 0.95 0.03 0.89 0.00 0.08 0.00 0.00 2.00 muscovite biotite Yg 46.21 0.32 29.09 0.00 1.02 3.69 1.96 0.01 0.00 0.18 10.38 4.15 0.31 0.00 97.32 -0.13 97.19 3.23 0.77 1.62 0.20 0.22 0.05 0.00 0.02 0.00 0.89 0.02 0.92 0.00 0.05 0.07 0.00 1.93 muscovite plag Yg 46.61 0.07 33.07 0.01 0.78 2.82 1.24 0.00 0.00 0.28 10.52 4.36 0.20 0.00 99.97 -0.08 99.88 3.14 0.86 1.77 0.12 0.16 0.04 0.00 0.00 0.00 0.91 0.04 0.90 0.00 0.06 0.04 0.00 1.96 alumino-celadonite plag Yg 47.11 0.01 27.83 0.00 1.57 5.64 1.85 0.00 0.00 0.22 10.51 4.25 0.13 0.02 99.13 -0.06 99.07 3.27 0.73 1.55 0.19 0.33 0.08 0.00 0.00 0.00 0.85 0.03 0.93 0.00 0.04 0.03 0.00 1.97 251 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 079 ser1 SP 079 ser2 SP 079 ser3 SP 081 bt2 SP 081 ser1 muscovite vein Yg 47.48 0.17 29.70 0.00 0.89 3.19 1.40 0.03 0.03 0.24 9.99 4.19 0.32 0.01 97.64 -0.14 97.51 3.28 0.72 1.69 0.14 0.18 0.05 0.00 0.01 0.00 0.93 0.03 0.88 0.00 0.09 0.07 0.00 1.93 alumino-celadonite vein Yg 46.64 0.28 28.64 0.01 1.16 4.16 2.54 0.03 0.00 0.20 10.49 4.12 0.44 0.01 98.72 -0.19 98.53 3.23 0.77 1.56 0.26 0.24 0.06 0.00 0.01 0.00 0.86 0.03 0.93 0.00 0.05 0.10 0.00 1.90 muscovite vein vein 46.99 0.02 28.72 0.00 0.98 3.53 1.21 0.02 0.07 0.23 9.86 4.10 0.34 0.02 96.09 -0.15 95.94 3.30 0.70 1.68 0.13 0.21 0.05 0.00 0.00 0.00 0.93 0.03 0.88 0.00 0.08 0.08 0.00 1.92 muscovite biotite Yg 48.52 0.18 29.13 0.00 0.80 2.90 1.61 0.03 0.00 0.16 10.39 4.10 0.59 0.02 98.42 -0.25 98.17 3.32 0.68 1.67 0.16 0.17 0.04 0.00 0.01 0.00 0.95 0.02 0.91 0.00 0.07 0.13 0.00 1.87 muscovite biotite Yg 46.52 0.21 30.72 0.00 0.94 3.37 1.59 0.02 0.01 0.23 10.49 4.18 0.38 0.02 98.66 -0.16 98.50 3.20 0.80 1.68 0.16 0.19 0.05 0.00 0.01 0.00 0.90 0.03 0.92 0.00 0.05 0.08 0.00 1.92 252 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 092 ser1 SP 092 ser2 SP 092 ser3 SP 097 bt1 SP 097 chl1 alumino-celadonite muscovite muscovite phlogopite clinochlore biotite vein vein biotite Yg Yg Yg Yg Yg 45.36 47.57 46.29 36.47 27.39 0.23 0.16 0.14 3.60 0.00 27.77 29.88 30.01 15.51 20.58 0.00 0.00 0.00 0.04 0.02 1.38 0.86 0.97 3.89 3.30 4.96 3.10 3.48 13.99 16.85 3.57 1.25 1.43 11.84 18.25 0.09 0.00 0.03 0.17 0.30 0.00 0.03 0.00 0.00 0.01 0.19 0.31 0.23 0.10 0.00 10.74 9.99 10.39 9.12 0.05 4.13 4.31 4.19 3.68 11.66 0.32 0.08 0.24 0.34 0.00 0.00 0.00 0.01 0.17 0.00 98.75 97.55 97.42 98.92 98.40 -0.14 -0.03 -0.10 -0.18 0.00 98.61 97.51 97.31 98.74 98.40 3.17 3.28 3.22 2.81 2.82 0.83 0.72 0.78 1.19 1.18 1.46 1.70 1.68 0.22 1.31 0.37 0.13 0.15 1.36 2.80 0.29 0.18 0.20 0.90 1.45 0.07 0.04 0.05 0.23 0.26 0.01 0.00 0.00 0.01 0.03 0.01 0.01 0.01 0.21 0.00 0.00 0.00 0.00 0.00 0.00 0.79 0.94 0.91 0.07 0.16 0.03 0.04 0.03 0.02 0.00 0.96 0.88 0.92 0.90 0.01 0.00 0.00 0.00 0.00 0.00 0.02 0.08 0.05 0.09 0.99 0.07 0.02 0.05 0.08 0.00 0.00 0.00 0.00 0.02 0.00 1.93 1.98 1.95 1.89 8.00 253 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 097 SP 097 ser1 SP 114 act1 SP 114 chl3 SP 114 chl2 kspar1 clinochlore phlogopite clinochlore alumino-celadonite muscovite biotite biotite biotite kspar Yg Yg Yg Yg Yg 27.46 36.55 26.48 48.53 46.20 0.07 1.06 0.19 0.15 0.46 18.30 17.18 18.95 23.13 29.97 0.03 0.00 0.00 0.00 0.02 3.38 3.55 3.85 1.56 1.08 17.25 12.77 19.62 5.63 3.88 18.62 13.60 16.12 4.95 1.82 0.32 0.18 1.68 0.22 0.11 0.01 0.00 0.04 0.04 0.02 0.06 0.11 0.01 0.02 0.25 0.04 8.73 0.00 9.92 10.51 11.16 3.62 11.23 4.12 4.31 0.55 0.52 0.25 0.36 0.08 0.00 0.14 0.00 0.00 0.00 97.28 98.01 98.43 98.65 98.70 -0.23 -0.25 -0.11 -0.15 -0.03 97.05 97.76 98.32 98.50 98.67 2.88 2.81 2.80 3.39 3.19 1.12 1.19 1.20 0.61 0.81 1.15 0.36 1.16 1.30 1.62 2.91 1.56 2.54 0.52 0.19 1.51 0.82 1.73 0.33 0.22 0.27 0.21 0.31 0.08 0.06 0.03 0.01 0.15 0.01 0.01 0.01 0.06 0.02 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.12 0.00 0.10 0.76 0.88 0.01 0.02 0.00 0.00 0.03 0.01 0.86 0.00 0.88 0.92 0.00 0.00 0.00 0.00 0.00 0.98 0.13 0.99 0.11 0.04 0.18 0.13 0.08 0.08 0.02 0.00 0.02 0.00 0.00 0.00 7.82 1.86 7.92 1.92 1.98 254 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 115 SP 115 SP 115 ser1 SP 123 bt1 SP 123 bt2 SP 123 chl1 kspar1 kspar2 muscovite muscovite clinochlore phlogopite phlogopite clinochlore kspar kspar biotite kspar biotite vein Yg Yg Yg Yg Yg Yg 45.23 44.64 28.00 34.27 35.56 26.91 0.17 0.28 0.18 3.15 3.00 0.06 33.71 33.50 19.75 16.64 14.69 18.37 0.00 0.00 0.01 0.01 0.01 0.00 0.85 0.90 3.41 4.36 4.28 4.02 3.06 3.25 17.40 15.71 15.42 20.48 0.70 0.61 14.04 10.70 11.75 16.50 0.02 0.05 1.46 0.35 0.34 0.49 0.01 0.00 0.20 0.00 0.00 0.05 0.72 0.30 0.04 0.10 0.10 0.06 10.07 11.18 0.52 9.47 9.44 0.00 4.40 4.19 11.21 3.60 3.53 11.35 0.00 0.37 0.19 0.43 0.57 0.01 0.00 0.00 0.00 0.04 0.08 0.01 98.93 99.27 96.40 98.84 98.80 98.32 0.00 -0.16 -0.08 -0.19 -0.26 -0.01 98.93 99.11 96.32 98.64 98.54 98.31 3.08 3.06 2.97 2.69 2.79 2.84 0.92 0.94 1.03 1.31 1.21 1.16 1.79 1.77 1.44 0.24 0.15 1.12 0.07 0.06 2.22 1.25 1.38 2.60 0.17 0.19 1.54 1.03 1.01 1.81 0.04 0.05 0.27 0.26 0.25 0.32 0.00 0.00 0.13 0.02 0.02 0.04 0.01 0.01 0.01 0.19 0.18 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.91 0.92 0.37 0.01 0.00 0.11 0.10 0.04 0.01 0.02 0.02 0.01 0.88 0.98 0.07 0.95 0.95 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.03 0.00 0.90 0.03 0.04 0.98 0.00 0.08 0.06 0.11 0.14 0.00 0.00 0.00 0.00 0.01 0.01 0.00 2.00 1.92 7.94 1.89 1.85 7.99 255 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. SP 123 SP 123 ser1 TC 001 bt1 TC 001 TC 001 TC 002 chl2 chl1 chl2 chl1 clinochlore phlogopite phlogopite clinochlore clinochlore clinochlore vein biotie biotite biotite vein Yg Yg Kpd Kpd Kpd Kpd 27.88 36.58 29.61 26.62 26.64 27.23 0.09 3.07 0.15 0.16 0.02 0.00 19.55 14.61 20.36 20.03 19.99 20.19 0.01 0.02 0.02 0.01 0.00 0.00 3.85 4.10 4.58 3.74 4.04 3.77 19.65 14.76 16.50 19.05 20.61 19.20 15.12 11.76 13.68 15.97 15.44 16.79 0.55 0.30 0.84 1.06 1.07 1.00 0.02 0.03 0.10 0.11 0.03 0.03 0.01 0.09 0.12 0.01 0.02 0.04 0.37 9.24 1.44 0.08 0.03 0.03 11.46 3.63 3.51 11.43 11.47 11.56 0.04 0.44 0.25 0.00 0.00 0.18 0.00 0.06 0.00 0.01 0.02 0.00 98.60 98.69 91.18 98.28 99.36 100.01 -0.02 -0.20 -0.11 0.00 0.00 -0.08 98.58 98.49 91.07 98.28 99.36 99.93 2.91 2.85 2.44 2.79 2.78 2.80 1.09 1.15 1.56 1.21 1.22 1.20 1.32 0.19 0.43 1.27 1.25 1.25 2.35 1.36 1.68 2.50 2.41 2.58 1.72 0.96 1.14 1.67 1.80 1.65 0.30 0.24 0.28 0.29 0.32 0.29 0.05 0.02 0.06 0.09 0.09 0.09 0.01 0.18 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.25 0.05 0.00 0.16 0.13 0.14 0.00 0.01 0.02 0.00 0.00 0.01 0.05 0.92 0.15 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.95 0.07 0.82 0.97 0.99 0.99 0.01 0.11 0.07 0.00 0.00 0.06 0.00 0.01 0.00 0.00 0.00 0.00 7.99 1.88 1.93 8.00 8.00 7.94 256 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. TC 002 TC 004 bt1 TC 004 bt2 TC 004 bt3 TC 004 TC 006 bt1 ser1 chl1 muscovite phlogopite phlogopite phlogopite clinochlore phlogopite vein biotite Khbg Khbg Khbg Khbg Khbg Kpd 47.25 36.47 37.22 36.89 27.13 37.74 0.26 3.53 3.14 3.08 0.07 3.39 31.15 14.47 14.34 14.25 18.78 14.53 0.00 0.03 0.02 0.00 0.00 0.00 0.77 4.04 4.09 4.24 3.62 3.73 2.77 14.52 14.74 15.27 18.46 13.43 1.93 11.88 11.80 11.41 16.71 13.14 0.11 0.94 0.90 0.94 1.52 0.53 0.06 0.00 0.01 0.06 0.05 0.01 0.42 0.08 0.13 0.04 0.00 0.11 10.33 9.31 9.19 9.07 0.09 9.67 4.43 3.69 3.86 3.59 11.38 3.61 0.00 0.33 0.00 0.52 0.00 0.71 0.00 0.10 0.10 0.08 0.03 0.02 99.48 99.38 99.55 99.44 97.83 100.63 0.00 -0.16 -0.02 -0.24 -0.01 -0.31 99.48 99.22 99.52 99.20 97.83 100.32 3.20 2.82 2.87 2.86 2.86 2.86 0.80 1.18 1.13 1.14 1.14 1.14 1.68 0.14 0.17 0.17 1.19 0.16 0.19 1.37 1.36 1.32 2.62 1.48 0.16 0.94 0.95 0.99 1.63 0.85 0.04 0.24 0.24 0.25 0.29 0.21 0.01 0.06 0.06 0.06 0.14 0.03 0.01 0.21 0.18 0.18 0.01 0.19 0.00 0.00 0.00 0.00 0.00 0.00 0.91 0.04 0.05 0.03 0.14 0.07 0.05 0.01 0.02 0.01 0.00 0.02 0.89 0.92 0.90 0.90 0.01 0.93 0.00 0.00 0.00 0.01 0.01 0.00 0.05 0.07 0.08 0.09 0.98 0.05 0.00 0.08 0.00 0.13 0.00 0.17 0.00 0.01 0.01 0.01 0.00 0.00 2.00 1.91 1.99 1.86 8.00 1.83 257 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. TC 008 bt1 TC 008 bt2 TC 009 TC 010' ser1 TC 011 bt1 chl1 phlogopite phlogopite clinochlore alumino-celadonite phlogopite biotite plag Yg Yg Yg Yg Yg 35.71 36.41 32.76 50.17 36.86 2.81 2.10 0.00 0.05 3.63 17.37 16.82 16.91 24.36 13.88 0.00 0.02 0.03 0.03 0.03 4.19 4.14 2.10 1.14 3.81 15.10 14.90 10.72 4.09 13.73 9.66 10.01 20.56 4.20 12.96 0.61 0.64 1.04 0.12 0.56 0.00 0.06 0.52 0.48 0.02 0.05 0.10 0.06 0.30 0.08 9.52 9.29 0.01 8.09 9.29 3.38 3.25 11.88 4.18 3.67 0.99 1.26 0.00 0.36 0.42 0.04 0.04 0.02 0.01 0.04 99.44 99.04 96.61 97.59 98.99 -0.43 -0.54 0.00 -0.16 -0.19 99.01 98.51 96.61 97.43 98.80 2.77 2.83 3.31 3.46 2.85 1.23 1.17 0.69 0.54 1.15 0.36 0.38 1.32 1.43 0.11 1.12 1.16 3.09 0.43 1.49 0.98 0.97 0.91 0.24 0.89 0.25 0.24 0.16 0.06 0.22 0.04 0.04 0.09 0.01 0.04 0.16 0.12 0.00 0.00 0.21 0.00 0.00 0.00 0.00 0.00 0.09 0.08 0.43 0.83 0.04 0.01 0.02 0.01 0.04 0.01 0.94 0.92 0.00 0.71 0.91 0.00 0.01 0.06 0.04 0.00 0.05 0.06 0.93 0.21 0.07 0.24 0.31 0.00 0.08 0.10 0.00 0.01 0.00 0.00 0.01 1.75 1.69 8.00 1.92 1.89 258 Sample number Mineral name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) Table 4. Normalized microprobe data: sheet silicates from Tea Cup. TC 011 TV07 08 chl1 ser1 clinochlore chamosite biotite biotite Yg Yg 29.98 34.79 0.00 1.84 19.03 16.40 0.00 0.01 2.04 3.21 10.39 16.39 23.87 8.41 1.89 1.12 0.08 2.01 0.01 0.06 0.07 4.64 12.07 11.44 0.13 0.59 0.01 0.04 99.56 100.95 -0.06 -0.26 99.50 100.69 2.96 3.56 1.04 0.44 1.18 1.53 3.52 1.28 0.86 1.40 0.15 0.25 0.16 0.10 0.00 0.14 0.00 0.00 0.14 1.30 0.00 0.01 0.01 0.61 0.01 0.22 0.98 0.16 0.04 0.19 0.00 0.01 