ANALYSIS OF COMPOSITION AND CHRONOLOGY OF DOME EMPLACEMENT

AT BLACK PEAK VOLCANO, ALASKA UTILIZING ASTER REMOTE SENSING

DATA AND FIELD-BASED STUDIES

A

THESIS

Presented to the Faculty

of the University of Alaska Fairbanks

In Partial Fulfillment of the Requirements

For the Degree of

MASTER OF SCIENCE

By

Jennifer Nicole Adleman, B.S.

Fairbanks, Alaska

May 2005 iii

Abstract Black Peak volcano is a —3.5lcin-diameter caldera located on the Alaska Peninsula that formed —4,600 years ago in an eruption that excavated >101cm 3 of material. The caldera floor is occupied by at least a dozen overlapping dacitic to andesitic lava domes and flows. Examination of XRF results and observations of the domes in and around the caldera reveals a range of 57-65wt% Si0 2 and variations in amphibole content. Evidence for magma mixing includes vesicular enclaves and geochemical trends that indicate involvement of a more mafic magma into a dacitic reservoir. The purpose of this study is to investigate if, and how, these differences in composition and mineralogy are detectable in satellite emissivity and TIR data (ASTER) and compare the results to ground-based field observations to discern changes in the mineralogical and chemical properties of the domes. This study incorporates the use of decorrelation-stretch image processing techniques and the deconvolution of laboratory emissivity spectra to assess the viability of discriminating variations in the lithologies observed at Black Peak volcano. Compositional results from XRD and electron microprobe analyses are comparable to those obtained through deconvolution processing. Surfaces of <10% amphibole and Si02 of 60-65wt% and those that correspond to > 10% and <6 Iwt% Si02 are distinguishable in the ASTER data. iv

Table of Contents

Page Signature Page Title Page ii Abstract iii Table of Contents iv List of Figures vi List of Tables viii List of Appendices ix Acknowledgements Introduction 12 Background 19 2.1 Thermal Infrared (TIR) Remote Sensing Background 19 2.2 ASTER Satellite Background 23 2.3 Previous TIR Linear Deconvolution Compositional Studies 25 Methods 28 3.1 General Field Observations and Sampling Techniques 28 3.2 Analytical methods 30 3.2.1 Geochemical analysis 30 3.2.2 X-ray Diffraction 33 3 2 3 Laboratory Emission Spectra 33 3.2.4 Linear Deconvolution 34 3.3 ASTER Remote Sensing data processing 37 3.3.1 Decorrelation Stretch 37 3.3.2 ASTER derived emissivity and temperature 44 Results 45 4.1 Field results 45 4.2 Whole Rock geochemical analyses 52 Page 4.3 Petrologic Analyses 55 4.3.1 Microprobe 55 4.3.2 X-ray Diffraction 55 4.3.3 Laboratory emissivity spectra 63 4.3.4 Linear deconvolution 72 4.4 Satellite data 73 4.4.1 Decorrelation stretching 73 4.4.2 ASTER emissivity profiles 76 Discussion 77 5.1 Age relationships 77 5.2 ASTER satellite image relationships 78 5.2.1 Comparison of ASTER satellite imagery and bulk dome 78 rock compositions 5.2.2 Comparison of ASTER and laboratory emissivity spectra 80 and petrologic data 5.2.3 Comparison of ASTER pixel color, emissivity and 81 mineralogy 5 3 Implications for ASTER assessment of volcanic regions 83 5.3.1 Correlations between ASTER and petrologic studies: 83 what worked 5.3.2 Limitations at Black Peak, Alaska 84 5.3.3 Applications along the Alaska Peninsula and Aleutian Arc 86 Conclusion 88 References Cited 90 vi

List of Figures

Page Figure 1. Location map of Black Peak caldera and historically active volcanoes 13 Figure 2. ASTER spectral bands 16 Figure 3. Blackbody radiance curve 21 Figure 4. Annotated Color Infrared (CIR) aerial photo of Black Peak caldera 29 Figure 5. Example of a TIR color composite of the Black Peak caldera region 38 Figure 6. Schematic representation of the decorrelation stretch 40 Figure 7. Laboratory and ASTER emissivity spectra 43 Figure 8 Images of domes and features at Black Peak caldera 46 Figure 9. Subset of USGS Chignik (C-3) Quadrangle topographic map 48 Figure 10. Total alkali vs. silica (TAS) diagram of 2001 and 2003 samples 53 Figure 11. Harker diagrams of 2001 and 2003 Black Peak samples 54 Figure 12. Plagioclase and pyroxene ternary plots 56 Figure 13a. Section 1 summary of linear deconvolution, XRD and probe results 57 Section 2 summary of linear deconvolution, XRD and probe results 58 Section 2 summary of linear deconvolution, XRD and probe results 59 Section 2 summary of linear deconvolution, XRD and probe results 60 Section 3 summary of linear deconvolution, XRD and probe results 61 f. Additional blue pixel region samples linear deconvolution results 62 Figure 14a. Dry grass and snow laboratory emissivity 65 Section 1 laboratory and ASTER satellite emissivity spectra 66 Section 2 laboratory and ASTER satellite emissivity spectra 67 Section 2 laboratory and ASTER satellite emissivity spectra 68 Section 2 laboratory and ASTER satellite emissivity spectra 69 f Section 3 laboratory and ASTER satellite emissivity spectra 70 g. Additional blue pixel samples laboratory and ASTER emissivity 71 Figure 15. July 2000 ASTER VNIR FCC (3, 2, 1) 74 vii

Page Figure 16. ASTER TIR bands 14, 12 and 10 decorrelation stretch 75 Figure Ala. Additional emissivity plots and pixel color of section 2 samples 137 Additional emissivity plot and pixel color of section 3 samples 138 Emissivity plot and pixel color samples 139 viii

List of Tables

Page Table 1. ASTER sensor specifics (JPL/NASA) 17 Table 2. ASTER scenes used in this study 18 Table 3. Electron microprobe settings 32 Table 4. End Member Spectral Library standards used in linear deconvolution 36 Table 5a. Section 1 Field sample descriptions 49 Section 2 Field sample descriptions 50 Section 3 Field samples, descriptions and petrology 51 Table Al. Section 1 additional field sample descriptions 98 Table A2. XRF Normalized Major Elements (weight %) 99 Table A3. XRF Unnormalized Trace Elements (ppm) 100 Table A4. ICP-MS Trace Elements (ppm) 101 Table A5. Probe analyses of pyroxene 104 Table A6. Probe analyses of amphibole 107 Table A7. Probe analyses of plagioclase 110 Table A8. X-ray diffraction analyses 119 Table A9a. Linear deconvolution results for section 1 121 Linear deconvolution results for section 2 123 Linear deconvolution results for section 3 130 d. Additional linear deconvolution results 132 Table A10. Additional analytical and pixel color results 136 ix

List of Appendices

Page Table A1. Section 1 additional field sample descriptions 98 Table A2. XRF Normalized Major Elements (weight %) 99 Table A3. XRF Unnormalized Trace Elements (ppm) 100 Table A4. ICP-MS Trace Elements (ppm) 101 Table AS. Probe analyses of pyroxene 104 Table A6. Probe analyses of amphibole 107 Table A7. Probe analyses of plagioclase 110 Table A8. X-ray diffraction analyses 119 Table A9a. Linear deconvolution results for section 1 121 Linear deconvolution results for section 2 123 Linear deconvolution results for section 3 130 d. Additional linear deconvolution results 132 Table A10. Additional analytical and pixel color results 136 Figure A Ia. Additional emissivity plots and pixel color of section 2 samples 137 Additional emissivity plot and pixel color of section 3 samples 138 Emissivity plot and pixel color samples 139 x

Acknowledgements First and foremost I humbly thank Brian Epler, who has supported and assisted me throughout my graduate career. His daily smiles, culinary delights, ability to sort the laundry, and his support and love are tremendous contributions to my recent successes. My parents, George Adleman, Mona Zeftel and Lynn Collar have been incredibly understanding and supportive in my efforts to obtain a Masters degree. They have provided a never-ending stream of positive words, suggestions and contributions towards my goals, and I am very grateful for them. On a more academic note I thank my committee. My advisor Dr. Jessica Larsen spent numerous hours working with me in the field, in the lab and on paper to confirm my achievement in this endeavor. I am also grateful for the wisdom and advice Jess has given me in regards to Fairbanks and cabin life, dog ownership and job procurement. She is a great advisor, friend and neighbor. Dr. Michael Ramsey also spent numerous hours working with me in the field and laboratory. He has been a true wealth of knowledge in my academic pursuits. In fact it is Mike's presentation of similar research at the 2002 International Seismic-Volcanic Workshop of Kamchatkan-Aleutian Subduction Processes held in Fairbanks, Alaska that directed me down the path towards this study. His staff and graduate students Dr. Jeff Byrnes, Rachel Lee and Topher Hughes have been of great assistance to me in the preparation and analyses of my samples at their Pittsburgh facility. Dr. John Eichelberger and I have known each other for years, and it is through his positive and thoughtful leadership that I came to study at the University of Alaska Fairbanks. The opportunities which I have been afforded are in no uncertain terms due to Eich's ability to accomplish just about anything he puts his mind and heart to. Jess, Mike and I had a technique that needed a volcano, and Game McGimsey offered one. Tina Neal and Game McGimsey graciously offered to share their helicopter, time, field work and knowledge to a motley crew of student, petrologist and remote sensor without hesitation. I am grateful to Game for supporting my use of this technique in such an interesting petrologic region and for providing a field experience unparallel to any I have had the pleasure to be a part of Game also provided a great deal of enlightenment in xi regards to field preparations and trainings, the art of writing, and being a productive member of a terrific field crew. Ken Dean has been the backbone of my remote sensing coursework as a student at UAF. The remote sensing classes, guidance and experiences Ken has provided have played an important role in my study. Numerous others have been instrumental in instructing me in the use and compilation of a dizzying assortment of software packages, laboratory instruments and data sets. Electron microprobe guru Dr. Ken Severin, GIS wizard Janet Schaefer, computer expert Dr. Bill Witte, and geochemistry connoisseur Dr. Chris Nye have answered every question I have thrown at them, and have graciously helped me sort out a variety of technical and challenging situations. Andrea Steffke, Courtney Kearney, Julie Elliott, Lily Wong, Sally Kuhn, and Steve Smith have been a great group of friends, colleagues and sounding boards for me over the last few years. I am indebted to them for their humor, discussion, criticism and friendship. Funding for this study was obtained from or provided by the Alaska Volcano Observatory, the Geophysical Society of Alaska, the USGS Volcano Hazards Program Jack Kleinman Internship for Volcanic Research, and the Geological Society of Alaska. Travel funds to present the result of this study were obtained through the University of Alaska Fairbanks Geophysical Institute Student Travel Grant, The University of Alaska Fairbanks Graduate School Travel Grant, and the Alaska Quaternary Center Student Travel Grant. Additional funding for my participation in the 2004 International Volcanologic Field School, Kamchatka, Russia and 2003 Cities on Volcanoes III Student Workshop, Hilo, Hawai'i was provided in part through the National Science Foundation. 12