7.96 7.80 259 Table 5. Normalized microprobe data: epidote from Tea Cup Sample SP 004 SP 007 SP 007 SP 014 SP 029 SP 032 ep1 ep1 number ep3 ep1 ep2 ep2 Mineral name epidote epidote epidote epidote epidote epidote Replacing kspar kspar kspar vein kspar plg Host rock Yg Yg Yg Yg Yg Kpd SiO2 38.10 37.53 37.31 37.75 37.37 36.76 TiO2 0.31 0.21 0.11 0.08 0.03 0.08 Al2O3 23.52 21.19 20.01 22.29 23.53 24.02 Cr2O3 0.00 0.01 0.00 0.01 0.00 0.03 Fe2O3 12.01 15.07 16.75 13.87 12.90 11.92 FeO 0.21 0.28 0.59 0.24 0.53 0.45 MgO 0.06 0.01 0.00 0.00 0.03 0.04 MnO 0.21 0.27 0.59 0.24 0.53 0.45 CaO 23.42 22.96 22.53 23.21 23.00 22.83 Na2O 0.00 0.00 0.00 0.00 0.00 0.00 K2O 0.00 0.02 0.00 0.01 0.00 0.00 H2O 1.81 1.82 1.85 1.87 1.81 1.69 F 0.16 0.07 0.00 0.00 0.15 0.37 Cl 0.01 0.00 0.00 0.01 0.00 0.00 Subtotal 99.81 99.43 99.74 99.56 99.89 98.63 O=F+Cl -0.07 -0.03 0.00 0.00 -0.07 -0.16 Total 99.74 99.40 99.74 99.56 99.82 98.47 Si (T) 3.03 3.03 3.02 3.03 2.98 2.96 Al (T) 0.00 0.00 0.00 0.00 0.02 0.04 Al (Oct) 2.20 2.02 1.91 2.11 2.19 2.24 Mg (Oct) 0.01 0.00 0.00 0.00 0.00 0.01 Mn 2+ (Oct) 0.01 0.02 0.04 0.02 0.04 0.03 Mn 3+ (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 Fe 3+ (Oct) 0.73 0.93 1.06 0.85 0.81 0.75 Ti (Oct) 0.02 0.01 0.01 0.00 0.00 0.00 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 Na (A) 0.00 0.00 0.00 0.00 0.00 0.00 K (A) 0.00 0.00 0.00 0.00 0.00 0.00 Ca (A) 1.99 1.99 1.96 1.99 1.96 1.97 F (X) 0.04 0.02 0.00 0.00 0.04 0.09 Cl (X) 0.00 0.00 0.00 0.00 0.00 0.00 OH (X) 0.96 0.98 1.00 1.00 0.96 0.91 SP 097 ep1 epidote kspar Yg 36.90 0.12 23.65 0.08 12.71 0.48 0.11 0.48 22.56 0.00 0.00 1.79 0.15 0.01 99.04 -0.07 98.98 2.96 0.04 2.20 0.01 0.03 0.00 0.80 0.01 0.01 0.00 0.00 1.94 0.04 0.00 0.96 260 Table 5. Normalized microprobe data: epidote from Tea Cup Sample TV07 08 TC 001 TC 002 TC 009 TC 010' TC 010' ep2 ep1 ep1 ep1 ep2 ep1 number epidote epidote epidote epidote epidote Mineral name epidote kspar vein biotite plag quartz quartz Replacing Yg Kpd Kpd Yg Yg Yg Host rock 37.08 37.16 36.77 37.32 38.40 37.73 SiO2 0.08 0.01 0.29 0.14 0.01 0.02 TiO2 22.88 23.98 23.08 20.65 25.28 20.51 Al2O3 0.03 0.00 0.00 0.01 0.00 0.00 Cr2O3 14.04 12.46 12.90 16.56 9.96 15.93 Fe2O3 0.52 0.40 0.38 0.34 0.60 0.67 FeO 0.00 0.06 0.05 0.00 0.00 0.00 MgO 0.51 0.40 0.37 0.33 0.59 0.66 MnO 22.82 22.88 22.70 22.90 23.28 22.36 CaO 0.05 0.04 0.04 0.07 0.00 0.03 Na2O 0.00 0.00 0.02 0.00 0.00 0.01 K2O 1.80 1.67 1.78 1.73 1.90 1.79 H2O 0.15 0.43 0.14 0.29 0.01 0.15 F 0.00 0.00 0.02 0.00 0.01 0.00 Cl 99.95 99.50 98.54 100.35 100.04 99.84 Subtotal -0.06 -0.18 -0.06 -0.12 0.00 -0.06 O=F+Cl 99.89 99.32 98.48 100.23 100.03 99.78 Total 2.96 2.97 2.97 3.00 3.02 3.05 Si (T) 0.04 0.03 0.03 0.00 0.00 0.00 Al (T) 2.12 2.23 Al (Oct) 2.17 1.96 2.35 1.95 Mg (Oct) 0.00 0.01 0.01 0.00 0.00 0.00 Mn 2+ (Oct) 0.03 0.03 0.03 0.02 0.04 0.05 Mn 3+ (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 Fe 3+ (Oct) 0.88 0.78 0.81 1.02 0.63 1.01 Ti (Oct) 0.00 0.00 0.02 0.01 0.00 0.00 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 Na (A) 0.01 0.01 0.01 0.01 0.00 0.00 K (A) 0.00 0.00 0.00 0.00 0.00 0.00 Ca (A) 1.95 1.96 1.97 1.97 1.96 1.93 F (X) 0.04 0.11 0.04 0.07 0.00 0.04 Cl (X) 0.00 0.00 0.00 0.00 0.00 0.00 OH (X) 0.96 0.89 0.96 0.93 1.00 0.96 261 Table 6. Normalized microprobe data: amphibole from Tea Cup Sample SP 007 act2 SP 007 chl1 TC 006 amph1 TC 006 amph2 Mineral Name actinolite actinolite actinolite actinolite Replacing biotite quartz biotite biotite Host rock Yg Yg Yg Yg SiO2 50.82 53.51 50.00 50.44 TiO2 0.64 0.06 0.59 0.64 Al2O3 4.86 1.96 5.21 4.87 Cr2O3 0.02 0.00 0.01 0.01 Fe2O3 5.54 3.50 5.40 4.90 FeO 7.62 7.62 8.44 8.47 MgO 15.18 13.96 14.50 14.79 MnO 0.82 4.57 0.81 0.81 CaO 11.68 11.71 11.61 11.72 Na2O 0.92 0.22 0.97 0.96 K2O 0.42 0.15 0.50 0.37 H2O 1.99 1.96 2.07 2.08 F 0.22 0.22 0.00 0.00 Cl 0.01 0.01 0.01 0.00 Subtotal 100.74 99.45 100.12 100.07 O=F+Cl -0.10 -0.09 0.00 0.00 Total 100.65 99.36 100.12 100.07 Si (T) Al (T) Al (6) Fe 3+ (6) Ti (6) Cr (6) Mg (8) Fe 2+ (8) Mn (8) Ca (8) Na (A) K (A) vac. F Cl OH 7.27 0.73 0.09 3.24 0.91 0.60 0.10 0.07 0.00 1.79 0.26 0.08 0.67 0.10 0.00 1.90 7.77 0.23 0.10 3.02 0.93 0.38 0.56 0.01 0.00 1.82 0.06 0.03 0.91 0.10 0.00 1.90 7.22 0.78 0.11 3.12 1.02 0.59 0.10 0.06 0.00 1.80 0.27 0.09 0.64 0.00 0.00 2.00 7.27 0.73 0.10 3.18 1.02 0.53 0.10 0.07 0.00 1.81 0.27 0.07 0.66 0.00 0.00 2.00 262 Table 6. Normalized microprobe data: amphibole from Tea Cup Sample TC 011 act1 TC 011 act2 Mineral Name actinolite actinolite Replacing biotite biotite Host rock Yg Yg SiO2 48.97 51.46 TiO2 0.79 0.35 Al2O3 5.95 4.18 Cr2O3 0.01 0.04 Fe2O3 5.29 4.54 FeO 8.96 7.91 MgO 14.06 15.45 MnO 0.72 0.73 CaO 11.76 12.04 Na2O 0.99 0.53 K2O 0.51 0.29 H2O 1.96 1.92 F 0.21 0.35 Cl 0.03 0.00 Subtotal 100.21 99.80 O=F+Cl -0.09 -0.15 Total 100.12 99.65 Si (T) Al (T) Al (6) Fe 3+ (6) Ti (6) Cr (6) Mg (8) Fe 2+ (8) Mn (8) Ca (8) Na (A) K (A) vac. F Cl OH 7.10 0.90 0.12 3.04 1.09 0.58 0.09 0.09 0.00 1.83 0.28 0.10 0.63 0.09 0.01 1.90 7.40 0.60 0.11 3.31 0.95 0.49 0.09 0.04 0.00 1.86 0.15 0.05 0.80 0.16 0.00 1.84 263 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 005a EP 005a EP 005a number kspar1 kspar2 plg1 Replacing Host Rock Tpd Tpd Tpd SiO2 64.60 65.02 66.74 Al2O3 18.85 18.73 21.65 TiO2 0.05 0.00 0.04 Cr2O3 0.00 0.03 0.01 Fe2O3 0.00 0.05 0.00 FeO 0.00 0.00 0.07 MgO 0.00 0.00 0.01 MnO 0.01 0.00 0.00 CaO 0.00 0.00 2.02 Na2O 0.85 1.23 11.23 K2O 15.28 14.78 0.17 F 0.08 0.00 0.00 Cl 0.00 0.00 0.00 Total 99.69 99.84 101.94 Based on IV=4 Si 2.98 2.98 2.89 Al 1.02 1.01 1.11 Fe3+ 0.00 0.00 0.00 Na 0.08 0.11 0.94 K 0.90 0.87 0.01 Ca 0.00 0.00 0.09 Mg 0.00 0.00 0.00 Ti 0.00 0.00 0.00 Cr 0.00 0.00 0.00 Mn 0.00 0.00 0.00 F 0.01 0.00 0.00 Cl 0.00 0.00 0.00 O 7.99 8.00 8.00 End Member Or # 0.92 0.89 0.01 An # 0.00 0.00 0.09 Ab # 0.08 0.11 0.90 EP 006 kspar1 EP 006 kspar2 EP 006 plg1 EP 007 kspar1 Yg 65.65 18.60 0.03 0.01 0.10 0.00 0.00 0.00 0.00 0.95 15.18 0.00 0.02 100.54 Yg 65.42 18.71 0.00 0.00 0.00 0.02 0.00 0.00 0.00 1.34 15.21 0.47 0.01 100.98 Yg 65.66 21.48 0.04 0.00 0.09 0.00 0.00 0.00 2.25 9.88 0.33 0.00 0.00 99.72 Tpd 64.63 18.36 0.00 0.01 0.00 0.18 0.00 0.00 0.00 0.47 15.80 0.39 0.00 99.68 2.99 1.00 0.00 0.08 0.88 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.99 1.01 0.00 0.12 0.89 0.00 0.00 0.00 0.00 0.00 0.07 0.00 7.93 2.88 1.11 0.00 0.84 0.02 0.11 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.99 1.01 0.00 0.04 0.93 0.00 0.00 0.00 0.00 0.00 0.06 0.00 7.94 0.91 0.00 0.09 0.88 0.00 0.12 0.02 0.11 0.87 0.96 0.00 0.04 264 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 007 number plg1 Replacing kspar Host Rock Tpd SiO2 58.07 Al2O3 25.99 TiO2 0.00 Cr2O3 0.00 Fe2O3 0.28 FeO 0.00 MgO 0.01 MnO 0.00 CaO 7.80 Na2O 6.89 K2O 0.13 F 0.00 Cl 0.00 Total 99.15 Based on IV=4 2.61 Si 1.38 Al 0.01 Fe3+ 0.60 Na 0.01 K Ca 0.38 Mg 0.00 Ti 0.00 Cr 0.00 Mn 0.00 F 0.00 Cl 0.00 O 8.00 End Member Or # 0.01 An # 0.38 Ab # 0.61 EP 016 kspar1 EP 016 plg1 EP 016 ser1 EP 017a EP 017a EP 017c kspar1 kspar2 plg1 Yg 65.52 18.41 0.00 0.01 0.12 0.00 0.00 0.01 0.01 0.53 15.62 0.01 0.01 100.23 Yg 68.03 20.07 0.00 0.00 0.00 0.00 0.01 0.00 0.32 11.73 0.08 0.00 0.00 100.25 Yg 63.31 19.65 0.12 0.01 0.94 0.00 0.16 0.03 0.00 0.48 15.64 0.00 0.00 100.34 Tpd 65.43 18.80 0.05 0.00 0.00 0.08 0.00 0.01 0.06 1.71 14.19 0.46 0.01 100.60 Tpd 64.54 18.46 0.04 0.00 0.63 0.00 0.00 0.01 0.00 0.39 15.95 0.00 0.01 100.02 Tpd 55.74 27.65 0.04 0.02 0.32 0.00 0.02 0.01 9.78 5.59 0.30 0.00 0.00 99.47 3.00 0.99 0.00 0.05 0.91 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.03 0.00 0.99 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.90 1.07 0.03 0.04 0.91 0.00 0.01 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 0.15 0.83 0.00 0.00 0.00 0.00 0.00 0.07 0.00 7.93 2.97 1.00 0.02 0.03 0.94 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.52 1.47 0.01 0.49 0.02 0.47 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.95 0.00 0.05 0.00 0.01 0.98 0.96 0.00 0.04 0.84 0.00 0.15 0.96 0.00 0.04 0.02 0.48 0.50 265 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 017c number plg2 Replacing Host Rock Tpd SiO2 62.54 Al2O3 23.27 TiO2 0.00 Cr2O3 0.00 Fe2O3 0.00 FeO 0.00 MgO 0.00 MnO 0.00 CaO 4.44 Na2O 8.64 K2O 0.08 F 0.00 Cl 0.00 Total 98.97 Based on IV=4 2.78 Si 1.22 Al 0.00 Fe3+ 0.74 Na 0.00 K Ca 0.21 Mg 0.00 Ti 0.00 Cr 0.00 Mn 0.00 F 0.00 Cl 0.00 O 8.00 End Member Or # 0.00 An # 0.22 Ab # 0.78 EP 021 kspar1 Yg 65.62 18.61 0.02 0.01 0.06 0.00 0.01 0.00 0.00 0.53 15.71 0.15 0.00 100.66 EP 021 plg1 kspar Yg 68.13 19.64 0.04 0.00 0.05 0.00 0.00 0.00 0.07 11.62 0.08 0.00 0.00 99.63 EP 022a EP 022b EP 022b EP 024 plg1 plg1 plg2 kspar1 plag Yg Yg Yg Yg 68.86 69.22 68.56 64.79 19.91 19.77 19.91 18.75 0.02 0.02 0.05 0.00 0.00 0.00 0.01 0.02 0.00 0.13 0.02 0.06 0.10 0.00 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.01 0.02 0.02 0.29 0.09 0.24 0.00 11.92 11.09 11.29 0.79 0.09 0.35 0.25 15.31 0.00 0.00 0.00 0.17 0.00 0.00 0.00 0.01 101.20 100.71 100.34 99.84 3.00 1.00 0.00 0.05 0.91 0.00 0.00 0.00 0.00 0.00 0.02 0.00 7.98 2.98 1.01 0.00 0.99 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 1.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.99 1.01 0.00 0.93 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 0.95 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 0.07 0.90 0.00 0.00 0.00 0.00 0.00 0.02 0.00 7.98 0.95 0.00 0.05 0.00 0.00 0.99 0.01 0.01 0.98 0.02 0.00 0.98 0.01 0.01 0.97 0.93 0.00 0.07 266 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 024 number plg1 Replacing Host Rock Yg SiO2 64.33 Al2O3 22.56 TiO2 0.00 Cr2O3 0.00 Fe2O3 0.00 FeO 0.05 MgO 0.00 MnO 0.01 CaO 3.46 Na2O 9.77 K2O 0.09 F 0.30 Cl 0.01 Total 100.45 Based on IV=4 2.83 Si 1.17 Al 0.00 Fe3+ 0.83 Na 0.01 K Ca 0.16 Mg 0.00 Ti 0.00 Cr 0.00 Mn 0.00 F 0.04 Cl 0.00 O 7.96 End Member Or # 0.01 An # 0.16 Ab # 0.83 EP 033 plg1 EP 033 plg2 EP 034 plg1 EP 034 EP 035b EP 035b plg2 kspar1 plg1 Yg 68.54 19.79 0.05 0.02 0.00 0.00 0.00 0.01 0.20 11.44 0.04 0.00 0.00 100.09 Yg 68.42 20.09 0.03 0.00 0.00 0.06 0.01 0.00 0.38 11.97 0.06 0.00 0.00 101.03 Yg 67.37 20.77 0.00 0.00 0.23 0.00 0.05 0.00 0.74 11.08 0.37 0.00 0.00 100.61 Yg 67.72 19.58 0.00 0.00 0.00 0.03 0.00 0.02 0.03 11.93 0.06 0.00 0.00 99.36 Yg 64.40 18.82 0.00 0.03 0.03 0.00 0.01 0.00 0.00 0.45 15.81 0.00 0.01 99.55 Yg 68.16 20.39 0.02 0.00 0.14 0.00 0.03 0.00 1.00 10.86 0.29 0.00 0.00 100.89 2.98 1.02 0.00 0.97 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.03 0.00 1.01 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.93 1.06 0.01 0.93 0.02 0.03 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 1.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.03 0.00 0.04 0.93 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.95 1.04 0.00 0.91 0.02 0.05 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.00 0.01 0.99 0.00 0.02 0.98 0.02 0.04 0.94 0.00 0.00 1.00 0.96 0.00 0.04 0.02 0.05 0.94 267 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 035b EP 037 number plg2 plg1 Replacing kspar Host Rock Yg Tpd SiO2 61.78 66.20 Al2O3 23.50 20.64 TiO2 0.00 0.00 Cr2O3 0.00 0.00 Fe2O3 0.02 0.00 FeO 0.00 0.13 MgO 0.00 0.00 MnO 0.01 0.00 CaO 4.80 1.39 Na2O 8.78 11.42 K2O 0.16 0.06 F 0.00 0.00 Cl 0.00 0.00 Total 99.06 99.83 Based on IV=4 2.76 2.92 Si 1.24 1.08 Al 0.00 0.00 Fe3+ 0.76 0.98 Na 0.01 K 0.00 Ca 0.23 0.07 Mg 0.00 0.00 Ti 0.00 0.00 Cr 0.00 0.00 Mn 0.00 0.00 F 0.00 0.00 Cl 0.00 0.00 O 8.00 8.00 End Member Or # 0.01 0.00 An # 0.23 0.06 Ab # 0.76 0.93 EP 038a EP 038a EP 038a EP 038a EP 038a kspar1 kspar2 plg1 plg2 plg3 Tpd 63.81 18.69 0.00 0.03 0.03 0.00 0.00 0.00 0.00 0.59 15.67 0.00 0.00 98.82 Tpd 63.71 18.69 0.04 0.06 0.10 0.00 0.00 0.00 0.00 0.69 15.31 0.00 0.01 98.60 Tpd 76.31 14.81 0.17 0.00 0.28 0.00 0.04 0.03 1.98 6.51 0.17 0.00 0.00 100.30 Tpd 56.90 27.28 0.07 0.00 0.31 0.00 0.01 0.00 8.91 6.34 0.18 0.00 0.00 100.01 Tpd 57.28 26.32 0.02 0.00 0.43 0.00 0.01 0.00 8.17 6.83 0.11 0.00 0.00 99.18 2.97 1.03 0.00 0.05 0.93 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.03 0.00 0.06 0.91 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 3.24 0.75 0.01 0.54 0.01 0.09 0.00 0.01 0.00 0.00 0.00 0.00 8.00 2.55 1.44 0.01 0.55 0.01 0.43 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.58 1.40 0.01 0.60 0.01 0.40 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.95 0.00 0.05 0.94 0.00 0.06 0.01 0.14 0.84 0.01 0.43 0.56 0.01 0.40 0.60 268 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 038c EP 038c number kspar2 plg1 Replacing plag Host Rock Yg Yg SiO2 64.72 58.77 Al2O3 18.87 25.01 TiO2 0.03 0.00 Cr2O3 0.00 0.00 Fe2O3 0.39 0.33 FeO 0.00 0.00 MgO 0.00 0.00 MnO 0.01 0.00 CaO 0.00 6.50 Na2O 0.72 7.43 K2O 15.43 0.26 F 0.25 0.00 Cl 0.00 0.00 Total 100.32 98.30 Based on IV=4 2.97 2.66 Si 1.02 1.33 Al 0.01 0.01 Fe3+ 0.06 0.65 Na 0.90 K 0.01 Ca 0.00 0.31 Mg 0.00 0.00 Ti 0.00 0.00 Cr 0.00 0.00 Mn 0.00 0.00 F 0.04 0.00 Cl 0.00 0.00 O 7.96 8.00 End Member Or # 0.93 0.02 An # 0.00 0.32 Ab # 0.07 0.66 EP 040 kspar 1 EP 040 kspar2 EP 040 plg3 plag Yxm 67.23 20.29 0.04 0.02 0.03 0.00 0.01 0.02 0.38 11.09 0.33 0.00 0.00 99.44 EP 042 kspar1 Yxm 64.33 18.70 0.00 0.01 0.00 0.07 0.00 0.00 0.00 0.56 16.18 0.16 0.00 99.93 EP 040 plg2 kspar Yxm 67.86 20.26 0.05 0.01 0.03 0.00 0.00 0.00 0.63 11.19 0.14 0.00 0.00 100.17 Yxm 64.97 18.55 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.46 15.66 0.07 0.01 99.71 2.99 1.01 0.00 0.04 0.92 0.00 0.00 0.00 0.00 0.00 0.01 0.00 7.99 2.98 1.02 0.00 0.05 0.96 0.00 0.00 0.00 0.00 0.00 0.02 0.00 7.98 2.96 1.04 0.00 0.95 0.01 0.03 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.95 1.05 0.00 0.94 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.02 0.00 0.05 0.93 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.96 0.00 0.04 0.95 0.00 0.05 0.01 0.03 0.96 0.02 0.02 0.96 0.95 0.00 0.05 Yxm 64.23 18.78 0.01 0.00 0.04 0.00 0.00 0.00 0.00 0.51 15.82 0.00 0.01 99.39 269 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 042 number kspar2 Replacing Host Rock Yxm SiO2 64.82 Al2O3 18.97 TiO2 0.00 Cr2O3 0.00 Fe2O3 0.00 FeO 0.00 MgO 0.00 MnO 0.00 CaO 0.00 Na2O 2.00 K2O 13.66 F 0.08 Cl 0.01 Total 99.52 Based on IV=4 2.97 Si 1.03 Al 0.00 Fe3+ 0.18 Na 0.80 K Ca 0.00 Mg 0.00 Ti 0.00 Cr 0.00 Mn 0.00 F 0.01 Cl 0.00 O 7.99 End Member Or # 0.82 An # 0.00 Ab # 0.18 EP 042 plg1 EP 046 kspar2 EP 070 kspar1 EP 070 kspar2 EP 070 plg1 Yxm 67.02 20.12 0.00 0.00 0.02 0.00 0.00 0.00 0.67 11.04 0.07 0.00 0.00 98.94 EP 042 plg2 kspar Yxm 67.58 19.84 0.00 0.01 0.00 0.03 0.00 0.00 0.46 11.58 0.11 0.00 0.00 99.62 Yg 65.21 18.34 0.00 0.01 0.12 0.00 0.00 0.00 0.00 0.38 16.23 0.01 0.00 100.31 Yg 64.69 18.59 0.04 0.02 0.00 0.07 0.00 0.00 0.00 0.74 15.54 0.32 0.02 99.90 Yg 64.71 18.58 0.05 0.02 0.27 0.00 0.00 0.02 0.00 0.41 16.14 0.02 0.04 100.23 Yg 69.34 19.82 0.00 0.03 0.04 0.05 0.01 0.00 0.21 11.76 0.15 0.00 0.02 101.42 2.95 1.05 0.00 0.94 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.97 1.03 0.00 0.99 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00 8.00 3.00 1.00 0.00 0.03 0.95 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 0.07 0.91 0.00 0.00 0.00 0.00 0.00 0.05 0.00 7.95 2.98 1.01 0.01 0.04 0.95 0.00 0.00 0.00 0.00 0.00 0.00 0.00 7.99 2.99 1.01 0.00 0.98 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 8.00 0.00 0.03 0.96 0.01 0.02 0.97 0.97 0.00 0.03 0.93 0.00 0.07 0.96 0.00 0.04 0.01 0.01 0.98 270 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 070 number plg3 Replacing Host Rock Yg SiO2 69.00 Al2O3 19.41 TiO2 0.00 Cr2O3 0.02 Fe2O3 0.00 FeO 0.13 MgO 0.00 MnO 0.00 CaO 0.15 Na2O 11.72 K2O 0.17 F 0.00 Cl 0.00 Total 100.59 Based on IV=4 3.00 Si 1.00 Al 0.00 Fe3+ 0.99 Na 0.01 K Ca 0.01 Mg 0.00 Ti 0.00 Cr 0.00 Mn 0.00 F 0.00 Cl 0.00 O 8.00 End Member Or # 0.01 An # 0.01 Ab # 0.98 EP 086 kspar1 EP 086 kspar2 EP 086 kspar3 EP 086 plg1 EP 086 plg2 EP 086 plg3 Yg 63.92 18.63 0.00 0.00 0.06 0.00 0.00 0.00 0.00 1.11 14.94 0.00 0.02 98.67 Yg 64.79 18.75 0.07 0.00 0.00 0.01 0.00 0.00 0.00 1.14 15.05 0.30 0.00 100.00 Yg 63.34 18.64 0.00 0.00 0.08 0.00 0.00 0.00 0.00 0.77 15.20 0.30 0.00 98.20 Yg 65.30 22.89 0.00 0.00 0.00 0.03 0.00 0.00 3.65 10.21 0.13 0.00 0.01 102.22 Yg 65.36 22.50 0.00 0.02 0.00 0.03 0.00 0.02 3.47 9.79 0.08 0.47 0.01 101.54 Yg 64.87 22.36 0.05 0.02 0.00 0.03 0.00 0.04 3.40 9.89 0.16 0.25 0.01 100.97 2.98 1.02 0.00 0.10 0.89 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.98 1.02 0.00 0.10 0.88 0.00 0.00 0.00 0.00 0.00 0.04 0.00 7.96 2.97 1.03 0.00 0.07 0.91 0.00 0.00 0.00 0.00 0.00 0.04 0.00 7.96 2.83 1.17 0.00 0.86 0.01 0.17 0.00 0.00 0.00 0.00 0.00 0.00 8.00 2.84 1.16 0.00 0.83 0.00 0.16 0.00 0.00 0.00 0.00 0.06 0.00 7.94 2.84 1.16 0.00 0.84 0.01 0.16 0.00 0.00 0.00 0.00 0.04 0.00 7.96 0.90 0.00 0.10 0.90 0.00 0.10 0.93 0.00 0.07 0.01 0.16 0.83 0.00 0.16 0.83 0.01 0.16 0.83 271 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample EP 086 MW 001 MW 001 MW ALT5' MW NACA2 MW NACA3 number plg4 plg1 plg2 plg1 plg1 plg1 Replacing kspar kspar kspar kspar kspar Host Rock Yg Yg Yg Yg Yg Yg SiO2 61.91 68.33 69.14 66.65 67.61 67.27 Al2O3 24.35 19.71 19.67 21.06 20.62 21.00 TiO2 0.04 0.00 0.00 0.00 0.06 0.00 Cr2O3 0.00 0.00 0.01 0.00 0.05 0.00 Fe2O3 0.00 0.34 0.04 0.08 0.00 0.01 FeO 0.06 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 0.00 0.00 MnO 0.00 0.00 0.00 0.00 0.00 0.01 CaO 5.57 0.08 0.13 1.49 0.85 1.05 Na2O 8.61 11.52 11.12 10.78 11.60 11.18 K2O 0.21 0.00 0.06 0.12 0.10 0.09 F 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.00 0.00 0.00 0.00 0.01 0.01 Total 100.75 99.99 100.18 100.19 100.90 100.62 Based on IV=4 2.73 2.98 2.99 2.91 2.94 2.92 Si 1.27 1.01 1.00 1.08 1.06 1.08 Al 0.00 0.01 0.00 0.00 0.00 0.00 Fe3+ 0.74 0.97 0.93 0.91 0.98 0.94 Na 0.01 0.00 0.00 0.01 0.01 0.00 K 0.26 0.00 0.01 0.07 0.04 0.05 Ca 0.00 0.00 0.00 0.00 0.00 0.00 Mg Ti 0.00 0.00 0.00 0.00 0.00 0.00 Cr 0.00 0.00 0.00 0.00 0.00 0.00 Mn 0.00 0.00 0.00 0.00 0.00 0.00 F 0.00 0.00 0.00 0.00 0.00 0.00 Cl 0.00 0.00 0.00 0.00 0.00 0.00 O 8.00 8.00 8.00 8.00 8.00 8.00 End Member Or # 0.01 0.00 0.00 0.01 0.01 0.00 An # 0.26 0.00 0.01 0.07 0.04 0.05 Ab # 0.73 1.00 0.99 0.92 0.96 0.95 272 Table 7. Normalized microprobe data: feldspars from Eagle Pass. Sample MW SPECHEM number plg1 Replacing Host Rock Yg SiO2 68.71 Al2O3 19.80 TiO2 0.00 Cr2O3 0.00 Fe2O3 0.18 FeO 0.00 MgO 0.11 MnO 0.00 CaO 0.29 Na2O 11.42 K2O 0.10 F 0.00 Cl 0.00 Total 100.61 Based on IV=4 2.98 Si 1.01 Al 0.01 Fe3+ 0.96 Na 0.01 K 0.01 Ca 0.01 Mg Ti 0.00 0.00 Cr Mn 0.00 F 0.00 Cl 0.00 O 8.00 End Member Or # 0.01 An # 0.01 Ab # 0.98 273 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 005a EP 006 bt1 EP 006 bt2 EP 006 ser1 EP 007 bt1 bt1 Mineral Name annite annite annite alumino-celadonite phlogopite Replacing biotite Host Rock Tpd Tpd Tpd Yg Tpd SiO2 36.72 37.36 36.98 46.41 38.11 TiO2 2.04 0.08 0.10 0.22 1.92 Al2O3 16.30 21.20 19.71 28.65 15.32 Cr2O3 0.00 0.01 0.01 0.00 0.13 Fe2O3 4.54 4.40 4.73 1.23 3.38 FeO 16.34 15.83 17.02 4.43 12.16 MgO 8.37 6.06 6.34 2.39 13.40 MnO 1.04 0.45 0.46 0.10 0.15 CaO 0.01 0.33 0.34 0.00 0.09 Na2O 0.08 0.09 0.04 0.12 0.02 K2O 9.48 3.43 4.19 10.48 8.23 H2O 3.05 3.80 3.58 4.12 3.89 F 1.60 0.00 0.37 0.40 0.00 Cl 0.05 0.00 0.02 0.02 0.04 Subtotal 99.62 93.01 93.88 98.58 96.86 