I. Introduction Black Peak caldera is one of approximately 80 Holocene volcanic centers that erupted along the 2,760km long Aleutian Arc that stretches from southern Alaska to Russia's Kamchatka Peninsula (Fig. 1; Miller et. al., 1998). Approximately one dozen, overlapping, post-caldera lava domes that are generally coeval in age and have bulk rock compositions that range from andesite to dacite are contained within the caldera with several that spill out onto the southeastern flank. Reconnaissance fieldwork conducted prior to the 2003 field season (unpublished data, McGimsey and Neal, 2001; Detterman et. al., 1981) and the 2003 field campaign at Black Peak provide the first comprehensive geologic investigation and data on the composition and surface textures of the domes within and surrounding Black Peak caldera. The contrasting ages, mineralogies, compositions, and surface alterations of the domes make Black Peak caldera an excellent location to use thermal infrared (TIR) remote sensing data, in combination with field mapping, petrology and geochemistry, to analyze the variations and features of the domes, and to compare field-based measurements to those resolved with satellite remote sensing imagery observations. The only satellite-based study conducted on Black Peak prior to this work focused on the volcanic landforms of the Alaska Peninsula and Aleutian Islands utilizing radar data from the European Remote Sensing Satellite-1 (ERS-1) launched in 1991 (Rowland et. al., 1994). In that study, Black Peak was identified as a large caldera with prominently visible dome features consisting of at least four domes or lobes. In the ERS-1 data study it is suggested that the young domes represent the present location of a magmatic center that has migrated westward through time. 6

BERING SEA * Black Peak volcano Historically active volcano

8°

56° 150° W GULF OF ALASKA ALEUTIAN ISLANDS Kodiak Ki Island Island Seguam Aniakcit Island Veniaminof 178° E i 0 200 400 mi Atka 158°W Island Islands Unalaska 0 200 400 km PACIFIC OCEAN 1 of Four 170°W Island I Mountains

6°30'

Figure 1. Location map of Black Peak caldera and historically active volcanoes of Alaska. 14

Unlike the prior study, and the routine satellite analyses currently used twice daily by the Alaska Volcano Observatory (AVO) to monitor and track thermal anomalies and airborne ash (Dean et. al., 2002), this research incorporates satellite image processing and analyses to enhance non-ephemeral properties inherent in the effusive volcanic products of Black Peak. This study also expands both on the work conducted by previous field parties and the tools available for analytical geochemistry analysis in order to further our understanding of Black Peak caldera beyond what could be gained from standard petrologic and field techniques alone. Satellite remote sensing techniques are currently applied to investigate volcanic regions and can provide composition and mineralogy information on the spatial coverage of volcanic deposits. Launched on board NASA's Earth Observing Satellite (EOS) Terra in 1999, the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) is the first sun-synchronous, polar orbiting satellite with more than two bands in the TIR (Fig. 2; Table 1; Yamaguchi et. al., 1998). Thus, ASTER satellite data is unique and well-suited for studies discerning textural, compositional and mineralogical variations on silicic domes using the emissivity properties of the ground surface collected in multiple thermal bands (Table 2). Previous work (Ramsey et. al., 1993; Ramsey et. al., 1999; Ramsey and Fink, 1999) has focused on applying satellite remote sensing techniques to studying variations in vesicularity and mineralogy to better understand lava dome formation and vesiculation processes. In particular, ASTER TIR data has been used to look at petrologic and compositional variations in the silicic domes of Medicine Lake Volcano, CA (Eisinger et. al., 2000) and the variety of volcanic rock types of the Erta Range, Ethiopian Rift Valley (Watanabe and Matsuo, 2003). Additionally, laboratory derived spectroscopic signatures are often used to augment and verify the satellite data and specific spectral characteristics are associated with rock and surface properties for the proportions of different rock types and/or surface features included within each pixel for a given area covered by a remote sensing image (Michalski et. al., 2004; Watanabe and Matsuo, 2003; Ramsey and Christensen, 1998). 15

The focus of this study combines field, petrologic, geochemical, and remote sensing methods to assess the viability of using TIR remote sensing data in a complex and remote volcanic region. The goal of this study is to develop a method for applying processed ASTER TIR satellite data to field and laboratory studies of volcanic rocks in order to constrain spatial and age relationships and to test the ability of satellite data to discern chemical and petrologic differences among overlapping lava domes. Given the amount of unstudied and unmapped volcanic regions in Alaska, the use of ASTER data for preliminary investigation of remote volcanoes, may be cost effective and efficient, and could be valuable in directing the focus of future studies along the Alaska Peninsula and Aleutian arc.

16

Solar Reflected 0 UV Visible NIR Infrared Mid Infrared 0. Far Infrared En E

0.5 1.0 1.5 2.0 3.0 20.0 VN1R SWIR T1R 15m 30m 90m Figure 2. ASTER spectral bands, Jet Propulsion Labs / National Aeronautic and Space Administration (JPL/NASA) 17

Table 1. ASTER sensor s pecifics (JPL/NASA Characteristic VNIR SWIR Tut Spectral Band 1: 0.52— 0.6 Band 4: 1.60 —1.700 Band 10: 8.125-8.475 Range Band 2: 0.63-0.69 Band 5: 2.14 —2.185 Band 11: 8.475-8.825 Band 3h1• : 0.76-0.86 Band 6: 2.185-2.225 Band 12: 8.925-9.275 Band 3B': 0.76-0.86 Band 7: 2.235-2.285 Band 13: 10.25-10.95 Band 8: 2.295 2.365 Band 14: 10.95-11.65 Band 9: 2.360-2.430 Ground Resolution 15m 30m 90m Swath 60km 60km 601cm Width Quantization 8bit 8bit 12bit • Nadir Looking . Backward looking 18

Table 2. ASTER scenes used in this stud Date Wave- Acquired length ASTER ID Day/Night Regions LIB AST_L113_0030711200022184605172003141236 July 11, 2000 VNIR, Daytime SWIR, TIR LIB AST_LIB003_10092002081047_10302002085721 October 9, 2002 TIR Nighttime L2 05 AS1'05_003100920020810470000000 October 9,2002* TIR Nighttime L2 08 AS1'08_003100920020810470000000 October 9, 2002* TIR Nighttime LIB is Level IB data L2 is Level 2 data 05 is the emissivity product 08 is the temperature product * produced from LIB data acquired on this date 19

II. Background 2.1 Thermal Infrared (TIR) Remote Sensing Background Electromagnetic (EM) energy that reaches the earth's surface is called incident radiation and it can be transmitted, absorbed, emitted, scattered and/or reflected by the target surface. The EM spectrum is divided into approximately a dozen general regions (Sabin, 1997), however it should be noted that the names and wavelength boundaries for the IR regions vary depending on the author. The Infrared region is further subdivided into the Visible or Near Infrared (VIS, MR, V-NIR), Short Wave Infrared (SWIR) and Thermal Infrared (TIR), —0.7gm to 1.5gm, —1.5gm to 3gm, and —8gm to 14gm, respectively. Emitted energy in the TIR region is a function of the mineral structure (chemistry) and its kinetic temperature. The spectral features arising from the mineral structure allow for the identification of the surface material. TIR spectroscopy is based on the principle that the vibrational motions occurring within a crystal lattice produce spectral features at fundamental frequencies that are directly related to the crystal's structure and composition (Feely and Christensen, 1999). It is the variation in absorption features in a TIR spectrum that allows the identification of a specific mineral using one of several feature identification techniques. Radiant energy (L) is a function of the object's kinetic temperature and its wavelength dependent emissivity (Gillespie et. al., 1999). These are described in a relationship through the Planck equation:

Lo„T) = EA{C1X-5/[eXp(CAT)-1}}

CI = 3.74 x 10I6 Wm2, C2 = 0.0144mK

E = emissivity, A= wavelength in gm, T = kinetic temperature in degrees Kelvin

An object that absorbs TIR wavelengths and reemits all of that energy as a function of temperature and wavelength is known as a blackbody radiator (zw=1.0). A blackbody 20

curve is featureless at all temperatures and wavelengths and shifts towards longer wavelengths with increasing temperature (Fig. 3). 21

A

0 2 4 6 8 10 Wavelength (in microns)

Figure 3. Blackbody radiance curve. Note the shift in peak radiant energy to shorter wavelengths as temperature increases.

22

Emissivity is the ratio of radiant flux from a surface to that of a blackbody at the same kinetic temperature. Emission varies with wavelength due to the vibrational properties of specific molecular bonds, spatial geometry and number and type of atoms inherent in the surface of a material (Lyon, 1965; Hunt, 1980; Siegal and Gillespie, 1980; Salisbury and Walter, 1989). These properties cause the selective absorption of energy at specific wavelengths. The main TIR spectral absorption feature in silicate minerals that occurs from — 9gm - —12gm is generated by the fundamental stretching frequency of the Si-0 bond. This feature shifts to lower frequencies with increasing depolymerization (Salisbury and Walter, 1989). This spectral feature is examined for the identification of geologic materials within the primary atmospheric windows on Earth (Salisbury and Walter, 1989). Absorption bands in the TIR can be affected by the passage of energy emitted from a surface through the atmosphere to the recording instrument. Water vapor, carbon dioxide and stratospheric ozone obscure a large volume of the TIR region. Wavelength regions where this obscuration is minimal are known as atmospheric windows. There are three primary TIR windows for the Earth's atmosphere: 3jn - 5gm, 8jum -12gm, and the 17ktm - 25gm regions. The TIR region from 3gm -5gm overlaps with reflected solar energy during daylight hours, making interpretation difficult, and the 17gm -25gm region transmits less incoming energy than the 8gm -12gm wavelength region (Sabins, 1997). The region from 8jim -12gm is an atmospheric window, having 80-90% (less than that the nearer to 8gm) transmission in the TIR (King et. al., 2004).This region corresponds to the maximum energy emitted from the Earth's surface (at its average global temperature of 25°C). It is also the region in which most silicate minerals have unique absorption bands (Doizer, 1981; Kahle and Alley, 1992; Kahle et. al., 1991). Therefore, detection of the silicate major rock-forming minerals using TIR-based remote sensing and spectroscopy becomes possible. Typically photons only interact once at the surface after being emitted from a particle, due to their short path length relative to particle size, and therefore contain information only about that single particle (Ramsey, 1996). Mixed TIR spectra can 23

therefore be interpreted as a linear composite (i.e., "checkerboard mixing") of end- members (Ramsey, 2004; Thomson and Salisbury, 1993; Ramsey, 1996; Ramsey and Christensen, 1998; Christensen et. al., 2000). Because of this phenomenon, the energy detected is a function of the aerial percentage of the end members present (Ramsey, 2004). Therefore a linear deconvolution technique using a least-squares approach is applicable in order to determine these end-members and their proportions from a single TIR spectrum This is accomplished by utilizing pure end-member spectra from a spectral library (Ramsey and Christensen, 1998; Christensen and Harrison, 1993).