O=F+Cl -0.68 0.00 -0.16 -0.17 -0.01 Total 98.93 93.01 93.72 98.41 96.85 Si (T) 2.88 2.95 2.95 3.22 2.93 Al (T) 1.12 1.05 1.05 0.78 1.07 Al (Oct) 0.39 0.92 0.80 1.57 0.31 Mg (Oct) 0.98 0.71 0.75 0.25 1.53 Fe 2+ (Oct) 1.07 1.05 1.14 0.26 0.78 Fe 3+ (Oct) 0.27 0.26 0.28 0.06 0.20 Mn (Oct) 0.07 0.03 0.03 0.01 0.01 Ti (Oct) 0.12 0.00 0.01 0.01 0.11 Cr (Oct) 0.00 0.00 0.00 0.00 0.01 vacant (Oct) 0.10 0.02 0.00 0.85 0.05 Na (A) 0.01 0.01 0.01 0.02 0.00 K (A) 0.95 0.35 0.43 0.93 0.81 Ca (A) 0.00 0.03 0.03 0.00 0.01 vacant (A) 0.04 0.61 0.54 0.06 0.18 F (X) 0.40 0.00 0.09 0.09 0.00 Cl (X) 0.01 0.00 0.00 0.00 0.01 OH (X) 1.60 2.00 1.90 1.91 1.99 274 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 007 bt2 EP 016 bt1 EP 017a EP 017a EP 017c EP 017c bt1 bt2 bt1 bt2 Mineral Name phlogopite phlogopite phlogopite phlogopite phlogopite phlogopite Replacing biotite biotite biotite biotite Host Rock Tpd Yg Tpd Tpd Tpd Tpd SiO2 38.45 38.67 37.16 37.59 36.14 36.15 TiO2 1.76 2.23 0.30 0.36 1.31 3.39 Al2O3 14.72 15.07 16.57 16.82 17.11 17.16 Cr2O3 0.85 0.01 0.00 0.00 0.00 0.00 Fe2O3 3.15 3.55 3.31 3.32 3.84 3.98 FeO 11.32 12.78 11.90 11.95 13.81 14.34 MgO 13.92 12.75 12.70 13.01 11.69 10.17 MnO 0.17 0.26 0.66 0.69 0.30 0.29 CaO 0.09 0.05 0.16 0.17 0.16 0.00 Na2O 0.00 0.12 0.05 0.11 0.04 0.10 K2O 7.73 9.57 8.11 8.31 9.45 9.22 H2O 3.71 3.57 2.88 2.98 3.57 3.87 F 0.39 0.79 1.98 1.88 0.59 0.00 Cl 0.04 0.02 0.02 0.02 0.01 0.06 Subtotal 96.31 99.43 95.78 97.20 98.01 98.72 O=F+Cl -0.17 -0.34 -0.84 -0.80 -0.25 -0.01 Total 96.13 99.10 94.94 96.40 97.76 98.70 Si (T) 2.95 2.94 2.92 2.91 2.81 2.79 Al (T) 1.05 1.06 1.08 1.09 1.19 1.21 Al (Oct) 0.29 0.28 0.45 0.44 0.38 0.35 Mg (Oct) 1.59 1.44 1.49 1.50 1.36 1.17 Fe 2+ (Oct) 0.73 0.81 0.78 0.77 0.90 0.92 Fe 3+ (Oct) 0.18 0.20 0.20 0.19 0.22 0.23 Mn (Oct) 0.01 0.02 0.04 0.04 0.02 0.02 Ti (Oct) 0.10 0.13 0.02 0.02 0.08 0.20 Cr (Oct) 0.05 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.04 0.11 0.03 0.03 0.05 0.11 Na (A) 0.00 0.02 0.01 0.02 0.01 0.01 K (A) 0.76 0.93 0.81 0.82 0.94 0.91 Ca (A) 0.01 0.00 0.01 0.01 0.01 0.00 vacant (A) 0.23 0.05 0.17 0.15 0.04 0.08 F (X) 0.09 0.19 0.49 0.46 0.15 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 0.01 OH (X) 1.90 1.81 1.51 1.54 1.85 1.99 275 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 017c ser1 EP 021 ser1 EP 021 EP 022a bt1 ser2 Mineral Name alumino-celadonite alumino-celadonite muscovite phlogopite Replacing biotite plag plag Host Rock Tpd Yg Yg Yg SiO2 45.92 48.58 45.00 37.89 TiO2 0.58 0.08 0.03 1.35 Al2O3 28.95 27.32 33.83 15.23 Cr2O3 0.03 0.00 0.02 0.01 Fe2O3 1.19 1.23 0.94 4.16 FeO 4.28 4.44 3.40 14.98 MgO 2.52 2.33 0.46 11.06 MnO 0.03 0.03 0.00 0.38 CaO 0.04 0.00 0.00 0.11 Na2O 0.23 0.21 0.24 0.07 K2O 10.74 10.84 10.62 8.78 H2O 4.23 4.25 4.38 3.12 F 0.21 0.24 0.00 1.54 Cl 0.01 0.02 0.00 0.00 Subtotal 98.97 99.56 98.93 98.68 O=F+Cl -0.09 -0.10 0.00 -0.65 Total 98.88 99.46 98.93 98.03 Si (T) 3.18 3.33 3.08 2.95 Al (T) 0.82 0.67 0.92 1.05 Al (Oct) 1.54 1.54 1.81 0.34 Mg (Oct) 0.26 0.24 0.05 1.28 Fe 2+ (Oct) 0.25 0.25 0.19 0.97 Fe 3+ (Oct) 0.06 0.06 0.05 0.24 Mn (Oct) 0.00 0.00 0.00 0.02 Ti (Oct) 0.03 0.00 0.00 0.08 Cr (Oct) 0.00 0.00 0.00 0.00 vacant (Oct) 0.85 0.90 0.90 0.05 Na (A) 0.03 0.03 0.03 0.01 K (A) 0.95 0.95 0.93 0.87 Ca (A) 0.00 0.00 0.00 0.01 vacant (A) 0.02 0.02 0.04 0.11 F (X) 0.05 0.05 0.00 0.38 Cl (X) 0.00 0.00 0.00 0.00 OH (X) 1.95 1.95 2.00 1.62 276 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 022a EP 022a EP 022a EP 022b EP 022b EP 022b bt2 bt3 bt4 bt1 ser1 ser2 Mineral Name phlogopite phlogopite phlogopite phlogopite muscovite muscovite Replacing biotite biotite biotite plag biotite Host Rock Yg Yg Yg Yg Yg Yg SiO2 36.70 37.47 37.79 37.31 47.37 47.61 TiO2 1.54 1.60 0.16 1.98 0.10 0.51 Al2O3 16.39 15.88 17.07 17.03 34.92 29.27 Cr2O3 0.03 0.02 0.00 0.00 0.00 0.00 Fe2O3 4.38 4.28 3.94 3.81 0.35 1.05 FeO 15.77 15.40 14.19 13.70 1.28 3.77 MgO 10.14 10.86 11.54 11.56 0.68 1.84 MnO 0.41 0.44 0.39 0.35 0.05 0.04 CaO 0.05 0.06 0.11 0.00 0.01 0.00 Na2O 0.05 0.07 0.08 0.03 0.27 0.20 K2O 9.23 9.15 8.23 9.74 9.93 10.55 H2O 3.77 3.76 3.60 3.62 4.47 4.39 F 0.15 0.25 0.59 0.64 0.08 0.00 Cl 0.03 0.01 0.01 0.03 0.01 0.01 Subtotal 98.63 99.25 97.72 99.80 99.52 99.24 O=F+Cl -0.07 -0.11 -0.25 -0.28 -0.04 0.00 Total 98.56 99.15 97.47 99.52 99.48 99.24 Si (T) 2.86 2.89 2.92 2.84 3.15 3.25 Al (T) 1.14 1.11 1.08 1.16 0.85 0.75 Al (Oct) 0.37 0.34 0.48 0.37 1.88 1.61 Mg (Oct) 1.18 1.25 1.33 1.31 0.07 0.19 Fe 2+ (Oct) 1.03 0.99 0.92 0.87 0.07 0.22 Fe 3+ (Oct) 0.26 0.25 0.23 0.22 0.02 0.05 Mn (Oct) 0.03 0.03 0.03 0.02 0.00 0.00 Ti (Oct) 0.09 0.09 0.01 0.11 0.00 0.03 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.05 0.05 0.01 0.09 0.95 0.90 Na (A) 0.01 0.01 0.01 0.00 0.04 0.03 K (A) 0.92 0.90 0.81 0.95 0.84 0.92 Ca (A) 0.00 0.00 0.01 0.00 0.00 0.00 vacant (A) 0.07 0.08 0.17 0.05 0.12 0.05 F (X) 0.04 0.06 0.14 0.15 0.02 0.00 Cl (X) 0.00 0.00 0.00 0.00 0.00 0.00 OH (X) 1.96 1.94 1.86 1.84 1.98 2.00 277 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 024 bt1 EP 024 bt2 EP 024 bt3 EP 033 EP 033 EP 033 ser1 ser2 ser3 Mineral Name annite annite annite muscovite muscovite muscovite Replacing biotite biotite plag plag plag Host Rock Yg Yg Yg Yg Yg Yg SiO2 35.50 35.67 36.86 47.08 49.58 48.06 TiO2 3.41 2.63 0.42 0.29 0.23 0.15 Al2O3 14.55 15.41 19.55 29.82 27.84 28.91 Cr2O3 0.01 0.03 0.01 0.05 0.02 0.00 Fe2O3 5.36 5.29 4.56 0.90 1.08 1.03 FeO 19.28 19.06 16.41 3.23 3.88 3.71 MgO 7.73 8.31 6.38 1.60 2.13 2.09 MnO 0.46 0.24 0.49 0.05 0.02 0.02 CaO 0.00 0.07 0.20 0.00 0.00 0.02 Na2O 0.21 0.07 0.45 0.14 0.11 0.13 K2O 9.39 9.04 8.12 9.52 10.42 10.04 H2O 3.48 3.58 3.80 4.30 4.18 4.08 F 0.55 0.40 0.00 0.08 0.52 0.63 Cl 0.09 0.07 0.07 0.00 0.00 0.00 Subtotal 100.02 99.86 97.33 97.05 100.00 98.87 O=F+Cl -0.25 -0.18 -0.02 -0.03 -0.22 -0.27 Total 99.77 99.68 97.31 97.02 99.78 98.61 Si (T) 2.83 2.82 2.89 3.26 3.36 3.29 Al (T) 1.17 1.18 1.11 0.74 0.64 0.71 Al (Oct) 0.19 0.26 0.70 1.69 1.58 1.62 Mg (Oct) 0.92 0.98 0.75 0.17 0.22 0.21 Fe 2+ (Oct) 1.28 1.26 1.08 0.19 0.22 0.21 Fe 3+ (Oct) 0.32 0.32 0.27 0.05 0.05 0.05 Mn (Oct) 0.03 0.02 0.03 0.00 0.00 0.00 Ti (Oct) 0.20 0.16 0.02 0.02 0.01 0.01 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.05 0.01 0.15 0.89 0.91 0.89 Na (A) 0.03 0.01 0.07 0.02 0.01 0.02 K (A) 0.95 0.91 0.81 0.84 0.90 0.88 Ca (A) 0.00 0.01 0.02 0.00 0.00 0.00 vacant (A) 0.01 0.07 0.10 0.14 0.08 0.10 F (X) 0.14 0.10 0.00 0.02 0.11 0.14 Cl (X) 0.01 0.01 0.01 0.00 0.00 0.00 OH (X) 1.85 1.89 1.99 1.98 1.89 1.86 278 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 034 EP 034 chl2 EP 034 chl4 EP 035b bt1 chl1 Mineral Name clinochlore clinochlore chamosite alumino-celadonite Replacing biotite shreddy biotite vein biotite Host Rock Yg Yg Yg Yg SiO2 26.88 26.15 24.90 45.23 TiO2 0.06 0.10 0.03 0.29 Al2O3 18.56 18.73 20.85 29.41 Cr2O3 0.01 0.04 0.00 0.00 Fe2O3 4.52 4.55 4.88 1.30 FeO 23.02 23.19 24.89 4.67 MgO 13.56 13.71 11.14 2.22 MnO 0.62 0.56 0.65 0.07 CaO 0.02 0.02 0.01 0.00 Na2O 0.00 0.01 0.12 0.25 K2O 0.02 0.00 0.02 9.99 H2O 11.24 11.18 11.10 4.24 F 0.00 0.00 0.00 0.09 Cl 0.01 0.01 0.04 0.00 Subtotal 98.53 98.23 98.63 97.77 O=F+Cl 0.00 0.00 -0.01 -0.04 Total 98.52 98.23 98.62 97.73 Si (T) 2.87 2.81 2.69 3.16 Al (T) 1.13 1.19 1.31 0.84 Al (Oct) 1.20 1.17 1.34 1.59 Mg (Oct) 2.16 2.19 1.79 0.23 Fe 2+ (Oct) 2.05 2.08 2.25 0.27 Fe 3+ (Oct) 0.36 0.37 0.40 0.07 Mn (Oct) 0.06 0.05 0.06 0.00 Ti (Oct) 0.00 0.01 0.00 0.02 Cr (Oct) 0.00 0.00 0.00 0.00 vacant (Oct) 0.16 0.12 0.16 0.82 Na (A) 0.00 0.00 0.03 0.03 K (A) 0.00 0.00 0.00 0.89 Ca (A) 0.00 0.00 0.00 0.00 vacant (A) 0.99 1.00 0.97 0.07 F (X) 0.00 0.00 0.00 0.02 Cl (X) 0.00 0.00 0.01 0.00 OH (X) 8.00 8.00 7.99 1.98 279 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 035b chl1 EP 035b chl2 EP 035b ser1 EP 037 chl1 EP 037 ser1 Mineral Name Replacing Host Rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Si (T) Al (T) Al (Oct) Mg (Oct) Fe 2+ (Oct) Fe 3+ (Oct) Mn (Oct) Ti (Oct) Cr (Oct) vacant (Oct) Na (A) K (A) Ca (A) vacant (A) F (X) Cl (X) OH (X) clinochlore shreddy biotite Yg 27.26 0.11 17.90 0.01 4.23 21.55 15.77 0.60 0.01 0.01 0.00 11.26 0.22 0.00 98.93 -0.09 98.84 2.88 1.12 1.10 2.48 1.90 0.34 0.05 0.01 0.00 0.11 0.00 0.00 0.00 1.00 0.07 0.00 7.93 clinochlore biotite Yg 26.71 0.05 18.14 0.00 4.34 22.14 14.89 0.45 0.03 0.00 0.06 11.04 0.40 0.01 98.25 -0.17 98.08 2.85 1.15 1.14 2.37 1.98 0.35 0.04 0.00 0.00 0.12 0.00 0.01 0.00 0.99 0.14 0.00 7.86 muscovite biotite Yg 46.49 0.51 31.38 0.00 0.95 3.44 0.64 0.01 0.00 0.37 10.33 4.22 0.31 0.01 98.66 -0.13 98.53 3.19 0.81 1.73 0.07 0.20 0.05 0.00 0.03 0.00 0.94 0.05 0.90 0.00 0.05 0.07 0.00 1.93 clinochlore biotite Tpd 29.35 0.40 19.00 0.03 3.46 17.64 14.72 0.73 0.19 0.03 1.29 11.54 0.00 0.03 98.41 -0.01 98.40 3.05 0.95 1.38 2.28 1.53 0.27 0.06 0.03 0.00 0.44 0.01 0.17 0.02 0.80 0.00 0.00 8.00 muscovite plag Tpd 48.55 0.00 30.01 0.01 0.74 2.65 1.75 0.01 0.00 0.22 10.65 4.28 0.30 0.01 99.18 -0.13 99.06 3.29 0.71 1.69 0.18 0.15 0.04 0.00 0.00 0.00 0.95 0.03 0.92 0.00 0.05 0.06 0.00 1.94 280 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 038a EP 038a EP 038a EP 038a EP 038a EP 038c bt1 bt2 bt3 bt4 bt5 bt1 Mineral Name phlogopite phlogopite phlogopite phlogopite phlogopite phlogopite Replacing plag biotite biotite biotite Host Rock Tpd Tpd Tpd Tpd Tpd Yg SiO2 36.29 35.49 36.67 36.17 37.09 38.30 TiO2 2.40 1.98 4.02 1.70 2.16 2.22 Al2O3 16.56 17.12 14.54 16.75 15.68 15.16 Cr2O3 0.03 0.06 0.04 0.00 0.01 0.00 Fe2O3 4.08 4.36 4.39 4.49 4.39 3.91 FeO 14.67 15.68 15.80 16.16 15.81 14.07 MgO 10.42 10.06 10.21 10.23 10.60 11.46 MnO 0.31 0.24 0.34 0.41 0.42 0.34 CaO 0.00 0.08 0.00 0.09 0.00 0.00 Na2O 0.09 0.00 0.07 0.09 0.14 0.04 K2O 9.52 9.16 9.22 9.14 9.30 9.37 H2O 3.61 3.51 3.62 3.70 3.75 3.73 F 0.51 0.65 0.41 0.32 0.26 0.35 Cl 0.02 0.03 0.15 0.03 0.03 0.03 Subtotal 98.50 98.40 99.50 99.29 99.62 98.99 O=F+Cl -0.22 -0.28 -0.21 -0.14 -0.11 -0.16 Total 98.29 98.12 99.29 99.15 99.51 98.83 Si (T) 2.83 2.79 2.85 2.82 2.87 2.94 Al (T) 1.17 1.21 1.15 1.18 1.13 1.06 Al (Oct) 0.35 0.37 0.18 0.35 0.30 0.31 Mg (Oct) 1.21 1.18 1.18 1.19 1.22 1.31 Fe 2+ (Oct) 0.96 1.03 1.03 1.05 1.02 0.90 Fe 3+ (Oct) 0.24 0.26 0.26 0.26 0.26 0.23 Mn (Oct) 0.02 0.02 0.02 0.03 0.03 0.02 Ti (Oct) 0.14 0.12 0.24 0.10 0.13 0.13 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.09 0.03 0.09 0.02 0.05 0.10 Na (A) 0.01 0.00 0.01 0.01 0.02 0.01 K (A) 0.95 0.92 0.91 0.91 0.92 0.92 Ca (A) 0.00 0.01 0.00 0.01 0.00 0.00 vacant (A) 0.04 0.08 0.07 0.07 0.06 0.08 F (X) 0.12 0.16 0.10 0.08 0.06 0.09 Cl (X) 0.00 0.00 0.02 0.00 0.00 0.00 OH (X) 1.87 1.84 1.88 1.92 1.93 1.91 281 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 038c EP 038c EP 040 bt2 EP 040 bt3 EP 040 EP 042 bt2 ser1 ser1 chl1 Mineral Name phlogopite muscovite muscovite muscovite muscovite chamosite Replacing plag biotite biotite plag biotite Host Rock Yg Yg Yxm Yxm Yxm Yxm SiO2 36.82 45.99 45.10 45.50 47.92 23.76 TiO2 3.17 0.51 0.20 0.37 0.14 0.02 Al2O3 15.12 30.39 29.14 31.83 29.63 19.03 Cr2O3 0.00 0.00 0.00 0.02 0.00 0.01 Fe2O3 4.20 1.11 0.93 1.25 0.96 5.16 FeO 15.12 3.99 3.36 4.49 3.45 26.29 MgO 10.65 1.80 1.31 0.07 1.66 8.08 MnO 0.33 0.05 0.10 0.13 0.01 2.10 CaO 0.00 0.02 0.02 0.00 0.05 0.06 Na2O 0.11 0.22 0.22 0.19 0.08 0.04 K2O 9.21 10.91 9.58 10.82 10.41 0.00 H2O 3.62 4.33 3.93 4.20 3.99 10.42 F 0.45 0.08 0.53 0.31 0.81 0.11 Cl 0.09 0.00 0.01 0.01 0.03 0.00 Subtotal 98.88 99.40 94.44 99.20 99.16 95.07 O=F+Cl -0.21 -0.03 -0.23 -0.13 -0.35 -0.05 Total 98.67 99.36 94.21 99.06 98.81 95.03 Si (T) 2.86 3.16 3.23 3.14 3.28 2.72 Al (T) 1.14 0.84 0.77 0.86 0.72 1.28 Al (Oct) 0.25 1.62 1.69 1.73 1.66 1.29 Mg (Oct) 1.23 0.18 0.14 0.01 0.17 1.38 Fe 2+ (Oct) 0.98 0.23 0.20 0.26 0.20 2.52 Fe 3+ (Oct) 0.25 0.06 0.05 0.06 0.05 0.44 Mn (Oct) 0.02 0.00 0.01 0.01 0.00 0.20 Ti (Oct) 0.19 0.03 0.01 0.02 0.01 0.00 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.08 0.88 0.90 0.91 0.91 0.17 Na (A) 0.02 0.03 0.03 0.02 0.01 0.01 K (A) 0.91 0.96 0.88 0.95 0.91 0.00 Ca (A) 0.00 0.00 0.00 0.00 0.00 0.01 vacant (A) 0.07 0.01 0.09 0.02 0.08 0.98 F (X) 0.11 0.02 0.12 0.07 0.18 0.04 Cl (X) 0.01 0.00 0.00 0.00 0.00 0.00 OH (X) 1.88 1.98 1.88 1.93 1.82 7.96 282 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 042 EP 046 EP 046 EP 070 EP 086 bt1 EP 086 bt2 kspar1 chl2 chl1 chl2 Mineral Name chamosite clinochlore muscovite chamosite annite annite Replacing biotite vein kspar biotite Host Rock Yxm Yxm Yxm Yg Yg Yg SiO2 27.20 26.79 47.97 25.40 36.99 36.26 TiO2 0.06 0.06 0.16 0.09 2.02 1.70 Al2O3 17.01 20.60 31.70 19.79 14.53 14.11 Cr2O3 0.00 0.00 0.00 0.01 0.00 0.00 Fe2O3 5.10 4.34 0.76 5.60 4.57 4.72 FeO 26.02 22.13 2.75 28.54 16.44 16.99 MgO 6.23 13.43 1.06 5.79 8.92 9.10 MnO 1.04 0.18 0.01 0.35 0.41 0.36 CaO 1.04 0.02 0.03 0.07 0.18 0.27 Na2O 0.00 0.01 0.12 0.03 0.04 0.15 K2O 0.10 0.18 9.94 0.91 7.65 7.70 H2O 10.51 11.25 4.44 10.70 3.24 3.43 F 0.00 0.35 0.00 0.00 1.01 0.52 Cl 0.02 0.01 0.00 0.05 0.05 0.05 Subtotal 94.32 99.36 98.95 97.32 96.05 95.36 O=F+Cl 0.00 -0.15 0.00 -0.01 -0.44 -0.23 Total 94.32 99.21 98.95 97.31 95.61 95.13 Si (T) 3.10 2.81 3.24 2.84 2.97 2.95 Al (T) 0.90 1.19 0.76 1.16 1.03 1.05 Al (Oct) 1.39 1.36 1.76 1.46 0.35 0.30 Mg (Oct) 1.06 2.10 0.11 0.97 1.07 1.10 Fe 2+ (Oct) 2.48 1.94 0.16 2.67 1.10 1.16 Fe 3+ (Oct) 0.44 0.34 0.04 0.47 0.28 0.29 Mn (Oct) 0.10 0.02 0.00 0.03 0.03 0.02 Ti (Oct) 0.00 0.01 0.01 0.01 0.12 0.10 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.53 0.22 0.93 0.39 0.05 0.02 Na (A) 0.00 0.00 0.02 0.01 0.01 0.02 K (A) 0.01 0.02 0.86 0.13 0.78 0.80 Ca (A) 0.13 0.00 0.00 0.01 0.02 0.02 vacant (A) 0.86 0.97 0.13 0.85 0.19 0.15 F (X) 0.00 0.12 0.00 0.00 0.26 0.13 Cl (X) 0.00 0.00 0.00 0.01 0.01 0.01 OH (X) 8.00 7.88 2.00 7.99 1.74 1.86 283 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number EP 086 bt3 EP 086 bt4 EP 086 bt5 MW NACA2 MW NACA2 chl1 chl2 Mineral Name annite phlogopite phlogopite clinochlore clinochlore Replacing biotite biotite biotite Host Rock Yg Yg Yg Yg Yg SiO2 36.67 36.65 37.31 28.42 29.08 TiO2 2.32 1.85 1.14 0.06 0.05 Al2O3 13.91 13.44 14.29 16.06 15.33 Cr2O3 0.00 0.03 0.00 0.01 0.03 Fe2O3 4.56 4.69 4.61 4.65 4.69 FeO 16.40 16.88 16.61 23.71 23.92 MgO 8.66 9.50 9.42 14.69 14.10 MnO 0.42 0.41 0.38 0.65 0.58 CaO 0.24 0.19 0.20 0.07 0.20 Na2O 0.11 0.04 0.05 0.01 0.00 K2O 7.88 7.31 8.19 0.02 0.01 H2O 3.21 3.29 3.49 11.14 11.29 F 1.00 0.82 0.49 0.41 0.00 Cl 0.04 0.04 0.05 0.02 0.00 Subtotal 95.41 95.13 96.23 99.93 99.28 O=F+Cl -0.43 -0.35 -0.22 -0.17 0.00 Total 94.98 94.78 96.01 99.75 99.27 Si (T) 2.98 2.98 2.99 3.01 3.09 Al (T) 1.02 1.02 1.01 0.99 0.91 Al (Oct) 0.31 0.27 0.35 1.01 1.01 Mg (Oct) 1.05 1.15 1.13 2.32 2.23 Fe 2+ (Oct) 1.11 1.15 1.11 2.10 2.12 Fe 3+ (Oct) 0.28 0.29 0.28 0.37 0.37 Mn (Oct) 0.03 0.03 0.03 0.06 0.05 Ti (Oct) 0.14 0.11 0.07 0.00 0.00 Cr (Oct) 0.00 0.00 0.00 0.00 0.00 vacant (Oct) 0.08 0.00 0.04 0.15 0.20 Na (A) 0.02 0.01 0.01 0.00 0.00 K (A) 0.82 0.76 0.84 0.00 0.00 Ca (A) 0.02 0.02 0.02 0.01 0.02 vacant (A) 0.15 0.22 0.14 0.99 0.98 F (X) 0.26 0.21 0.12 0.14 0.00 Cl (X) 0.00 0.01 0.01 0.00 0.00 OH (X) 1.74 1.78 1.87 7.86 8.00 284 Table 8. Normalized microprobe data: sheet silicates from Eagle Pass. Sample number MW NACA3 ser1 MW SPECHEM ser1 Mineral Name alumino-celadonite Replacing biotite Host Rock Yg SiO2 43.91 TiO2 0.00 Al2O3 29.87 Cr2O3 0.00 Fe2O3 1.24 FeO 4.45 MgO 4.91 MnO 0.06 CaO 0.09 Na2O 0.11 K2O 8.19 H2O 4.29 F 0.00 Cl 0.01 Subtotal 97.14 O=F+Cl 0.00 Total 97.14 Si (T) 3.06 Al (T) 0.94 Al (Oct) 1.52 Mg (Oct) 0.51 Fe 2+ (Oct) 0.26 Fe 3+ (Oct) 0.06 Mn (Oct) 0.00 Ti (Oct) 0.00 Cr (Oct) 0.00 vacant (Oct) 0.64 Na (A) 0.01 K (A) 0.73 Ca (A) 0.01 vacant (A) 0.25 F (X) 0.00 Cl (X) 0.00 OH (X) 2.00 phlogopite plag Yg 41.61 0.04 17.09 0.00 3.29 11.86 10.20 0.17 0.54 1.70 4.06 0.75 6.74 0.01 98.06 -2.84 95.21 3.16 0.84 0.69 1.15 0.75 0.19 0.01 0.00 0.00 0.20 0.25 0.39 0.04 0.31 1.62 0.00 0.38 285 Sample number Mineral Name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Based on T+O+A=8 Si (T) Al (T) Al (Oct) Mg (Oct) Mn 2+ (Oct) Mn 3+ (Oct) Fe 3+ (Oct) Ti (Oct) Cr (Oct) Na (A) K (A) Ca (A) F (X) Cl (X) OH (X) Table 9. Normalized microprobe data: epidote from Eagle Pass. EP 022a EP 037 EP 038a MW SPECHEM MW NACA2 ep1 ep1 ep1 ep1 act1 epidote epidote epidote epidote epidote kspar vein vein kspar vein Yg Tpd Tpd Yg Yg 36.90 38.01 37.44 38.26 37.73 0.12 0.09 0.11 0.03 0.19 22.06 22.74 21.25 23.18 22.96 0.00 0.00 0.00 0.00 0.02 14.58 13.55 15.11 13.06 13.42 0.37 0.43 0.28 0.20 0.22 0.02 0.00 0.00 0.00 0.00 0.37 0.42 0.28 0.20 0.22 22.23 22.67 22.48 23.11 23.24 0.00 0.01 0.00 0.00 0.02 0.00 0.09 0.00 0.00 0.00 1.84 1.88 1.74 1.88 1.88 0.00 0.00 0.22 0.00 0.00 0.00 0.00 0.00 0.01 0.01 98.50 99.88 98.92 99.94 99.92 0.00 0.00 -0.09 0.00 0.00 98.50 99.88 98.83 99.94 99.92 3.00 0.00 2.11 0.00 0.03 0.00 0.92 0.01 0.00 0.00 0.00 1.94 0.00 0.00 1.00 3.03 0.00 2.14 0.00 0.03 0.00 0.84 0.01 0.00 0.00 0.01 1.94 0.00 0.00 1.00 3.04 0.00 2.03 0.00 0.02 0.00 0.94 0.01 0.00 0.00 0.00 1.96 0.06 0.00 0.94 3.04 0.00 2.17 0.00 0.01 0.00 0.80 0.00 0.00 0.00 0.00 1.97 0.00 0.00 1.00 3.01 0.00 2.16 0.00 0.01 0.00 0.82 0.01 0.00 0.00 0.00 1.99 0.00 0.00 1.00 286 Sample number Mineral Name Replacing Host rock SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 FeO MgO MnO CaO Na2O K2O H2O F Cl Subtotal O=F+Cl Total Based on T+O+A=8 Si (T) Al (T) Al (Oct) Mg (Oct) Mn 2+ (Oct) Mn 3+ (Oct) Fe 3+ (Oct) Ti (Oct) Cr (Oct) Na (A) K (A) Ca (A) F (X) Cl (X) OH (X) Table 9. Normalized microprobe data: epidote from Eagle Pass. MW NACA3 MW ALT5' MW NACA2 ep1 ep1 EP1 epidote epidote epidote vein vein vein Yg Yg Yg 37.25 37.18 37.19 0.02 0.12 0.08 22.00 23.25 23.08 0.00 0.00 0.00 15.42 14.23 13.68 0.00 0.00 0.00 0.00 0.00 0.00 0.07 0.10 0.25 23.15 23.25 23.26 0.00 0.00 0.00 0.00 0.00 0.02 1.87 1.88 1.87 0.00 0.00 0.00 0.01 0.00 0.00 99.78 100.00 99.44 0.00 0.00 0.00 99.78 100.00 99.44 2.99 0.01 2.07 0.00 0.00 0.00 0.93 0.00 0.00 0.00 0.00 1.99 0.00 0.00 1.00 2.96 0.04 2.15 0.00 0.00 0.01 0.85 0.01 0.00 0.00 0.00 1.99 0.00 0.00 1.00 2.98 0.02 2.16 0.00 0.00 0.02 0.82 0.00 0.00 0.00 0.00 2.00 0.00 0.00 1.00 287 Table 10. Normalized microprobe data: amphibole from Eagle Pass. Sample number EP 007 act1 EP 086 act1 MW NACA3 MW NACA3 act2 act1 Mineral Name Alumino-actinolite Alumino-ferro-actinolite actinolite actinolite Replacing biotite biotite biotite biotite Host rock Tpd Yg Yg Yg SiO2 45.44 42.48 51.21 51.37 TiO2 1.96 1.54 0.03 0.05 Al2O3 9.86 8.64 4.05 4.11 Cr2O3 0.03 0.04 0.00 0.00 Fe2O3 4.49 5.05 2.61 2.54 FeO 7.18 18.13 11.57 11.79 MgO 14.24 7.20 14.37 14.21 MnO 0.20 0.82 0.34 0.34 CaO 11.32 11.16 12.54 12.59 Na2O 1.74 1.48 0.60 0.48 K2O 0.77 1.20 0.17 0.15 H2O 1.99 1.77 1.66 1.86 F 0.13 0.34 0.83 0.41 Cl 0.02 0.05 0.04 0.04 Subtotal 99.37 99.91 100.03 99.92 O=F+Cl -0.06 -0.15 -0.36 -0.18 Total 99.31 99.75 99.67 99.74 Si (T) 6.61 6.55 7.45 7.46 Al (T) 1.39 1.45 0.55 0.54 Al (6) 0.30 0.13 0.14 0.17 Fe 3+ (6) 0.49 0.59 0.29 0.28 Ti (6) 0.21 0.18 0.00 0.01 Cr (6) 0.00 0.01 0.00 0.00 Mg (8) 3.09 1.66 3.12 3.08 Fe 2+ (8) 0.87 2.34 1.41 1.43 Mn (8) 0.02 0.11 0.04 0.04 Ca (8) 1.76 1.85 1.96 1.96 Na (A) 0.49 0.44 0.17 0.14 K (A) 0.14 0.24 0.03 0.03 vac. 0.37 0.32 0.80 