2.2 ASTER Satellite Background Launched on board NASA's first Earth Observing Satellite (EOS) Terra on December 18, 1999, ASTER, at a 705km orbital altitude, is the first commercial, sun- synchronous, polar orbiting satellite collecting five bands in the TIR (Abrams, 2000). ASTER was developed through a collaborative effort between NASA and Japan's Ministry of Economy, Trade and Industry (METI) with the cooperation of scientific and industry organizations in both countries ASTER was designed to acquire quantitative spectral data from reflected and emitted radiation of the earth's surface at the spectral and spatial resolutions necessary for scientific objectives (Abrams and Hook, 2002). The ASTER tasks were developed in order to make contributions to understanding the local and regional phenomena on the earth's surface and within its atmosphere (Abrams and Hook, 2002). Areas of scientific investigation identified by the international ASTER Science Team are: land surface climatology; vegetation and ecosystem dynamics; volcano monitoring; hazards monitoring; aerosols and clouds; carbon cycling in the marine ecosystem; hydrology; geology and soil; and land surface and land cover change (Yamaguchi et. al., 1998). ASTER's unique capabilities include spectral data acquisition at high spatial resolution and stereoscopic capability in the along track direction (Abrams, 2000). ASTER consists of three different subsystems; the VNIR covering 0.52gm -0.86gm, the SWIR covering 1.60gm -2.43gm, and the TIR covering 8.125gm -11.65gm. The ASTER 24

subsystems have the spatial resolutions of 15m, 30m and 90m and three, six and five spectral bands, respectively (Yamaguchi et. al., 1998). ASTER has the highest spectral resolution in the TIR of any spaceborne imaging instrument. The VNIR subsystem has an additional backward-viewing (27.6°) band at 0.76 - 0.861.1m (Yamaguchi et. al., 1998). This feature allows the generation of digital elevation models (DEM) with a posting dimension of up to 15m pixel and the capability to create orthorectified data sets (Yamaguchi et. al., 1998). All three ASTER subsystems cover a 60km swath width and have a nominal repeat time of 16 days. However, with ASTER's cross-track point capability (±116km from nadir), this repeat time can decrease to as little as five days at the equator and one day closer to the poles (Yamaguchi et. al., 1998). The TIR subsystem, the source of the data utilized in this study, has a fixed telescope with pointing and scanning done by a rotating mirror. This subsystem uses an array of ten mercury-cadmium-tellurium (Hg-Cd-Te) detectors per scan line, totaling 50 detectors (Abrams and Hook, 2002). The TIR instrument uses a whiskbroom scanner, five band pass filters and blackbodies at 270-340K for calibration. Additional specifics about the ASTER instrument and subsystems can be found in Kahle et. al. (1991), Yamaguchi et. al. (1998), and Abrams and Hook (2002). A range of different image and data products are available from the science team. For specific product generation and descriptions see Abrams and Hook (2002). The ASTER Level 1B and the validated Level 2 products are utilized in this work. The Level 1B Registered Radiance at Sensor product contains radiometrically calibrated, atmospherically corrected, and geometrically co-registered data for all bands (Abrams and Hook, 2002). The Level 2 (L2_05) emissivity and (L2_08) temperature products are produced from the temperature/emissivity (TES) separation algorithm by Gillespie et. al. (1999). The TES algorithm relies on an empirical relationship between spectral contrast and minimum emissivity, determined from laboratory and field emissivity spectra, in order to equalize the number of unknowns and measurements so that the set of Planck equations for the measured thermal radiances can be inverted (Gillespie et. al., 1999). Emissivities can be recovered with an accuracy and precision of 0.010-0.015 (Gillespie 25

et. al., 1999). The relative emissivities are found by ratioing the normalized emissivities, calculated from the normalized emissivity method temperature and the atmospherically corrected radiances, to the average emissivity. Because emissivities themselves are generally restricted to 0.7 < average emissivity < 1.0, and 0.75 < relative emissivity < 1.32, errors in emissivity are due to inaccuracy in the normalized emissivity method temperatures and are systematic. Thus, this technique of temperature-emissivity extraction can produce emissivity values over 1.00 which are an artifact of the ASTER L2_05 processing (Gillespie, 1999). ASTER products are atmospherically corrected using climate models or the Environmental Monitoring Center (EMC) global assimilation forecast system and NASA EOS (GEOS-1) (Gillespie et. al., 1999). The ASTER acquisition schedule algorithm allows the specificity of starting and ending times, and determines ASTER's activities one in advance (Abrams and Hook, 2002). This daily schedule has a prioritization mechanism making it possible to rank observations with higher scientific or program value using modifiable weighting factors prescribed by the Science Team (Abrams and Hook, 2002).

2.3 Previous TIR Linear Deconvolution Compositional Studies Spectral linear deconvolution was utilized in the determination of dune field composition and movement at Kelso Dunes, Mojave Desert, CA by Ramsey et. al. (1999). Results of previous linear deconvolution studies of felsic and mafic sands (Ramsey et. al., 1999) clearly identified surface mineralogy and the mixing patterns of the components (Ramsey, 2004). In the case of Kelso Dunes, laboratory and field analyses determined previously unidentified source inputs into the dune field and were compared to the airborne thermal infrared multispectral scanner TIMS TIR derived spectra (Ramsey, 2004). The mineral end-members identified through linear deconvolution of airborne data were confirmed with petrographic studies. Although ASTER has decreased spatial and spectral resolution compared to the airborne data, the majority of the end-members are expected to be identified through its use (Ramsey, 2004). However it is also noted that the lack of a 9pm band in ASTER (compared to the 26 airborne sensor) due to ozone absorption jeopardizes the recognition of many feldspar minerals in ASTER TIR (Ramsey, 2004). Airborne data from the Thermal Infrared Multispectral Scanner (TIMS) was utilized for a spectral deconvolution least squares approach to look at three sedimentary units of Meteor Crater, Arizona by Ramsey (2002). Subtle variations and patterns within Meteor Crater ejecta deposits validated the use of this technique for geologic mapping of a complex and mixed terrain (Ramsey, 2002). It was also determined that lithologic end- members derived from the image itself can be advantageous in a situation where prior knowledge of the region is limited or rapid image interpretation was necessary (Ramsey, 2002). Additionally, rock end-members, not mineral end-members, were utilized and thus the image derived maps compared more closely to geologic surveys (Ramsey, 2002). This implies that the lower spatial resolution of spacebome collectors such as ASTER is valid and useful where applied to a linear retrieval analysis, but the selection of end- members relies heavily on the input of additional information (Ramsey, 2002). Feely and Christensen (1999) determined the mineral compositions of a suite of igneous and metamorphic rocks using the thermal infrared emission spectra of these rocks in a linear spectral deconvolution algorithm. In this study, each major rock type was distinguished via its spectral characteristics. The qualitative determination of the rock type and dominant minerals and the quantitative reproduction of absorption features and mineral composition were obtained for igneous rock samples. As Hamilton and Christensen (2000) conclude, Feely and Christensen (1999) also found that the abundances derived from this technique are comparable to the error for traditional thin section mode estimates, which are ±5-15% for major minerals and < 5% for minor minerals. Feely and Christensen (1999) concluded that the quality of the obtained results demonstrates that a linear deconvolution of infrared emission spectra provides an accurate, rapid technique for determining the quantitative mineral composition of rock samples in a laboratory. Michalski et. al. (2004) used thermal infrared spectroscopic and remote-sensing analyses to determine the composition of weathered granitoid rock surfaces of the 27

Sacaton Mountains, Arizona. This study also applies a linear spectral deconvolution approach to determine the mineralogies of naturally exposed, weathered surfaces and exposed, clean rock surfaces. The deconvolution results from clean rock surfaces obtained comparable bulk mineralogy to that determined from results of point counting of rock slabs and thin sections. The deconvolution of weathered rock spectra indicate that compared to fresh samples, weathered surfaces are deficient in feldspar and are enriched in clay minerals. In conclusion, Michalski et al. (2004) determined that deconvolutions of multispectral remote-sensing data show a deficiency of total feldspar in the weathered rock units and lacks sufficient spectral resolution for the discrimination between different feldspars. 28

HI. Methods 3.1 General Field Observations and Sampling Techniques Field work for this project occurred over a one week period during July 2003 at Black Peak caldera (Fig 1). A color infrared (CIR) aerial photo was used in field work assessments (Fig. 4). General field observations involved examination of the age- relationships of the dozen overlapping lava domes, sampling for petrologic and spectroscopic analyses, and reconnaissance mapping of the mineralogy, vesicularity, surface cover and alteration within, and outside, of the caldera. These observations were compared to radiometric values of specific pixel locations in the satellite data. Collection of the geochemistry samples involved sampling outcrops and then chipping away the rock in the field to get to a clean surface for geochemical analyses. Also included were hand specimens for thin sectioning. A suite of samples with representative, flat, and intact surfaces was collected for lab spectra. At each sample location a GPS waypoint and description of the ground surface and notable features were recorded. In order to determine the relative ages of the domes, field observations were made of the contacts between each dome to discern, if possible, whether one was overlapping the other. The domes were also mapped with respect to structures such as creases, spines, cooling fractures and flow features, degree of weathering, and the amount and type of vegetative cover. Previously described fumerolic regions, and zones of past hydrothermal activity were visited and described (Knappen, 1929). The location of select pixels regions that may represent varying silicate types and abundances of silicates minerals identified in the ASTER TIR decorrelation stretch image were entered into a Trimble differential GPS Pathfinder Pro XRS (dGPS). The corresponding pixel areas on the ground were visited, sampled, and described in detail. 29

Red pixel dome

Blue Southeast pixel Avalanche dome Area Black Peak (1,032m)

Figure 4. Annotated Color Infrared (CIR) aerial photo of Black Peak caldera. The image was acquired on August 26, 1983 by the NASA Ames Research Center Alaska High Altitude Photography Program (AHAP). This image is an enlargement of the eastern corner of exposure no. 6034 on roll no. 3275. The scale is 1:18,000 and the caldera is -'3.5km in diameter. 30