0.84 F 0.06 0.17 0.38 0.19 Cl 0.01 0.01 0.01 0.01 OH 1.93 1.82 1.61 1.80 288 Table 10. Normalized microprobe data: amphibole from Eagle Pass. Sample number MW ALT5' MW ALT5' MW ALT5' act1 act3 act2 Mineral Name actinolite actinolite actinolite Replacing biotite biotite biotite Host rock Yg Yg Yg SiO2 51.86 52.34 55.80 TiO2 0.06 0.04 0.04 Al2O3 3.26 3.76 1.75 Cr2O3 0.02 0.03 0.00 Fe2O3 2.04 1.52 0.01 FeO 10.71 10.78 9.03 MgO 15.14 15.61 17.81 MnO 0.15 0.18 0.26 CaO 12.36 12.72 12.79 Na2O 0.48 0.60 0.31 K2O 0.17 0.24 0.11 H2O 1.72 1.82 2.13 F 0.69 0.56 0.00 Cl 0.01 0.01 0.00 Subtotal 98.69 100.21 100.05 O=F+Cl -0.29 -0.24 0.00 Total 98.39 99.97 100.05 Si (T) 7.58 7.53 7.87 Al (T) 0.42 0.47 0.13 Al (6) 0.14 0.16 0.16 Fe 3+ (6) 0.22 0.17 0.00 Ti (6) 0.01 0.00 0.00 Cr (6) 0.00 0.00 0.00 Mg (8) 3.30 3.35 3.74 Fe 2+ (8) 1.31 1.30 1.06 Mn (8) 0.02 0.02 0.03 Ca (8) 1.94 1.96 1.93 Na (A) 0.14 0.17 0.09 K (A) 0.03 0.04 0.02 vac. 0.83 0.79 0.89 F 0.32 0.26 0.00 Cl 0.00 0.00 0.00 OH 1.68 1.74 2.00 289 APPENDIX E: TEA CUP U-PB GEOCHRONOLOGY Zircon crystals were extracted from samples by traditional methods of crushing and grinding, followed by separation with a Wilfley table, heavy liquids, and a Frantz magnetic separator. Samples were processed such that all zircons were retained in the final heavy mineral fraction. A split of these grains (generally 50-100 grains) were selected from the grains available and incorporated into a 1” epoxy mount together with fragments of our Sri Lanka standard zircon. The mounts were sanded down to a depth of ~20 microns, polished, imaged, and cleaned prior to isotopic analysis. U-Pb geochronology of zircons was conducted by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) at the Arizona LaserChron Center (Gehrels et al., 2008). The analyses involve ablation of zircon with a New Wave UP193HE Excimer laser (operating at a wavelength of 193 nm) using a spot diameter of 30 microns. The ablated material is carried in helium into the plasma source of a Nu HR ICPMS, which is equipped with a flight tube of sufficient width that U, Th, and Pb isotopes are measured simultaneously. All measurements are made in static mode, using Faraday detectors with 3x1011 ohm resistors for 238 U, 232 Th, 208 Pb206 Pb, and discrete dynode ion counters for 204 Pb and202 Hg. Ion yields are ~0.8 mv per ppm. Each analysis consists of one 15-second integration on peaks with the laser off (for backgrounds), 15 one-second integrations with the laser firing, and a 30 second delay to purge the previous sample and prepare for the next analysis. The ablation pit is ~15 microns in depth. 290 For each analysis, the errors in determining 206 Pb/238 U and 206 Pb/204 Pb result in a measurement error of ~1-2% (at 2-sigma level) in the 206 Pb/238 U age. The errors in measurement of 206 Pb/207 Pb and 206 Pb/204 Pb also result in ~1-2% (at 2-sigma level) uncertainty in age for grains that are >1.0 Ga, but are substantially larger for younger grains due to low intensity of the 207 Pb signal. For most analyses, the cross-over in precision of206 Pb/238 U and 206 Pb/207 Pb ages occurs at ~1.0 Ga. 204 Hg interference with 204 Pb is accounted for measurement of 202 Hg during laser ablation and subtraction of 204 Hg according to the natural 202 Hg/204 Hg of 4.35. This Hg is correction is not significant for most analyses because our Hg backgrounds are low (generally ~150 cps at mass 204). Common Pb correction is accomplished by using the Hg-corrected 204 Pb and assuming an initial Pb composition from Stacey and Kramers (1975). Uncertainties of 1.5 for 206 Pb/204 Pb and 0.3 for 207 Pb/204 Pb are applied to these compositional values based on the variation in Pb isotopic composition in modern crystal rocks. Inter-element fractionation of Pb/U is generally ~5%, whereas apparent fractionation of Pb isotopes is generally <0.2%. In-run analysis of fragments of a large zircon crystal (generally every fifth measurement) with known age of 563.5 ± 3.2 Ma (2-sigma error) is used to correct for this fractionation. The uncertainty resulting from the calibration correction is generally 1-2% (2-sigma) for both 206 Pb/207 Pb and 206 Pb/238 U ages. Concentrations of U and Th are calibrated relative to our Sri Lanka zircon, which contains ~518 ppm of U and 68 ppm Th. 291 Locations of the samples are shown in Table 1, and the analytical data are reported in Table 2. Uncertainties shown in these tables are at the 1-sigma level and include only measurement errors. Inheritance was tested in the samples by examining both the core and tip of each zircon where possible. Ages older than Oligocene were interpreted to represent inheritance in the samples. Many of these ages are Proterozoic in age, which would be expected due to the Proterozoic age of the country rock in the study area. The resulting interpreted ages are shown on weighted mean diagrams using the routines in Isoplot (Ludwig, 2008) (Fig. 2). The weighted mean diagrams show the weighted mean (weighting according to the square of the internal uncertainties), the uncertainty of the weighted mean, the external (systematic) uncertainty that corresponds to the ages used, the final uncertainty of the age (determined by quadratic addition of the weighted mean and external uncertainties), and the MSWD of the data set. REFERENCES Gehrels, G.E., Valencia, V., Ruiz, J., 2008, Enhanced precision, accuracy, efficiency, and spatial resolution of U-Pb ages by laser ablation- multicollector-inductively coupled plasma- mass spectrometry: Geochemistry, Geophysics, Geosystems, v. 9, Q03017, doi:10.1029/2007GC001805. Ludwig, K., 2008, Isoplot 3.6: Berkeley Geochronology Center Special Publication 4, 77 p. Stacey, J.S., and Kramers, J.D., 1975, Approximation of terrestrial lead isotope evolution by a two-stage model: Earth and Planetary Science Letters, v. 26, p. 207-221. 292 TABLE 1. Location of U-Pb geochronology samples Sample Latitude Longitude SP 100 33°02’33.6” N 111°13’07.5” W SP 102 33°04’42.8” N 111°14’26.9” W SP 103 33°05’31.0” N 111°04’11.9” W GB 202 33°04' 16.3" N 111°06' 29.2" W GB 203 33°05' 15.0" N 111°03' 06.9" W 293 TABLE 2. U-Pb geochronologic analyses Isotope ratios Analysis U 206Pb (ppm) 204Pb U/T h Apparent ages (Ma) 206Pb* ± 207Pb* ± 206Pb* ± error 206Pb* ± 207Pb* ± 206Pb* ± Best age ± 207Pb* (%) 235U* (%) 238U (%) corr. 238U* (Ma) 235U (Ma) 207Pb* (Ma) (Ma) (Ma) SP102-1T 554 2084 3.5 25.9006 10.2 0.0544 10.3 0.0102 1.3 0.13 65.5 0.9 53.7 5.4 -443.2 269.7 SP102-1TC 374 44171 7.1 10.1237 0.4 3.7854 2.3 0.2779 2.3 0.99 1581.0 32.4 1589.7 18.8 1601.2 7.0 65.5 0.9 1601.2 SP102-2T 1184 5164 2.2 20.6269 4.7 0.0707 5.0 0.0106 1.6 0.33 67.8 1.1 69.3 3.3 122.8 110.4 67.8 7.0 1.1 SP102-2C 339 33256 0.7 10.9727 0.7 2.9485 1.3 0.2346 1.1 0.86 1358.8 14.0 1394.4 10.0 1449.4 12.7 1449.4 12.7 SP102-4T 487 1432 1.8 21.9176 6.7 0.0697 6.8 0.0111 1.1 0.16 71.0 0.8 68.4 4.5 -22.1 162.2 71.0 0.8 SP102-5TB 478 2086 3.2 24.3408 16.8 0.0632 17.1 0.0112 2.8 0.17 71.5 2.0 62.2 10.3 -282.4 431.0 71.5 2.0 SP102-5C 64 4292 1.4 11.4185 4.1 1.9761 7.9 0.1637 6.8 0.85 977.1 61.4 1107.4 53.6 1373.2 79.5 1373.2 79.5 SP102-11T 756 3194 2.1 21.5728 8.3 0.0733 8.3 0.0115 1.1 0.13 73.5 0.8 71.9 5.8 16.1 198.7 73.5 0.8 SP102-12T 501 1854 2.3 23.3944 7.1 0.0632 7.5 0.0107 2.4 0.31 68.8 1.6 62.3 4.5 -182.4 177.9 68.8 1.6 SP102-13T 343 2183 3.5 23.0149 11.9 0.0611 12.1 0.0102 1.7 0.14 65.5 1.1 60.3 7.1 -141.7 296.8 65.5 1.1 SP102-13C 109 791 1.4 33.3635 46.5 0.0458 46.6 0.0111 2.4 0.05 71.0 1.7 45.5 20.7 -1161.7 1496.8 71.0 1.7 SP102-13T B 427 1830 2.8 27.5381 12.5 0.0500 12.5 0.0100 0.8 0.06 64.1 0.5 49.5 6.0 -607.3 341.0 64.1 0.5 SP102-13C 158 12966 3.2 10.9774 1.4 2.5057 3.1 0.1995 2.7 0.90 1172.6 29.4 1273.7 22.2 1448.6 26.0 1448.6 26.0 GB0203-1T 336 1475 2.3 27.6397 19.4 0.0548 19.5 0.0110 2.0 0.10 70.4 1.4 54.1 10.3 -617.3 534.5 70.4 1.4 GB0203-2T 385 2581 2.3 23.8034 16.1 0.0625 16.1 0.0108 1.0 0.06 69.2 0.7 61.6 9.6 -225.9 406.5 69.2 0.7 GB0203-3T 634 2715 1.5 24.7508 9.6 0.0625 9.9 0.0112 2.4 0.24 72.0 1.7 61.6 5.9 -325.1 247.6 72.0 1.7 GB0203-4T 418 2105 2.3 24.7288 12.8 0.0618 13.0 0.0111 2.4 0.19 71.1 1.7 60.9 7.7 -322.8 329.9 71.1 1.7 GB0203-5T 457 2611 2.2 26.0598 9.4 0.0601 9.8 0.0114 2.5 0.26 72.9 1.8 59.3 5.6 -459.3 249.6 72.9 1.8 GB0203-6T 564 2301 1.9 24.7621 9.7 0.0614 10.0 0.0110 2.4 0.24 70.7 1.7 60.5 5.9 -326.3 248.9 70.7 1.7 GB0203-7T 420 2024 2.2 24.4885 12.2 0.0611 12.4 0.0109 1.9 0.15 69.6 1.3 60.2 7.2 -297.8 313.9 69.6 1.3 GB0203-8T 377 1790 2.9 25.4820 10.6 0.0581 10.7 0.0107 1.6 0.15 68.9 1.1 57.3 6.0 -400.5 277.1 68.9 1.1 1.0 GB0203-9T 451 3620 2.1 23.0475 13.6 0.0645 13.7 0.0108 1.5 0.11 69.1 1.0 63.5 8.4 -145.2 339.2 69.1 GB0203-10T 645 3799 1.8 21.3759 4.4 0.0705 4.7 0.0109 1.5 0.32 70.1 1.0 69.2 3.1 38.1 105.6 70.1 1.0 GB0203-11T 257 1244 2.8 26.4254 23.4 0.0579 23.5 0.0111 1.7 0.07 71.1 1.2 57.1 13.0 -496.3 629.5 71.1 1.2 GB0203-12T 403 2414 2.7 25.5956 15.3 0.0612 15.4 0.0114 1.7 0.11 72.8 1.2 60.3 9.0 -412.1 402.2 72.8 1.2 GB0203-13T 334 1476 2.5 29.3068 21.3 0.0535 21.4 0.0114 2.2 0.10 72.8 1.6 52.9 11.0 -779.9 608.0 72.8 1.6 GB0203-14T 351 3453 2.3 23.5910 12.1 0.0668 12.2 0.0114 1.0 0.08 73.3 0.7 65.7 7.7 -203.3 305.0 73.3 0.7 GB0203-15T 510 5247 1.9 20.6048 9.9 0.0719 10.0 0.0107 1.3 0.13 68.9 0.9 70.5 6.8 125.3 234.2 68.9 0.9 GB0203-16T 367 1813 2.3 24.8912 16.1 0.0607 16.2 0.0110 2.1 0.13 70.3 1.5 59.9 9.4 -339.7 416.1 70.3 1.5 GB0203-17T 418 2082 2.6 24.5240 16.9 0.0617 17.0 0.0110 2.1 0.12 70.3 1.4 60.8 10.1 -301.5 435.0 70.3 1.4 294 GB0203-18T 555 2847 1.7 25.3655 12.6 0.0591 12.8 0.0109 1.8 