3.2 Analytical methods 3.2.1 Geochemical analysis Samples collected for chemical analysis at Black Peak in 2003 were chipped, separated, labeled, and sent to the Washington State University (WSU) Geo-Analytical Laboratory. The lab analyzed the samples for major elements using a Rigaku automated X-ray fluorescence spectrometry (XRF). The lab prepared the samples by first grinding approximately 28g of the material in a swing mill with tungsten carbide surfaces (samples submitted in 2003) or an agate ball mill (samples submitted in 2004) for two minutes. Then, three and a half grams of the sample powder was weighed into a plastic mixing jar with 7.0g of spec pure dilithium tetraborate and mixed for ten minutes. The mixed powders were emptied into graphite crucibles that were placed on a silica fray and loaded into a muffle furnace for fusion. Each sample, now a fused bead, was reground in the swing mill or agate ball mill for 35 seconds. The resulting glass powder was first replaced in the graphite crucibles and re-fused for five minutes, then loaded into the XRF spectrometer. The concentrations of elements in the unknown samples were measured by comparing the X-ray intensity for each element with the intensity for two beads for each of nine standard samples and two beads of pure vein quartz was used as blanks for all elements except Si. A rhodium (Rh) target was run at 50keV/50mA with full vacuum and a 25mm mask for all elements (Johnson et. al., 1999). Instrument precision measured over a period of eight months on a single bead (standard GSP-1) normalized results standard deviations are < 0.004wt% for TiO2 and MnO, and 0.01 to 0.10wt% for FeO, CaO, MgO, K2O, P2O5, Na2O, SiO2 and Al203 (Johnson et. al., 1999). The precision measured on ten separate beads from the same basalt powder during a single XRF run at WSU normalized results standard deviations are <0.007wt% for TiO2 and MnO, and 0.02 to 0.09wt% for K 2O, P2O5, SiO2, Al203, FeO, CaO, MgO and Na2O (Johnson et. al., 1999). For a discussion on accuracy of the XRF results refer to Johnson et. al.(1999). Electron Microprobe analyses of polished thin sections were performed on the University of Alaska Fairbanks Cameca SX-50 electron microprobe equipped with four 31

wavelength dispersive and one energy dispersive spectrometer. The probe provides elemental analysis of areas as small as 2gm for all elements Z > 5 (Boron). Typical detection limit is 500-1000 ppm. Mineral analyses of plagioclase, pyroxene and hornblende used a 1-2 micron focused beam, spot size 0, an accelerating voltage of 15keV and a beam current of 10nA. See Table 3 for calibration element assignments, standards and working standards. Working standards were analyzed after calibration at the beginning of a run and before data collection at the beginning of a run that had been calibrated the day before. For analyses of each sample and the working standards back scatter electron (BSE) imaging allowed identification of the select mineral type and an EDAX Energy Dispersive X-ray Fluorescence Spectrometer (EDS) with the Genesis Spectrum SEM Quant ZAF software for x-ray peak chemistry to identify the potential sample point. For this identification process operating conditions were 30keV and 20nA. Once a mineral was identified and selected, three to five analyses were collected on each of five to ten separate crystals within each sample. Only data totals 98.5% to 101% for the working standards and sample analyses were acceptable. 32

Table 3. Electron microprobe settings: calibration, working standards and element assignments Hornblende and Pyroxene Calibration Element Standard F, Ca 334 Fluorite (CaF2) Na, Al, Si 615 TALBITE Mg 339 Spinel Cl 231 Scapolite (Meonite), USMN R6600-1 K 302 ORIO CT Ti 307 SPHENE lA Mn 328 Willemite Fe 620 Synthetic Almandine (SALM)

Hornblende and Pyroxene Working Standards 218 Hornblende (1-1B1), USNM 111356 219 Hornblende (HB2), USNM 143965

Feldspar Calibration Element Standard Ca, Al 202 Anorthite, USNM 137041 K, Fe 302 ORIO CT Na, Si 615 TALBITE

Feldspar Working Standards 416 Anal Feldspar glass 228 Plagioclase (Labradorite), USNM 115900 33

3.2.2 X-ray Diffraction Powders for X-ray diffraction analyses were ground from selected samples in an agate mortar and pestle to a grain size of < 11.1m. The powders were adhered to glass slides with petroleum jelly. The samples were analyzed using the University of Alaska, Fairbanks Rigaku Geigerflex X-ray diffractometer (XRD), with a solid state detector, at an operating voltage of 30kV and 30mA. The patterns were collected in a digitized manner using Materials Data Incorporated (MDI) DataScan. Samples were analyzed at 2- 60°, an initial 20 of 1.0, a step size of 0.05° and a dwell time of two seconds. Using MDI Jade, peaks with a relative intensity range of 10% to 100% were labeled with their 20 and d-spacing values. A report of these peaks was obtained using the software. Pattern indexing was conducted by identifying the 100% intensity peak in each pattern, identifying the mineral for which that is one of the strongest peaks, then each subsequent less intense peak. This process repeated until all peaks were either discarded, not matching any particular mineral, or labeled. Diffraction data for the mineral identification came from the Mineral Power Diffraction File Search Manual, 1981 and the Catalog of Joint Committee on Powder Diffraction Standards (JCPDS).

3 2.3 Laboratory Emission Spectra The surface samples collected during the 2003 field season were analyzed at the Image Visualization and Infrared Spectroscopy (IVIS) Laboratory at the University of Pittsburgh (UPITT) and at the Temperature Emissivity Spectrometer (TES) Laboratory at Arizona State University (ASU) using a Nicolet Nexus 670 Fourier Transform Infrared Radiometer (FTIR) Spectrometer that collects reflectance and emission spectra over the 0.4 - 25jim wavelength region, comparable to ASTER's TIR bands. The sample chamber was purged to minimize spectral signatures from H 2O and CO2 vapor. The instrument field of view is an ellipse with a —3cm major axis. The samples were heated for a minimum of 12 hours at 80°C to increase the signal to noise ratio because heating the sample increases the emissivity to measurable values above background. The top and bottom surfaces of each sample were photographed, recorded into a web-based database 34 and spreadsheet, and then placed in the sample chamber. The spectra from each surface, interior and top, are referred to as "i" and "t", and subsequent surfaces as "i2" and "t2", respectively. The samples were analyzed with 256 scans over 5 minutes 8 seconds per surface. At the beginning and again every four hours throughout the data collection session a blackbody heated at 70°C and at 100°C were used for calibration. The laboratory collection of emissivity has a resolution of —1%. The collected spectra collected were then linearly deconvolved.

3.2.4 Linear Deconvolution Ramsey and Christensen (1998) determined that spectra can describe a continuum consisting of pure endmembers. In the TIR, assuming that the emission from all components combines linearly in direct proportion to their area percentage, the spectra can be deconvolved to estimate the abundances of each endmember. Silicates have diagnostic absorption features in the TIR wavelength region indicating that spectral variations observed in thermal remote sensing satellite-based instruments may represent potential mineralogic variation and/or heterogeneities that may be confirmed with laboratory analyses (Ramsey and Fink, 1999). Laboratory emission spectra of select Black Peak samples were deconvolved with an algorithm that utilizes a Chi-squares minimization technique and the application of an input library of 45 known spectral endmembers (Table 4) to model the measured, mixed spectrum. This algorithm is a statistical determination of the best-fit endmembers for a mixed spectrum (Adams et. al., 1986; Sabol et. al., 1992). This technique uses a linear regression analysis, assuming normal distribution of the data, to solve for the matrix of unknown endmember fractions. The algorithm weighs the appropriate library endmembers to minimize the error difference between the modeled and the measured spectrum (Ramsey and Christensen, 1998). The Chi-squared equation is a summation of the square of the differences between the measured and calculated emissivities, divided by the standard deviation (Ramsey, 1996). The error is calculated by subtracting the model predicted emissivity obtained from the measured emissivity at each wavelength 35

(Ramsey, 1996). This measure is expressed as a single value for the entire wavelength region and is the root-mean-squared (RMS) error, which varies from 0 to 1. Lower values correspond to a better fit. There are two columns of results, one with a blackbody library spectra included and the other with the black body normalized out. Pure end-member spectra display greater spectral contrast than the rocks in which they occur and to account for differences in spectra band depth between the rock and the end-members, a blackbody end-member is included in the end-member suite (Table 4; Hamilton et. al., 1997). The normalized results are used in this analysis. 36

Table 4. End Member Spectral Library Standards used in linear deconvolution algorithm, ,, , la i'' ,111 ..i Andesine WAR-0024 8-17-95 Magnesio-homblende HS-115.4b Labradorite WAR-4524 1-2-96 Unknown amphibole WAR-0219 Bytownite WAR-5859 Anthophyllite (Amphibole) BUR-4760 Albite WAR-0235 8-16-95 Phlogopite HS-23.3B 12-27-95 Microcline AK-01 8-17-95 Perthite WAR-5802 1-3-96 Quartz Clinochlore (Chlorite) WAR-1924 Hornblende WAR-0404 12-27-95 Magnetite WAR-0384 12-15-97 Biotite flakes (oxides from BUR-840) Ilmenite WAR-4119 12-15-97 Obsidian Glass Sanidine WAR-RGSANO1 6-12-97 Oligoclase (Peristerite) BUR-060D Kaolinite (solid) Labradorite BUR-3080A 8-17-95 Dickite (powder; Kaolinite group) Anorthite WAR-5759 Illite (granular) Richterite (Amphibole) ASU-03 Blackbody Katophorite (Amphibole) BUR-2660 Albite (Cleavelandite) WAR-0612 12-23-95 Amazonite WAR-0650 8-17-95 Chlorite BUR-1340 12-29-95 Andesine BUR-240 8-4-95 Albite WAR-5851 Orthoclase WAR-5919 Enstatite (En93) NMNH-34669 Bronzite (Bz72) NMNH-C2368 Diopside (Di50) NMNH-107497 Augite (Wo44 En29 Fs20 Ac8) WAR-6474 Augite (Wo44 En28 Fs28) NMNH-9780 Hedenbergite (Wo50 En3 Fs47) NMNH-R11524 Anorthoclase WAR-0579 1-2-96 Muscovite WAR-5474 12-15-97 Actinolite HS-116.4B Gedrite (Amphibole) BUR-1700 Actinolite WAR-0354 Tremolite (High Fe) HS-315.4b From the Arizona State University Thermal Emission Spectroscopy Laboratory Spectral Library (Christensen et. al., 2000) 37

3.3 ASTER Remote Sensing data processing 3.3.1 Decorrelation Stretch Multispectral remote sensing satellite imagery is often analyzed by displaying three of the spectral bands in a red, green and blue (R, G, and B) color composite image. Gillespie et. al. (1986) describes this process in detail, which is reviewed here. The spectral information contained in the data are represented as colors displayed in the image. Multispectral images of spectrally featureless scenes are highly correlated from one band to the next, and a color composite made from these images have little dynamic range (Fig. 5.) Spectral information is not easily visible or useful in this type of image presentation. In order to view highly correlated, or redundant, information in multiple bands as a color image, the least correlated part of the spectra must be exaggerated selectively. The intent is to exaggerate the color saturation independent of lightness and without changing the hues. One technique for achieving this goal is the decorrelation stretch. A data array recorded by a satellite sensor can be displayed as an image that is analyzed by the user. Throughout this suite, data, scene, and image, different classification names are used to describe the characteristic ultimately displayed in color. Radiant fluxes from a scene are measured and integrated over time and wavelengths, and converted to digital numbers (DN) in the image domain. DN from the ASTER TIR used here varies linearly with calculated ground surface radiance of a subset of 90m pixels over a 601cm width scene. The DN values are thus measurements of intensity, or energy. 38

N / 158050'W 1km

Figure 5. Example of a TIR color composite of the Black Peak caldera region using ASTER TIR data as R=band 14 (10.95-11.65gm), G=band 12 (8.925-9.275um), B=band 10 (8.125-8.475pm) 39

Color pictures are created by assigning the primary colors (R, G, and B) to three planes of bands of image data taken in different spectral regions. In this case the spectral bands are outside of the visible wavelength region and thus these color portrayals are known as false color composites. These colors are interpreted by the viewer and perceived in three ways: hue, saturation and lightness (Gillespie et. al., 1986). The earliest work on the decorrelation stretch was by Taylor (1973) and augmented by Soha and Schwartz (1975). The three step technique consists of transformation of the original input bands to their principal components, separately stretched transformation of the variable and then the application of the inverse principal component transformation. The decorrelation stretch expands the pixel value region of highly correlated data along its principal axes P1 and P2, which are statistically independent so that the covariance of the principal components is zero (Fig. 6; Gillespie et. al., 1986). These principal components are numbered in order of descending variance, such that Pi describes the major fluctuations in the lightness of a scene and P2 describes the variance from PI. Increasing the contrast along P2 will exaggerate the image color (Gillespie et. al., 1986). The P1 and P2 images are independently stretched to equalize the variance to fill much of the data plane (Gillespie et. al., 1986). The axes are then transformed back to their original locations and displayed as a color composite picture (Gillespie et. al., 1986). 40

1

0 1

P A

0 11 1 0 B Figure 6. Schematic representation of the decorrelation stretch from Gillespie et. al., 1986: I. Example of variation diagram of data (A, B) with principal axes; II. Data cluster following principal component transformation and a random translation so there are only positive values; III. Linear contrast stretches applied to the "decorrelated" principal axes channels so that the variances of the principal axes are equalized; IV. The stretched data is reoriented to the original (A, B) coordinate system. The data cluster fills the plane and the data can be displayed in a wide range of colors. 41

Framework silicate structure is composed of interconnected Si-0 tetrahedrons forming a lattice. Also, framework silicates have their primary absorption features at shorter wavelengths than their primary emissivity features. Progressively more mafic silicates, chain and isolated silicates, have their primary absorption band in longer wavelengths and thus emission at shorter wavelengths. These fundamental spectral features are the basis for discriminating between rock types using decorrelation stretching of ASTER TIR bands 14, 12 and 10, decreasing wavelength regions (Fig. 7). Thus in the decorrelation stretch false color composite of R=band14, G=band12, and B —bandl 0 the pixels with predominately framework silicates appear red because the colors represented by the band wavelength region associated with the absorption bands, blue and green, would be deficient. In contrast, chain and isolated silicates appear as blue pixels, the color assignment of the band associated with the highest emissivity, and are deficient in red and green, the bands with highest absorption (personal communication, Ramsey, 2002). This technique has been effectively used for additional remote sensing and geologic applications in the VNIR and SWIR wavelength regions beginning with the use of aerial and simulated data sets by Abrams (1984) using simulated Landsat-4 imagery of a porphyry copper deposit, with aircraft images over the East Tintic Mountains of Utah by Kahle and Rowan (1980), and mapping alluvial fans in Death Valley California by Gillespie et. al. (1984). Additional studies also include the use of Landsat TM data in mapping the Xigaze (Tibet) ophiolite complex (Matthews and Jones, 1992), and in assessing groundwater in Hoggar, Algeria (Andersson et. al., 1992). This technique has also been used with TIR satellite remote sensing data by Ramsey et. al. (1999) to assess the silicate variations between a few large, monomineralic bodies such as those found at the Kelso Dunes, California. Using the Research Systems Inc. (RSI) Environment for Visualizing Images (ENVI) software package, the five bands of the ASTER Level 1B TIR product of the October 9, 2002 scene were subset into a — 70km 2 region including and immediately surrounding Black Peak caldera. The ENVI automated decorrelation stretch function was 42

used with the subset bands 14, 12 and 10. These bands were then used to generate a false color composite R=band14, G=bandl2, and 13—bandl 0 43

ASTER Bands 10 11 12 13 14

8 9 10 11 Wavelength (in microns)

Figure 7. Laboratory and ASTER emissivity spectra for example framework (quartz) and chain (hornblende) silicates and ASTER spectral bands R=14, 0=14, B=10 utilized in decorrelation stretch (after Rowan and Mars, 2003). The laboratory spectra a thin and ASTER spectra are thick. 44

3.3.2 ASTER derived emissivity and temperature The ENVI software Z-profile function was used to obtain emissivity profiles from the ASTER Level 2 emissivity product acquired in October 9, 2002, of specific, sampled pixel locations. The ENVI pixel value function was used to obtain radiance temperatures from the ASTER Level 2 temperature product acquired in October 9, 2002, of specific, sampled pixel locations. Laboratory emissivity profiles for snow and grass were obtained from the MODIS UCSB (University of California Santa Barbara) Emissivity Library and are also used for comparison. 45

IV. Results 4.1 Field results The domes in and around Black Peak have previously been described as dacitic (Detterman et. al., 1981). Little was known about their relative ages and the chronology of dome emplacement at the time of the publication of the regional geologic map (Detterman et. al., 1981). Combined results from fieldwork, petrologic and geochemical analyses now provide a general framework of dome composition and ages within and around the Black Peak caldera. The domes and flows within and spilling out of Black Peak caldera vary in composition, mineralogy and in the amount of alteration, weathering, and vegetative cover (Fig. 8). Domes below approximately 900m elevation tend to be covered with grasses and lichens and the higher elevation domes showed more freeze-thaw fractures and weathered surfaces. There are weathered and altered outcrops along the caldera walls and outside of the caldera with the appearance of altered volcanic necks and pre-caldera domes. In some instances, these domes and lavas appear as conglomeritic masses. Many of the domes along the margin of the complex have flow structures and localized collapse features. No large variations in the amount of vesicularity appeared to consistently exist over the entire complex. Vesicular and fine grained enclaves exist in many of the Black Peak lava domes both in the caldera and along the caldera rim. The dome directly north of the central depression has three distinctly different rock types cropping out (Fig. 8A; Fig. 9.). They consist of: 1) A red-colored matrix with mica, feldspar, and up to 4mm- long hornblende phenocrysts, and few visible vesicles, <0.5cm in size. 2) A pink-colored matrix with feldspar and hornblende phenocrysts, and no notable vesicles, and 3) A gray- colored matrix with homblende up to 2mm-long, feldspar phenocrysts and visible, numerous vesicles. These variations may correspond to cooling and oxidization during dome emplacement. 46

spine

rat ncalderaw all ,caldera II all 4 flow s VP* ta llus grasses

dome boundaries

Figure 8. Images of domes and features at Black Peak caldera A. This dome consists of rocks that appear distinctly different, which may correspond to cooling and oxidization during dome emplacement, referenced in the text. B. Dome along the margin of the complex, southeastern shore of Purple Lake, note tallus of neighboring dome contacts, vegetative cover and spine-like feature. C. Note flows with visible ridges perpendicular to flow direction. Photos A. and B by J. Adleman, 2003; Photo C. by R. G. McGimsey, 2003. Image locations are labeled on Figure 9. 47

Figure 9 depicts the dome complex divided into three sections for thrther discussion of relative age relationships. Section 1 is comprised of pre-caldera forming eruption (pre-cfe) domes and lavas outside the caldera and within the caldera walls (Table 5a.). The domes in section 2 are central to the complex, the highest in elevation, have freeze-thaw, and cooling fracture patterns, and are oxidized, probably from significant, prolonged weathering. The weathered and oxidized characteristics, including altered amphibole and overall dome contact relationships identify these domes as the oldest in the interior caldera complex and include the "red" and "blue" pixel domes noted in the satellite imagery described later in the text. This section includes the southeastern dome avalanche region which has a dated soil horizon (from below the avalanche) of —5000 years BP obtained from samples collected in 2001 (Table 5b; McGimsey et. al., 2003). Section 3 is comprised of domes and flows along the margin of the central dome field (Table 5c.). These domes and flows are lower in elevation, less weathered, have shallower slopes, and are more significantly covered in vegetation than those in section 2, and are identified here as younger than the section 2 domes. The more abundant vegetative cover on the section 3 domes and flows is most likely due to their lover elevation and thus less persistent snow covering. Section 3 flows also have flow ridge features expressed as undulating surfaces perpendicular to the southern caldera wall. 48

39 54.:" Amu " I $ 49' • Calaira Rim USGS, Chignik (C-3) Quadrangle 2001 Sample location Contour interval I OOft 2003 Sample locations dottetlines 50111 eComplete data set sample locations 0 Other sample Ictinliens referenced in text Other samples • :

•

N 19" 00 1 mile AptiVroximate mean declination. 1963 1 km 4 4 Unit wt% SiO2; brief description Section 3 { • 57.84-58.88; domes and flows • 58.64; dome in caldera, "blue" pixel dome 14 — 500 C yrs BP • 60.43-62.70; avalanched domes Section 2 58.64-63.28; domes in caldera • 63.28; oldest dome in caldera; "red pixel" dome I4 — 4,600 C yrs BP • 61.08-64.44; ash & pf from cfe Section I 0 60.49-65.35; pre-cfe domes & volcanics

Figure 9. Subset of USGS Chignik (C-3) Quadrangle topographic map. The domes and depicted age relationships, water bodies and locations A, B and C shown in Figure 8 are labeled. Unmarked regions within the dome complex are talus. Relative chronology has been determined combining field relationships and observations with geochemical and geochronological results. C m dates are from 2001 field sample data collected by C. A. Neal and R. G. McGimsey. etc—caldera forming eruption, pf=pyroclastic flow. 49

Table 5a. Section 1 Field sample descriptions e 03JABP_08 outcrop on varied lichen types rich with vesicular, fine caldera rim represent an older gr enclaves, plag and above Camp dome or flow hbl Lake 03JABP_11 dome host - hbl and plag outside phenos enclaves - more caldera mafic, rounded 03JABP_12 area of high brecciated surface vesicular alteration lichen and outside alteration caldera 03JABP_13 dome on highly altered large hbl and plag phenos, rim? boulder on ridge enclaves with lg. but just above "Mucky few vesicles Lake" 03JABP_15 dome? highest point vesicular, plag rich, no caldera rim vesicles CNB03_3 dome enclaves with few vesicles, lg plag phenos 03Mc_06 lava lava flow from lg plag few hbl phenos, columnar jointed vesicular block. 03Mc_07 lava breccia/flow that fragmental, clast floors pre-caldera supported valley 03Mc 09 lava Old (?) thermal area sulfur deposition 03Mc_l 0 lava altered volcanic biotite, muscovite? neck, pre- caldera, exposed in wall. 03Mc_l 8 dome From outer wall of blocks in dome - caldera, pre- breccia, altered caldera? 03Mc_1 9 dome or outside caldera wall non-vesicular enclaves, flow hbl and plag rich plag plagioclase phenos=phenocrysts, Ig= large, gr=grain, hbl=hornblende 50

Table 5b. Section 2 Field sample descriptions

p 03JABP_01, dome upper spine of "red oxidized, red, little hbl, 02 pixel" dome no vesicles, some plag phenos 03JABP_04rr dome cluster area of colored close qtz, mica, little hbl, packed rocks feldspar, little vescularity, biotite 03JABP_04g dome cluster area of colored close hbl, qtz?, vesicular, packed rocks fspar? 03JABP_09 flow out of from Black Peak? hbl rich, large plag caldera spilling out from dome 03JABP_10 collapsed altered, surface lg hbl and plag, hbl dome region may be altered 03JLBP_0 1 dome above camp redish matrix, plag and little hbl, altered, enclaves-rounded 03JLBP_02 dome on edge of smaller hbl rich, with plag dome at edge of phenos crease point 03JLBP_04 dome from spine on lower vesicular enclaves with dome above camp altered hbl, host lg phenos pf plag, some hbl 03JLBP_05 dome non-vesicular enclaves 1.5 to 11.0 cm long axis, finely crystalline, little hbl, more plag 03JLBP_06 dome in central valley dark vesicular-free enclaves, rounded, host hbl and plag phenos 03JLBP_07 dome crease structure lg plag phenos. and looks younger some hbl, no vesicles 03JLBP_08 dome contrast between vesicular enclave with dome and pumice qtz? or plag? host - breccia little hbl, some plag phenos CNB03_1 dome rounded, coarse gr inclusions 03Mc_03 dome top of dome south porphyric dacite, hbl of Black Peak and plag phenos proper 03Mc_05 dome dome west of Black few hbl, lg. plag Peak phenos 03Mc_16 dome homblende dacite, plag phenos and rounded enclaves with a few vesicles qtz=quartz, fspar=feldspar 51