0.14 69.7 1.3 58.3 7.2 -388.6 329.9 69.7 1.3 GB0203-19T 384 2507 2.2 23.3687 21.3 0.0648 21.5 0.0110 2.5 0.12 70.4 1.7 63.8 13.3 -179.7 537.5 70.4 1.7 GB0203-20T 457 3568 2.1 24.6856 20.2 0.0616 20.2 0.0110 1.6 0.08 70.7 1.2 60.7 11.9 -318.4 521.8 70.7 1.2 SP100-1C 222 20336 2.1 11.0287 0.8 3.2721 2.0 0.2617 1.8 0.91 1498.7 24.2 1474.4 15.6 1439.7 16.2 1439.7 16.2 SP100-2C 418 23023 8.5 10.9802 0.7 3.0050 1.6 0.2393 1.4 0.89 1383.1 17.3 1408.9 11.9 1448.1 13.6 1448.1 13.6 SP100-4T 580 2116 2.9 21.8092 8.7 0.0722 9.0 0.0114 2.2 0.25 73.2 1.6 70.7 6.1 -10.1 210.5 73.2 1.6 SP100-5T 490 1455 3.2 21.7016 9.0 0.0697 9.2 0.0110 1.7 0.19 70.4 1.2 68.5 6.1 1.8 217.7 70.4 1.2 SP100-7T 874 3148 2.4 21.3921 8.2 0.0743 8.3 0.0115 1.2 0.15 73.9 0.9 72.8 5.8 36.3 196.6 73.9 0.9 SP100-13T 767 2392 3.6 22.6571 17.5 0.0687 17.6 0.0113 0.8 0.05 72.4 0.6 67.5 11.5 -103.1 433.9 72.4 0.6 SP100-15T 420 1732 3.3 20.2081 18.4 0.0753 18.5 0.0110 1.8 0.10 70.8 1.2 73.7 13.1 170.9 432.3 70.8 1.2 SP100-15C 320 33485 7.0 11.0198 0.7 3.1595 1.5 0.2525 1.3 0.89 1451.4 17.0 1447.3 11.3 1441.3 12.6 1441.3 12.6 SP100-17T 629 2960 2.9 24.8627 16.0 0.0615 16.1 0.0111 1.3 0.08 71.1 1.0 60.6 9.5 -336.7 414.5 71.1 1.0 SP100-19T 751 2960 2.9 22.1286 11.6 0.0698 11.7 0.0112 2.0 0.17 71.9 1.4 68.5 7.8 -45.4 281.7 71.9 1.4 SP100-23T 611 2340 3.5 25.8368 13.5 0.0594 13.7 0.0111 2.1 0.15 71.3 1.5 58.6 7.8 -436.7 357.1 71.3 1.5 SP100-24T 729 2422 2.6 21.4870 8.4 0.0693 9.2 0.0108 3.5 0.39 69.2 2.4 68.0 6.0 25.7 202.7 69.2 2.4 SP100-25C 139 10405 2.0 10.9099 0.9 3.1787 2.9 0.2515 2.8 0.95 1446.3 35.9 1452.0 22.5 1460.3 17.1 1460.3 17.1 SP100-26T 440 1839 4.4 26.4061 29.3 0.0584 29.3 0.0112 0.8 0.03 71.7 0.6 57.6 16.4 -494.3 792.0 SP100-26C 285 36626 4.5 10.9478 0.4 3.1677 0.9 0.2515 0.8 0.88 1446.3 10.1 1449.3 6.8 1453.7 7.9 SP103-1T 569 2221 2.1 24.2841 16.6 0.0633 16.7 0.0111 1.0 0.06 71.4 0.7 62.3 10.1 -276.5 425.8 71.7 0.6 1453.7 7.9 71.4 0.7 SP103-2T 452 1693 3.1 22.3991 13.3 0.0690 13.3 0.0112 1.0 0.07 71.9 0.7 67.8 8.7 -75.0 325.9 71.9 0.7 SP103-3T 1733 6503 7.0 19.9099 11.0 0.0729 11.0 0.0105 1.5 0.13 67.5 1.0 71.5 7.6 205.5 254.7 67.5 1.0 SP103-6T 411 1987 2.0 22.9376 22.5 0.0668 22.5 0.0111 1.1 0.05 71.2 0.7 65.6 14.3 -133.4 561.8 71.2 0.7 SP103-7T 531 2409 4.2 23.6806 16.5 0.0669 16.7 0.0115 2.4 0.14 73.7 1.7 65.8 10.6 -212.9 417.3 73.7 1.7 SP103-9T 593 2793 1.6 23.7847 14.7 0.0643 14.8 0.0111 1.3 0.09 71.1 0.9 63.3 9.1 -223.9 372.3 71.1 0.9 SP103-10T 676 2782 2.1 22.8659 11.8 0.0685 12.1 0.0114 2.6 0.22 72.9 1.9 67.3 7.9 -125.7 292.4 72.9 1.9 SP103-14T 411 1754 2.7 21.2957 22.5 0.0724 22.7 0.0112 3.1 0.14 71.6 2.2 70.9 15.6 47.1 544.4 71.6 2.2 SP103-17T 310 1093 7.0 24.5262 45.5 0.0617 45.6 0.0110 2.7 0.06 70.4 1.9 60.8 26.9 -301.8 1218.4 70.4 1.9 SP103-18T 1013 4386 5.3 22.7836 11.4 0.0629 11.6 0.0104 1.9 0.16 66.6 1.3 61.9 7.0 -116.8 282.5 66.6 1.3 SP103-19T 422 1395 2.4 22.2374 37.3 0.0686 37.6 0.0111 5.0 0.13 70.9 3.5 67.4 24.5 -57.3 936.4 70.9 3.5 SP103-20T 574 2345 1.8 25.1058 20.6 0.0609 20.7 0.0111 2.0 0.10 71.1 1.4 60.1 12.1 -361.8 538.2 71.1 1.4 SP103-22T 722 2979 2.0 20.6063 13.3 0.0723 13.8 0.0108 3.6 0.26 69.2 2.5 70.8 9.4 125.1 315.2 69.2 2.5 SP103-25T 619 2588 3.0 24.9157 29.2 0.0564 29.3 0.0102 1.2 0.04 65.4 0.8 55.8 15.9 -342.2 767.0 65.4 0.8 GB0202-1T 484 2419 2.9 19.0447 18.7 0.0825 19.2 0.0114 4.3 0.23 73.0 3.2 80.4 14.8 307.6 428.1 73.0 3.2 GB0202-2T 547 3555 2.0 21.2216 10.7 0.0699 11.2 0.0108 3.4 0.30 69.0 2.4 68.6 7.5 55.4 256.1 69.0 2.4 GB0202-3C 1322 11485 14.0 14.8926 9.6 0.1465 12.0 0.0158 7.1 0.59 101.2 7.1 138.8 15.5 842.4 200.7 101.2 7.1 GB0202-4T 951 3509 3.3 20.8842 10.1 0.0715 10.1 0.0108 1.1 0.11 69.5 0.8 70.2 6.9 93.5 239.0 69.5 0.8 GB0202-6T 393 1889 1.1 30.1605 28.0 0.0473 28.3 0.0104 4.4 0.15 66.4 2.9 47.0 13.0 -861.7 816.5 66.4 2.9 295 GB0202-6C 279 38033 3.2 11.1258 0.8 2.4492 2.4 0.1976 2.3 0.95 1162.6 24.5 1257.2 17.5 1423.0 14.9 1423.0 GB0202-8T 638 3514 12.7 20.7915 13.1 0.0708 13.8 0.0107 4.1 0.30 68.4 2.8 69.4 9.2 104.0 311.4 68.4 14.9 2.8 GB0202-9T 1144 5814 5.1 21.2041 4.8 0.0682 5.2 0.0105 2.1 0.40 67.2 1.4 66.9 3.4 57.3 114.7 67.2 1.4 296 1. Analyses with >10% uncertainty (1-sigma) in 206Pb/238U age are not included. 2. Analyses with >10% uncertainty (1-sigma) in 206Pb/207Pb age are not included, unless 206Pb/238U age is <500 Ma. 3. Best age is determined from 206Pb/238U age for analyses with 206Pb/238U age <900 Ma and from 206Pb/207Pb age for analyses with 206Pb/238Uage > 900 Ma. 4. All uncertainties are reported at the 1-sigma level, and include only measurement errors. 5. Systematic errors are as follows (at 2-sigma level): [sample 1: 2.5% (206Pb/238U) & 1.4% (206Pb/207Pb)] 6. Analyses conducted by LA-MC-ICPMS, as described by Gehrels et al. (2008). 7. U concentration and U/Th are calibrated relative to Sri Lanka zircon standard and are accurate to ~20%. 8. Common Pb correction is from measured 204Pb with common Pb composition interpreted from Stacey and Kramers (1975). 9. Common Pb composition assigned uncertainties of 1.5 for 206Pb/204Pb, 0.3 for 207Pb/204Pb, and 2.0 for 208Pb/204Pb. 10. U/Pb and 206Pb/207Pb fractionation is calibrated relative to fragments of a large Sri Lanka zircon of 563.5 ± 3.2 Ma (2-sigma). 11. U decay constants and composition as follows: 238U = 9.8485 x 10-10, 235U = 1.55125 x 10-10, 238U/235U = 137.88. 12. Weighted mean plots determined with Isoplot (Ludwig, 2008). 297 APPENDIX F: (U- TH)/HE DATING OF HEMATITE FROM TEA CUP AND EAGLE PASS INTRODUCTION Multiple varieties of hydrothermal hematite have been dated using the (U-Th)/He system (Tables 1,2). While questions remain regarding fundamental aspects of this dating system in hematite (e.g., closure temperature), specular and botryoidal hematite have been demonstrated to retain helium over geologically significant periods of time (Lippolt et al., 1993; Bahr et al; 1994), and geologically meaningful ages have been generated. For example, dating of paragenetic hydrothermal specular hematite (specularite) and adularia from Elba, Italy, yielded concordant (U-Th)/He and K-Ar ages respectively (Lippolt et al., 1995). Hydrothermal botryoidal hematite from Schwarzwald, Germany, was dated by Wernicke and Lippolt (1994) but yielded varying results. In this study, samples of hematite from Tea Cup and Eagle Pass interpreted to have formed during episodes of iron-oxide rich alteration, sodic (-calcic) alteration. and supergene weathering were dated using the (U-Th)/He technique. Hematite was removed from the samples with a “dremel” tool or by scratching them with a piece of steel. Pieces of hematite were then picked and packed into Nb foil packets or tubes. Forty total aliquots from nine samples, as well as six zircon standards, were then lased between three and fifteen minutes using a Nd:YAG laser to extract He. The ratio of 4 He/3 He was measured in a quadrupole mass spectrometer after a spike with a known amount of 3 He 298 was added. Re-extractions were performed until the re-extracted helium was less than the five percent of the original helium extraction. Uranium and thorium were measured in each aliquot by ICP-MS after dissolving them in a Parr bomb with a two-stage HF-HNO3 and HCl method and spiking them with known amounts of 233 U, 229 Th, and 147 Sm. RESULTS Tea Cup Four samples of hematite were collected near the Red Hills prospect (Fig. 1) for (U-Th)/He dating (Tables 1-2; Figure 2). Samples SP 076 and SP 092 are specular hematite that is interpreted to have formed as part of iron oxide-rich alteration in the Tea Cup porphyry system at ~71 Ma. Samples SP 079 and SP 097 contained hematite that occurs in quartz veins containing oxidized sulfide minerals, which is interpreted to have formed during a younger, supergene weathering event superimposed on earlier hypogene potassic alteration. The results of the (U+Th)-He dating of hematite from four samples are shown in Table 2 and Figure 2. Aliquots from samples SP076, SP092, and SP097 showed variations in their ages of greater than 10 m.y. Aliquots from sample SP079 yielded ages within a range of four m.y. and a weighted average age of 14.4 ± 0.24 Ma. Samples SP076, SP092, and SP097 yielded a wide variation in age, varying from 76 Ma (near the age of the porphyry system) to 10 Ma, with one extremely low-He sample at 1 Ma. so Due to the variation, weighted averages are not reported for these samples (Table 2). Results from SP 079 are much more consistent and provide a plausible 299 age for supergene alteration. The dates correspond approximately with the last stages of normal faulting in the area at ~15 Ma (Richard and Spencer, 1997; Nickerson et al., 2010). All the samples lie in the footwall of a normal fault which structurally denuded overlaying rocks (Nickerson et al, 2010). Hematite in sample SP 079 was then produced by the oxidation of Laramide aged potassic alteration which may have begun as when extension ended. Eagle Pass Five samples of hematite were collected at Eagle Pass (Tables 1-2; Figures 3-4). Samples EP 027 and EP 086 were collected from hematite veins hosted in sodic (-calcic) alteration interpreted to have formed concurrently with the intrusion of the Eagle Pass dike swarm at ~26.5 Ma (U-Pb; Appendix A). Sample EP 034 was collected from sodic (-calcic) alteration interpreted to be assocatiated with slip on the Eagle Pass which began after the intrusion of the Eagle Pass dikes (Appendix A). Sample EP 033 was collected in the heart of the Eagle Pass dike swarm from sulfide-bearing potassic alteration that had been affected by intense supergene