Table 5c. Section 3 Field samples, descriptions and petrolo

P felt 03JAB13_06 flow or crease structure orientated dome 310-degrees, by Purple Lake 03JABP_07 flow or outer reach of lowest hbl dome dome at Purple Lake 03Mc_11 flow or "split" dome between hbl, maybe dome Purple Lake and main biotite, few dome cluster vesicles, vesicular enclaves, rounded 52

4.2 Whole Rock geochemical analyses Whole rock chemical analyses of the 2001 and 2003 Black Peak sample suite of pre and post-caldera eruption products span a range from --57-65wt% SiO2 (Fig. 10). Section 1, the pre-caldera forming eruption volcanics (altered volcanic necks, domes and conglomeratic masses) range from -'60-65wt% SiO2, andesites and dacites, and include the most siliceous sample material from the southern part of the caldera wall. Within the caldera the central overlapping domes of section 2 range between -'60-63wt% SiO2, all of which are andesitic except for the "red pixel" dome which is dacitic. Section 3, the marginal andesitic domes and associated flows, range from -'57-59wt% SiO2. There is a trend of decreasing silica content for each successively younger dome section identified via the field work (Fig 9; Fig. 10.), as shown in the generated Harker diagrams (Fig. 11). Na2O and 1(20 increase, and Al203, TiO2, MgO, CaO and FeO decrease with increasing wt% SiO 2 and outline a mixing trend between dacitic and andesitic endmembers. This information, combined with the addition of vesicular enclaves found in some, but not all, of the domes during field work is evidence for magma mixing of successively more mafic magma entering a shallower dacitic magma chamber (Browne et. al., 2004). CaO and Al 203 values for the red pixel dome sample may reflect a product of contamination or alteration. 53

10 9 Trachyte (Q<20%) Trachydacite (Q>20%) 8

0 7 + 6 0,,, 5 10 4 3 2 1 0 55 57 59 61 63 65 67 69 71 wt % Si02 Section 3 { n Youngest lava domes and flows Southeastern avalanched area * Blue pixel dome identified in ASTER imagery Section 2 • Domes in caldera Red pixel dome identified in ASTER imagery

Section 1 f + Pumice, Ash and PF from CFE 1 • Pre-cfe domes and lavas outside the caldera

Figure 10. Total alkali vs. silica (TAS) diagram of 2001 and 2003 samples from Black Peak (after Le Maitre, 2002) 54

19.0 0.18 A/2°3 • s•n P2CS 18.8 - 0.16' ASS A L L 18.6 - 0.14 • its • • • • 18.4 - • 0.12 18.2 - • 0.10- 18.0 - t • • A • A• A 0.08 17.8 - ! S 17.6 - 0.06 ' 17.4 - A 4. 0.04 17.2 - 0.02 17.0 0.00 0.7 3.75 TiO2 3.70 ••• Nap 0.6 • •AIVA a 3.65 • 0.5 . allakA, • • 3.60 • • 40 • •• t A. 40. 0 0.4 . • 3.55 • . • 3.50 0.3 . Ale A 3.45 • * • 3.40 0.2 • 3.35 • 0.1 . 3.30 . , • 3.25 0.0 3.20 5.00 7 MgO i • FeO Aff „At 4.50' - 6 - • • • AY • • 4.00 - 5 . Oa • * a 3.50 - 00 • •• 4 ' 3.00 - Mk sf 3 2.50 - 0•00 • 2 2.00 - • 1.50 - 1 0.00 0 9.0 1.6 CaO K20 8.5 - 1.4 ' • a AS• • . • 8.0 - U 1.2 -•A Se*ar 11 • AO 7.5 - sist 1.0 . di E . •

7.0 - Wars‘ 0.8 • 6.5 - •• 0.6 • -•• 6.0 - • • 0.4 5.5 - 0.2 5.0 L 0.0 57 58 59 60 61 62 63 64 66 57 518 59 60 61 62 63 64 65 6( Si02 Si02 Figure 11. Harker diagrams of 2001 and 2003 Black Peak samples (after Le Maitre, 2002). Symbols are explained in Figure 10 55

4.3 Petrologic Analyses 4.3.1 Microprobe

Dome lavas from all age sections contain An43-85 plagioclase. Dome pyroxenes comprise augite W035-44, En42.49, FS13-16 and enstatite W01-2, En63.72, Fs24.34 (Fig. 12), and also include a variety of sodic-calcic and calcic amphiboles. The pyroxenes also contain both compositions, which cluster in the enstatite and augite regions in the ternary plot on Figure 12. Amphibole contents vary between each identified dome-age section. The youngest section, 3, lacks amphibole in this data set, while both older sections have calcic, and sodic-calcic amphibole. In addition section 3 domes and lavas appear to lack orthopyroxene.

4.3.2 X-ray Diffraction X-ray diffraction patterns demonstrate that regardless of the dome and flow age relationships established here, several mineral types are identified in all three sections (Fig. 13). Micas, feldspars, amphiboles, pyroxenes and oxides are found in all three dome and flow sections. The oxides indexed include magnetite and ilmenite, and the micas include phlogopite, muscovite, the clay-mica montmorillionite, illite and lepidolite. Section 1 dome rocks also contain plagioclase, sanidine, and orthoclase feldspars, anthophyllite amphibole and muscovite. Section 2 lava feldspars include plagioclase, anorthoclase and sanidine. The pyroxenes in section 2 are diopside, augite and enstatite. Additionally, section 2 patterns identified include magnesio-hornblende and anthophyllite amphiboles, the micas muscovite, montmorillionite, illite, phlogopite and lepidolite, and the oxide magnetite. Section 3 includes plagioclase, and sanidine feldspars and pigeonite and augite pyroxenes, but lacks orthopyroxene. The micas found in section 3 are montmorillionite, muscovite, phlogopite, and illite. 56

50 50

Piegoni

A. n 50

An

50 50

B. Ab

Figure 12. Plagioclase and pyroxene ternary plots A. Pyroxene and B Plagioclase compositions 57

03Mc_l 0 61.31wt% S102 50 45 40 35 30 25 20 15 10 5 0 coo ° ttPc* 0At>. P s•4'' ‘c-t° At --- Top surface 03JABP_08 61.49 wt% Si02 — Interior surface 60 Mineral found 50 in probe and/or XRD Mineral found 40 in petrographic thin section

30 Decorrelation stretch ASTER image pixel color is top right 20

10

0

• N9 sre . (0(4 %QC) o 4).

Figure 13a. Section 1 summary of linear deconvolution, XRD and probe results 58

CNB03_2 59.91 wt% 5102 80

70

60 50

40

30 20 10 0 st • * c, 4`b.0° te 4. 4\ a ,zsv 4,` Oro CNB03_1 60.56 wt% Si02 60 0 0 50 Top surface 8 40 -80 Interior surface is 30 Mineral found E in probe and/or XRD 20 7r Mineral found in petrographic thin section •5 10 Decorrelation stretch ASTER image 0 pixel color is top right

s„4 o

03JABILO4g 80

70

60

50

40

30

20

10 0

Figure 13b. Section 2 summary of linear deconvolution, XRD and probe results 59

80

70

60

50

40

30

20

10

0

60

--- Top surface Top surface 2 — Interior surface Mineral found in probe and/or XRD -1-1.- 7 20 Mineral found in petrographic thin section 10 Decorrelation stretch ASTER image pixel color is top right 0

e .s? cte e /

Figure 13c. Section 2 summary of linear deconvolution, XRD and probe results (cont) 60

03Me 03 6136 wt% 60 . - Red 50

40

30

20

10

0 laza

, et r Reetr.> x ' ‘.,g •

0 20 0 --- Top surface tl — Interior surface Mineral found in probe and/or XRD Mineral found in petrographic thin section I Decorrelation stretch ASTER image pixel color is top right # .49 OE .i 0 # 4 • Qs 41 „i5, reç' ,e- .n:.i 0I' es .0,q , q * 0 its, et 6., 90 80 70 60 50 40 30 20 10 0

Figure 13d. Section 2 summary of linear deconvolution, XRD and probe results (cont) 61

03Mc_11 57.92 wt% Si02 50 45 40 35 30 25 20 15 10 5 0 case 4 e 4' tto, l\bg  (cc' / (14°

--- Top surface — Interior surface Mineral found in probe and/or XRD Mineral found in petrographic thin section

Decorrelation stretch ASTER image pixel color is top right

Figure 13e. Section 3 summary of linear deconvolution, XRD and probe results 62

2. 03JLBP_0 1 61.21 wt% SiO2 3. 03Mc_06 57.84 wt% 5102 70 50 60 45 40 50 35 40 30 25 30 20 20 15 10 10 5 O O 0 0 e, ve N.61\ tee els „JP 9-\ .00 c—fre 0+ ‘o. 44,0 e,so 40si•?2,4 sr -C" • et,  E 4

2. 03Mc_05 58.64 wt% SiO2 None CNB03_4 60.78wt% SiO2 80 70

C 70 60 60 50 50 40 40 30 30 20 20 10 10 0 0 / 0e, 4 / ../ 4\ (1/41, 6., ‘, tt1G eV/,j „S tb‘ 43/4' 3 cis 04?tt e ci e, 4' 4,. zt eP

--- Interior surface — Top surface Figure 131 Additional blue pixel region samples linear deconvolution results, 03JLBP 01 and 03Mc 05 are from section 2, 03Mc_06 is from section 3, CNB03_4 is not in an identified section 63

4 3 3 Laboratory emissivity spectra Emission spectra obtained from the IVIS and TES laboratories and the modeled spectra resulting from linear deconvolutions are shown in Figure 14 and are referred to as original and reconstructed, respectively. Figure 14a shows the MODIS UCSB Emissivity Library spectra at the wavelength range equivalent to that of the ASTER TIR subsystem. Section 1 samples shown in Figure 14b include 03JABP_08 which has deep emissivity lows of the interior spectra of —0.90 at —8.7pm and 9.2gm and an emissivity peak of —0.92 at —8.9pm and spreads from —8.0pm to —12.4gm The top surface spectra of 03JABP_08 is relatively flat with an emissivity of —0.99 spanning the entire wavelength region. Sample 03Mc_l 0 provides an interior surface spectra with an emissivity low of —0.95 at —9.2pm and a top surface spectra emissivity low of —0.97at —9.8pm. The overall emissivity low spectra of 03Mc_l 0 spans from —8pm to —12.2pm. Laboratory emissivity spectra from section 2 lava samples are shown in Figures 14c, 14d and 14e. Sample 03JLBP_07 top and interior surfaces produce spectra with an emissivity low of —0.95 at 9.1pm and range from —8pm to —14pm Spectra from the top surfaces of samples 03MBP_04 and 03Mc_16 have smaller amplitudes than those from their interior, and range from —8.1gm - —12.4pm The interior surface spectra of 03JLBP_04 has an emissivity low of 0.93 at —8.9pm. The second top surface spectra of 03Mc_16 has an emissivity low of 0.90 at —10pm and the interior surface emissivity low of 0.89 is at 9.5gm. The top surface spectra of 03JABP_04g emissivity low is 0.94 at —9.1pm and spans from —8 to — 12 gm. Sample CNB03_2 top and interior surface samples have emissivity lows of 0.93 and 0.86 at —9.1pm and span the wavelength region of —8.1 gm to —12.7pm. The interior and top surface spectra of samples 03JABP_01, 03Mc_03 and CNB03_1 are all similar in shape and range from —8pm to — 12.6gm. 03JABP_01 and CNB03_1 interior spectra have emissivity lows of 0.92 and 0.83 at —9.4pm and —9.2pm, respectively. Their top surface spectra have emissivity lows of 0.94 and 0.90 at —9.1gm and —8 9pm, respectively. The interior surface spectra of 03Mc_03 has an emissivity low of 0.87 at —8 9gm, and the top surface spectra has an emissivity low of 0.92 at —9.2gm. The interior surface spectra of 03Mc_12 has two separate 64

emissivity lows at —9.1iim and 10 2pm with emissivities of 0.89 and 0.90, respectively. The top surface spectra has an emissivity low of 0.93 at —9.5pm The general emissivity low curve ranges from —8.8pm to —12.7pm Figure 14f shows laboratory emissivity spectra of section 3 sample 03Mc_11. There are two top surface spectra for sample 03Mc_11, both have an emissivity lows at 0.98 and 0.94, both at —9.2pm and the low spans —8.1 µm to —12gm. The interior laboratory spectra for the section 1 sample suite emissivity lows of 0.90 and 0.95 are at same wavelength of —9.2pm. The top laboratory spectra for the section 1 samples are also similar, varying from 0.96 to 0.99 in emissivity throughout the wavelength region. The interior and top surface laboratory spectra for the section 2 samples have emissivity lows of 0.85 to 0.95 and 0 90 to 0.97, respectively at 9.0±0.2pm. The section 3 sample emissivity values fall within the range of sections 1 and 2, at the same wavelength of section 1. 65

1 01 1.00 0.99 0.98 Vl 0.97 0.96 0.95 0.94 0.93 7 8 9 10. 11 12 13 14 15 Wavelength (microns) Dry Grass Snow

Figure 14a. Dry grass and snow laboratory emissivity from the Moderate Resolution Imaging Spectrometer (MODIS) University of California Santa Barbara (UCSB) Emissivity Library 66

03JABP_08 Red 1.00 0.98 0.96 0.94 0.92 0.90 0.88 03Mc_l 0 Red 1.00 0.98. 0.96. 0.94. 0.92. 0.90 0.88 7 8 9 10 11 12 13 14 15 7 8 9 10 14 15 Wavelength (microns) — Original t — Original i — Reconstructed t — Reconstructed i — Oct 02 ASTER

Figure 14b. Section 1 laboratory and ASTER satellite emissivity spectra. i=interior surface, t=top surface, original=collected spectra, reconstructed —linear deconvolution best-fit. Decorrelation stretch pixel color is indicated after the sample name. 67

03JLBP_07 Blue

1.00 0.99 0.98 0.97 0.96 0.95 0 94 03Mc_16 1.02 Red 1.00 0.98 •E 0.96 0.94 0.92 0.90 0.88 031LBP 04 Red 1.00

0.98

0.96

0.94

0.92 7 8 9 10 11 12 13 14 15 7 8 9 10 11 12 13 14 15 Wavelength microns) Original t — Original i Reconstructed t — Reconstructed i Original t2 Reconstructed C — Oct 02 ASTER

Figure 14c. Section 2 laboratory and ASTER satellite emissivity spectra. i=interior surface, t, t2=different top surfaces, original—collected spectra, reconstructed—linear deconvolution best-fit. Decorrelation stretch pixel color is indicated after the sample name. 68

03JABP 01 Red 1.00

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0 90

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0.87

7 8 9 10 11 12 13 14 15 7 8 9 10 11 12 13 14 15 Wavelength (microns) — Original t Original i — Reconstructed t Reconstructed i — Oct 02 ASTER

Figure 14d. Section 2 laboratory and ASTER satellite emissivity spectra. i=interior surface, t, t2=different top surfaces, original=collected spectra, reconstructed=linear deconvolution best-fit. Decorrelation stretch pixel color is indicated after the sample name. 69

03Mc_12 Red 1.00 0.98 0.96 0.94 0.92 0.90 0.88

CNB03 1 Red I 05

1 00

0.95

0.90

0.85

0 80 Red

7 8 9 10 11 12 13 14 15 7 8 9 10 11 12 13 14 15 Wavelength (microns) Original t — Original i Reconstructed t — Reconstructed i — Oct 02 ASTER

Figure 14e. Section 2 laboratory and ASTER satellite emissivity spectra. i=interior surface, t, t2=different top surfaces, original=collected spectra, reconstructed=linear deconvolution best-fit. Decorrelation stretch pixel color is indicated after the sample name. 70

03Mc_11 1 01 Red 1.00 0.99 0.98 Vi 0.97 0.96 0.95 0.94 0 93 7 8 9 10 11 12 13 14 15 Wavelength (microns)

Original t Reconstructed t Original t2 Reconstructed t2 — Oct 02 ASTER

Figure 14f. Section 3 laboratory and ASTER satellite emissivity spectra. i=interior surface, t, t2= different top surfaces, original=collected spectra, reconstructed=linear deconvolution best-fit. Decorrelation stretch pixel color is in top right corner. 71

1. 1.02 1.00

0.98 0.96

0.94 0.92 0.9 Blue 2. 1 02 03Mc 05 1.00 0.98

VJ 0.96 5 0.94 0.92 0.9 0 88

3. 03Mc 06 Blue 1.00

0.98

0.96

0.94

0.92 7 8 9 10 11 12 13 14 15 7 8 9 10 11 12 13 14 15 Wavelength microns) Original t Original i Reconstructed t Original t2 Reconstructed i Reconstructed t2 — Oct 02 ASTER Figure 14g. Additional blue pixel samples laboratory and ASTER emissivity spectra from sections 1, 2 and 3 as labeled. 72

4.3.4 Linear deconvolution Figure 13a summarizes the linear deconvolution results for samples from the section 1 lava domes. 03Mc_1 0 interior and top surface deconvolution results are similar in mineralogy yet more obsidian glass, micaceous minerals and illmenite peaks resolved from the top surface spectra. The interior and top surface linear deconvolution results for 03JAB13_08 vary in mineralogy although both surfaces are predominately bytownite and anorthoclase feldspar. Spectral deconvolution results indicate abundant glass and micas from the top surface spectra. Figures 13b, 13c and 13d summarize the linear deconvolution results of samples from section 2. The 03JABI3_04g top surface spectra are best fit by the framework silicates bytownite and albite, followed by the pyroxene enstatite (En 93). The interior and top surface spectra for sample CNB03_2 are best fit with the model of bytownite and the next most abundant mineral type is amphibole. The majority of minerals modeled to best fit the spectra of the top and interior surface results of CNB03_1 are framework silicates, followed by amphibole. Both interior and top surface spectra for sample 03JLBP_04 are best fit by the framework silicates bytownite and oligoclase, respectively. The next most abundant mineral fit to the top surface spectra is diopside. The modeled minerals for the top surface spectra of sample 03JLBP_07 consists principally of bytwonite and labradorite, however the most predominant mineral in the interior surface results in an amphibole. The sample 03Mc_16 deconvolution result is mostly plagioclase for both interior and top surfaces, followed by illite for the interior surface. 03JABP_0 1 linear deconvolution results for the interior and top surfaces are predominately illite. The top surface model results also contain equivalent amounts of quartz and dickite. The interior surface spectral modeled results of 03Mc_03 is the framework silicate bytownite in general, followed by quartz, and then anorthoclase. The top surface best fit minerals are mainly anorthoclase, followed by obsidian glass and anorthite. Bytownite and oligoclase are the most abundant modeled minerals in sample 03Mc_12 interior and top surface results, respectively. 73

Linear deconvolution results for section 3 are summarized in Figure 13e. The resulting modeled top surface mineralogy of sample 03Mc_11 is principally the framework silicate bytownite and then, less abundant, are dickite and obsidian glass. The interior surface modeled result of the same sample is dominated by illite, followed by quartz.

4.4 Satellite data 4.4.1 Decorrelation stretching Figures 13 and 14 display the pixel colors for the sample locations. The pixel color changes are gradual between each section of the caldera (Fig. 16.). The majority of section 2 and 3 domes in the eastern and northern portions of Black Peak caldera are dominated by red pixels in the ASTER imagery (Fig. 9; Fig. 16). The ridge extending northwest of the caldera and the low-lying region extending southeast of the caldera, including the dome avalanche region of section 2 and regions characterized in section 1 (Fig.9 ) also consist of predominately red and orange pixels. A red and orange region approximately 7-10 pixels wide exists south of the caldera and extends from the southwest to the northeast, as is visible on the lower section of Figure 16B. The southwestern region of the caldera is dominated by blue pixels, including the flows in section 3 and domes in section 2 (Fig. 9; Fig.16). The lowlands to the west and east of the caldera show predominately green and blue pixels in the ASTER decorrelation stretch image. 74

In tn 0 O 1/4t, tn lilac': Peal. olcuno

0 en O in V1

cimminol

159°45'W 159°15'W

Figure 15. July 2000 ASTER VNIR FCC (3, 2, 1), a —701cm2 subset area of the October 2002 scene is in the black box. The scene visible here is —551cm wide. 75

r \ I 1).110(( I pit • I \ n Aril ,1 I h n iii

kr) O In Caldera Rim

"Red pixel" dome

"Blue pixel" done -

SE alanched Area

1km 158°50'W

Figure 16. A. ASTER T1R bands 14, 12, and 10 decorrelation stretch of October 9, 2002 scene draped on an ASTER derived digital elevation model (DEM) with 20% vertical exaggeration. B. Map view of same decorrelation stretch. Black dots are 2001 and 2003 sample points. 76