weathering. Sample EP 069 was collected from a shear zone between two Proterozoic units ~10 km northwest of the Eagle Pass dike swarm. In all the samples, ages from some aliquots yielded nearly reproducible ages. In some cases the 4 He versus mol eU plots Figure 2 indicate irreproducibility may be the result of excess 4 He in the aliquots. Samples EP 027 and EP 085 did not yield ages that match the inferred age of the sodic (-calcic) alteration in which they are hosted (~26.5 Ma). Instead five aliquots from samples EP 027 yield a weighted average age of 13.2 ± 300 0.02 Ma. Aliquot EP 027_5 was omitted from the weighted average because it shows anomalously low eU and an old age. Assuming that loss of U-Th is less likely than gain of extraneous He in these samples, this sample is tentatively interpreted as having“excess” 4 He (Figure 4B) . Sample EP 087 yielded also yielded a weighted average age (10.49 ± 0.06 Ma) significantly younger than predicted 26.5 Ma age of the sodic (-calcic). Aliquots from sample EP 034 yielded a range of ages that ~22 Ma and ~17 Ma, and a weighted average age of 18.93 ± 0.12. While not internally consistent, the ages do provide a reasonable timing for slip along the Eagle Pass fault. The onset of supergene weathering is not constrained at Eagle Pass, but the ages yielded from four aliquots, which range from ~8-6 Ma, are geologically reasonable. Aliquot EP 033_1 was not included in the weighted average because it has low eU and, by comparison to other aliquots and with the assumption that gain of unsupported He is more likely than loss of U-Th, likely contains may excess 4 He(Figure 4A). No geologic constraints are able to be placed on the age of formation of hematite found in the shear zone between two Proterozoic units where EP 069 was collected. The shear zone likely formed as the result of deformation in the Proterozoic or during the Late CretaceousEarly Tertiary Laramide Orogeny. The weighted average age of 10.49 ± .06 Ma suggests the hematite from this sample records anevent which post dates the formation of the shear zone. 301 SIGNIFICANCE OF AGES At both localities hematite (U-Th)/He ages of aliquots from the same sample varied significantly. In some instances this may be the result of aliquots having contained excess 4 He. Geologically plausible ages were obtained from hematite formed as the result of supergene weathering (SP 079 and EP 033), and sodic (-calcic) alteration associated with slip on the Eagle Pass fault (EP 034). Samples EP 027, EP 085, and EP 069 yielded weighted averages between ~13-10 Ma that do not appear to coincide with the formation of the hematite in each sample for reasons discussed above. The consistency of these ages suggests that instead the hematite is recording a younger event, which may reflect regional fluid flow or cooling. No known nearby magmatism was ongoing at this time. The most likely cause of the ~13-10 Ma thermal event is tectonic denudation via normal faulting. The timing of the youngest normal faulting that is not well constrained at Eagle Pass but did occur in the Late Miocene in the nearby Catalina core complex (Davis et al., 2004). Going forward, the main uncertainties surrounding the interpretation of all the (UTh)/He ages spring from the lack of understanding of diffusive loss of He from hematite. Results from this study indicate that (U-Th)/He ages from hematite record post- magmatic events such as supergene weathering or cooling associated with exhumation. Further analytical studies on the system, such as diffusion experiments, will be a necessary step in determining the geologic significance of hematite (U-Th)/He ages. 302 REFERENCES Bähr, R., Lippolt, H.J., and Wernicke, R.S., 1994, Temperature- induced 4He degassing of specularite and botryoidal hematite: A 4He retentivity study: Journal of geophysical research, v. 99, no. B9, p. 17695–17. Davis, G.H., Constenius, K.N., Dickinson, W.R., Rodríguez, E.P., and Cox, L.J., 2004, Fault and fault-rock characteristics associated with Cenozoic extension and corecomplex evolution in the Catalina-Rincon region, southeastern Arizona: Geological Society of America Bulletin, v. 116, no. 1-2, p. 128–141. Lippolt, H.J., Wernicke, R.S., and Boschmann, W., 1993, 4 He diffusion in specular hematite: Physics and Chemistry of Minerals, v. 20, no. 6, p. 415–418. Lippolt, H. J., Wernicke, R. S., and Bahr, R., 1995, Paragenetic specularite and adularia (Elba, Italy): Concordant (U+Th)-He and K-Ar ages: Earth and Planetary Science Letters, v 132, p. 43-51. Nickerson, P.A., Barton, M.D., and Seedorff, E., 2010, Characterization and reconstruction of multiple copper-bearing hydrothermal systems in the Tea Cup porphyry system, Pinal County, Arizona, in Goldfarb, R.J., Marsh, E.E., and Monecke, T., eds., The Challenge of Finding New Mineral Resources: Society of Economic Geologists Special Publication 15, p. 299-316. Richard, S. M., and Spencer, J. E., 1997, Geologic map of the North Butte area, central Arizona: Arizona Geological Survery Open-File Report 97-4, scale 1:24,000, text 18 p. 303 Wenicke, R. S., and Lippolt, H. J., 1994, 4 He age discordance and release behavior of a double shell botryoidal hematite from Schwarzwald, Germany: Geochimica et Cosmochimica Acta, v 58, p. 421-329. 304 TABLE 1. Location and weighted average ages of (U-Th)/He samples fro m Tea Cup and Eagle Pass Weighted Average (Ma) Standard Error (Ma) 14.36 0.24 Sample Location Latitude Longitude SP 076 Tea Cup 33° 2'46.30"N 111°13'5.97"W SP 079 Tea Cup 33° 2'42.89"N 111°13'4.57"W SP 092 Tea Cup 33° 2'33.73"N 111°13'9.76"W SP 097 Tea Cup 33° 2'23.49"N 111°13'5.42"W EP 027 Eagle Pass 32°49'11.37" N 110° 6'42.72"W 13.39 0.10 EP 033 Eagle Pass 32°44'57.03" N 110° 7'49.89"W 7.46 0.60 EP 034 Eagle Pass 32°44'58.11" N 110° 7'46.61"W 18.95 0.12 EP 069 Eagle Pass 32°51'30.58" N 110°11'49.01"W 10.10 0.07 EP 085 Eagle Pass 32°48'49.30" N 110° 6'48.08"W 9.98 0.06 305 TABLE 2. (U-Th)/ He Isotopic Analysis from Tea Cup and Eag le Pass 4 Sample Location Hematite source SP076A Tea Cup FeOx rich alt 10.18 1.64 2.47 37.68 1.07 SP076B Tea Cup FeOx rich alt 9.91 1.67 1.12 42.28 1.21 SP076C Tea Cup FeOx rich alt 24.55 2.29 1.58 75.77 1.88 SP079A Tea Cup Supergene 16.94 5.98 10.43 16.58 0.48 SP079B Tea Cup Supergene 14.02 6.12 5.92 15.43 0.43 SP079C Tea Cup Supergene 29.46 16.06 15.38 12.37 0.36 SP092A Tea Cup FeOx rich alt 6.76 0.95 0.90 47.79 1.41 SP092B Tea Cup FeOx rich alt 6.28 1.47 1.15 29.78 0.99 SP092C Tea Cup FeOx rich alt 3.09 2.49 0.24 10.05 0.22 He (ncc) U (ng) Th (ng) Raw age (Ma) ± (Ma) SP097A Tea Cup Supergene 11.04 5.33 1.83 15.86 0.47 SP097B Tea Cup Supergene 0.03 0.24 0.03 1.00 0.05 SP097c Tea Cup Supergene 0.19 0.17 0.11 7.88 0.12 EP027_1 Eagle Pass NaCa alt 0.29 0.15 0.14 13.05 0.22 EP027_2 Eagle Pass NaCa alt 0.19 0.08 0.09 14.64 0.21 EP027_3 Eagle Pass NaCa alt 0.82 0.40 0.37 14.12 0.20 EP027_4 Eagle Pass NaCa alt 0.33 0.17 0.17 12.74 0.20 EP027_5 Eagle Pass NaCa alt 0.22 0.03 0.03 48.73 0.68 EP027_6 Eagle Pass NaCa alt 0.16 0.09 0.10 11.47 0.29 EP033_1 Eagle Pass Supergene 1.00 0.56 0.13 13.97 0.24 EP033_2 Eagle Pass Supergene 0.64 0.87 0.02 6.07 0.13 EP033_3 Eagle Pass Supergene 0.71 0.84 0.12 6.78 0.12 EP033_4 Eagle Pass Supergene 0.61 0.65 0.03 7.74 0.13 EP033_5 Eagle Pass Supergene 1.19 1.15 0.03 8.57 0.15 EP033_6 Eagle Pass Supergene 0.34 0.35 0.01 8.16 0.14 EP034_1 Eagle Pass NaCa alt 1.73 0.57 0.58 20.08 0.28 EP034_2 Eagle Pass NaCa alt 2.06 0.64 0.59 21.87 0.33 EP034_3 Eagle Pass NaCa alt 3.40 1.42 0.40 18.69 0.43 EP034_4 Eagle Pass NaCa alt 1.18 0.43 0.36 18.89 0.25 EP034_5 Eagle Pass NaCa alt 1.45 0.67 0.24 16.59 0.34 EP034_6 Eagle Pass NaCa alt 1.39 0.58 0.34 17.51 0.28 EP069_1 Eagle Pass NaCa alt 0.19 0.07 0.35 10.40 0.14 EP069_2 Eagle Pass NaCa alt 0.08 0.03 0.12 10.57 0.16 EP069_3 Eagle Pass NaCa alt 0.10 0.03 0.21 10.96 0.15 EP069-5 Eagle Pass NaCa alt 0.06 0.02 0.12 8.79 0.14 EP069-6 Eagle Pass NaCa alt 0.11 0.04 0.22 10.02 0.14 306 EP085-1 Eagle Pass NaCa alt 0.21 0.14 0.25 8.84 0.12 EP085-2 Eagle Pass NaCa alt 1.59 0.56 1.32 15.17 0.21 EP085-3 Eagle Pass NaCa alt 0.13 0.07 0.17 9.93 0.14 EP085-4 Eagle Pass NaCa alt 0.14 0.07 0.15 10.52 0.15 EP085-5 Eagle Pass NaCa alt 0.20 0.12 0.24 9.57 0.15 EP085-6 Eagle Pass NaCa alt 0.11 0.07 0.14 8.91 0.16 307 Figure 1. Location map of (U- Th)/He samples at Tea Cup. 308 Figure 2. Moles of equivalent U (eU) vs mole of 4 He in Tea Cup samples. Red colored samples are hematite derived from sodic (-calcic) alteration, and blue colored samples are hematite derived from supergene alteration. Lines represent predicted moles of 4 He and eU at for ages of 1 Ma, 10 Ma, 15 Ma, and 70 Ma. 309 Figure 3. Location map of (U- Th)/He samples at Eagle Pass. A: Geologic map of the northern portion of the Pinaleño MCC including endpoints of cross section A-A’ through the dike swarm. EPF = Eagle Pass fault; PDF=Pinaleño detachment fault. B: Location map of MCCs in western North America. C: Regional location Map Dashed box is area shown in Fig. 1A. D. Cross section oriented perpendicular the Eagle Pass dike swarm. AA’ located in Fig. 1A. 310 Figure 4. Moles of equivalent U (eU) vs mole of 4 He in Red Hills samples. Red colored samples are hematite derived from sodic (-calcic) alteration or iron-oxide rich alteration, and blue colored samples are hematite derived from supergene alteration. . Lines represent predicted moles of 4 He and eU for ages of 1 Ma, 10 Ma, 15 Ma, and 20 Ma. A) Data from all samples. B) Graph with axis values changed to highlight samples with lower mol 4 He and mol eU values. A) B)