4.4.2 ASTER emissivity profiles Figure 14 displays emissivity data from the ASTER Level 2 emissivity product acquired in October 2002, and snow and dry grass spectra from the MODIS UCSB Emissivity Library. This section will focus on describing the ASTER derived emissivity spectra of the three regions sampled and labeled in Figure 9. Figure 14b displays emissivity plots for two sample locations in section 1. ASTER spectra of sample region 03JABP_08 shows the emissivity low is 0.98 at —9.1p.m. There is an emissivity low of 0.98 at —9.34gm for the location of sample 03Mc_10. The emissivity low region of the ASTER spectra for both locations span —8.4gm to —10.6gm The ASTER emissivity spectra for section 2 locations are shown in Figures 14c, 14d, and 14e. 03Mc_16 and 03JAB13_04g both have an emissivity low of 0.98 at —9.3gm, and the emissivity low of 03JLB13_07 is 0.95 at —9.2gm. The emissivity low region spans the range of —8.9gm to 10.9pm for all three pixels. ASTER derived emissivity spectra of the CNB03_2 sample location has a low of 0.99 at —9.2gm and spans the range of —8.8gm to —10.9gm. The sample location for 03JABP_01 has an emissivity low of 0.99 at —9.6gm. The emissivity low region spans —8.9pm to —10.8gm. The emissivity low of 03Mc_03 is 0.97 and is at —9.3pm and spans the range from —8.8gm to —10.8pm The ASTER derived emissivity spectra for location CNB03_1 has an emissivity low of 0.99 at —8.9gma. The ASTER derived spectra for sample location 03JLBP 04 has an emissivity low of 0.98 at —9 1pm, and the emissivity peak of 0.99 is at —10.8pm. The emissivity plot for 03Mc_12 is relatively flat in shape and features a subtle emissivity low of 0.98 at —9.4pm. Figure 14f shows the emissivity low of 0.97 is at —9.1pm and the emissivity peak of 0.99 is at —10.8gm for location 03Mc_11. The ASTER emissivity spectra for the red pixel sample regions do not show a distinct feature separating them from the blue pixel ASTER emissivity spectra. Both red and blue pixel region ASTER emissivity spectra have emissivity lows at approximately the same wavelength and emissivity. 77

V. Discussion 5.1 Age relationships The section 1 domes and flows are identified as the oldest features in this study and likely pre-date the caldera forming eruption (Fig. 9). The reason for this age constraint is because the domes and volcanic neck features cropping out within the caldera walls are clearly truncated by the caldera forming eruption. Additional section 1 domes and lava flows outside of the caldera are also grouped as pre-caldera in age because they appear stratigraphically older than the caldera forming eruption products and show extreme alteration and weathering features not seen in any of the interior caldera domes. The section 2 samples include evidence of altered hornblende, possibly due to prolonged exposure and weathering. The section 2 domes centrally located within the caldera are thought to be the oldest domes to erupt after the caldera forming eruption due to their extensive freeze-thaw fractures. The southeastern dome avalanche region of section 2 has developed wide-spread soil and vegetated cover (Fig. 9). Altered hornblende is absent in section 3 domes, in which this magmatic mineral appears more fresh. The section 3 domes and flows along the margins of the complex are thought to be the youngest because they are less weathered and have significant flow ridges, creases and spine features preserved on their surfaces (Fig. 9). The surfaces of these preserve some primary lava dome and flow creases and undulating features perpendicular to the caldera walls that may reflect flow emplacement directions (Fig. 8). The geochemical data reveal decreasing SiO 2 content for each successively younger dome section (Fig. 9; Fig. 10). The section 1 pre-caldera and caldera forming eruption products range between —60-65wt% SiO 2 with the highest value resulting from the southern caldera wall. The "red pixel" dome within section 2 has the highest intra- caldera SiO2 content of —63wt%. The rest of the section 2 caldera domes and the related dome avalanche deposits represent a decrease in SiO2 down to 60wt%. The section 3 lava domes and flows are the least Si02-rich with —57-59wt%. The decreasing SiO2 with age, and the apparent linear mixing trends visible in the Harker diagrams shown in Figure 11, indicate that mafic magma additions to a crustal dacite reservoir occurred during the 78

period of time in which the intra-caldera dome lavas erupted at Black Peak. Additional evidence for inputs of mafic magma into the Black Peak system includes non-vesicular and vesicular, rounded, mafic enclaves occurring in equal proportions in domes from all age sections. Apparently, a relatively long-lived, continuous magma series interacted prior to, throughout, and after the caldera forming eruption. This may indicate a relatively short-term series of events encompassing all of these eruptive products. For if there were long periods of time in between the pre-caldera domes, the caldera forming eruption and the post-caldera domes, a less agreeable mixing trend, and perhaps more of a fractionation signature would characterize the geochemical data. Additionally, the section 3 lavas do not contain orthopyroxene, whereas the older domes do. This change in mineralogy away from what is consistently present in the older more siliceous domes may suggest a significant change in the chemistry of the magmatic system towards a more mafic bulk composition. Although many arc andesites and dacites contain two pyroxenes (ortho and clino), it is worth noting that orthopyroxene is also absent in the andesite at neighboring Aniakchak volcano, although it appears to be a stable phase in the rhyodacite (Fig. 1; Dreher et. al., in press). Thus, its absence in the section 3 domes could also indicate the addition of more mafic magma with time at Black Peak.

5.2 ASTER satellite image relationships 5.2.1 Comparison of ASTER satellite imagery and bulk dome rock compositions A comparison between the bulk lava dome compositions and pixel colors in the decorrelation stretch derived from the ASTER TIR data reveals a general agreement between pixel color and bulk SiO2 content. Specifically, the red pixels identified and compared to laboratory results correspond with domes between 60 to 65wt% SiO 2, while the blue pixel regions identified and compared to laboratory results correlate with samples containing <6 1 we% SiO2. Despite the small overlap in ranges, this outlines a rough trend where pixel color may give an indication of the bulk SiO 2 content of the dome lavas. Since bulk composition also changes as a function of dome age (Fig. 10), the pixel colors should also group accordingly. For example, samples from sections 1 and 2 79 tend to have the highest SiO2 compositions between 60 to 65wt% while section 3 contains rocks with 57-59wt%. Thus, it is expected that most of the blue pixels would lie within section 3, and most of the red pixels would be confined to sections 1 and 2 However, blue and red pixels are found among all of the age sections, regardless of the mapped trends in SiO2. There are two reasonable explanations for this. First, it is possible that more extensive sampling and characterization of the dome compositions would reveal more overlap in the compositions of the domes from each of the outlined age sections. Second, it is possible that the small, —lwt% overlap in S10 2 content between the red and blue pixel-related samples explains the occurrence of both pixel types in each age section. For example, the red pixel regions within sections 2 and 3 are identified with samples that contain —61 wt% SiO 2 - at the lower end of the range described above. In addition, some samples identified with blue pixel regions have SiO 2 up to 61wt%. Thus, although a correlation does exist, it may not represent a complete separation of pixel colors based on bulk rock SiO2 content. The compositional overlap among the age sections found thus far will most likely be maintained even if additional sampling and characterization is completed, in fact, half of the samples reviewed here have —61 wt% SiO2. This would indicate that more field work and laboratory analyses would reveal additional compositions within the lwt% overlap in the compositions of the domes from each of the outlined age sections, and it is likely that the limited compositional range overlap explains the occurrence of both pixel types in each age section. In this study, the red pixels appear to correlate with higher bulk rock SiO 2 content, and the blue pixels correspond with lavas with lower SiO 2. Watanabe and Matsuo (2003) using a decorrelation stretch of ASTER data, report similar findings in their study of a suite of basaltic to rhyolitic rocks in the axial volcanic chain of the Ethiopia Rift Valley. In particular, they found that red pixels correlate well with bulk rock types in their region with the highest SiO2wt%, similar to what is determined at Black Peak. Watanabe and Matsuo (2003) also report that blue pixel regions correspond to areas of lowest wt% Si02. Ramsey et. al. (1999) utilized the decorrelation stretch processing technique in the investigation of the quartz-rich Kelso dunes in proximity to the basaltic cinder cones of 80

the Cima volcanic field. In the decorrelation stretch of a thermal infrared multispectral scanner (TIMS) airborne scene of this region the more siliceous dunes appear red and the less siliceous basaltic cinder cones appear blue-green. These three studies demonstrate that the use of decorrelation stretch applied to thermal remote sensing data can be used to relatively assess the SiO2wt% for a given, specific region. For example, a red pixel in the Black Peak ASTER decorrelation stretch imagery does not necessarily represent the same SiO2wt% as a red pixel region in the TIMS data from Kelso dunes, but both do represent the highest SiO2wt% for their specific scene and location. Additionally, this may resolve why there are both red and blue pixels for the samples at Black Peak that have —61wt%SiO2. In essence, the rock types in and around the dome complex consist predominately of andesite and dacite and their compositional variation may not be distinct enough to be resolved using this technique.

5.2.2 Comparison of ASTER and laboratory emissivity spectra and petrologic data The use of ASTER emissivity spectra to identify the mineralogy of 90m by 90m pixel sized ground surface regions applied to a young volcanic area has seldom been employed, especially in remote regions known for consistent cloud cover and potentially vegetated surfaces like those in the North Pacific. In general, the ASTER emissivity spectra agree well with the laboratory spectra. The emissivities obtained from ASTER data are approximately 0.04 to 0.15 higher, but their shape and the position of the emissivity lows, centered between 8.9pm and 9.3pm, are similar to those of the laboratory emissivity spectra collected from the sample surfaces and interiors. This indicates that the ASTER satellite data did resolve the spectral signatures of the predominant magmatic and alteration-product minerals present in much of the Black Peak lavas (Table 5; Fig. 16). As noted above, the ASTER derived emissivity spectra are higher than those produced by the laboratory spectrometer. Apart from the primary rock features that are reflected in the ASTER emissivity profiles, additional factors contribute to the shape and amplitude of the ASTER spectra. Thus, the increased emissivity of the ASTER spectra is 81

due to the variety of additional features which affect the spectral response of a pixel region on the ground surface. Additional factors that need to be considered when examining the ASTER data from Black Peak, but are absent from the samples analyzed in the laboratory are. vegetation, snow, weathering, soil development, scattering, and atmospheric affects. There are ASTER emissivity spectra that have a similar shape and trend to the UCSB MODIS emissivity of snow (Fig. 14a). However, these are restricted to only three spectra from all three age sections combined. The October 02 ASTER emissivity spectra for the pixel region of sample CNB03_1, 03Mc_19 (Fig. 14e) and 03Mc_12 (Fig. 14g) are relatively flat at an emissivity of —0.98 for the entire wavelength region and reflect the shape the snow emissivity spectra. Temperatures of these pixels obtained from the ASTER Level 2 temperature product of the October 2002 scene are —0°C indicating the presence of snow within the pixel area. Although a few of the sample locations appear to be compromised by snow, it appears that a portion of the ASTER spectra reflect the rock properties themselves in these cases.

5.2.3 Comparison of ASTER pixel color, emissivity and mineralogy Additional correlations between the decorrelation stretch image and the dome lava mineralogies may also contribute to pixel colors. A comparison between the samples from red pixel locations dispersed in all three age sections, and the mineralogies derived from linear deconvolutions of the laboratory spectra demonstrates that red correspond well with samples dominated by micas/clays (sheet silicates) and plagioclase and potassium-rich feldspars (framework silicates) in both top and interior surfaces (Fig. 13). The interior caldera walls and the ridge extending northwest from the caldera rim are also dominated by red pixels and generally consist of clay and mica alteration products identified in hand samples and field observations. There is an additional region in the Black Peak image that is dominated by red pixels, but that was not sampled or visited during the field season. This region may also be clay and mica or feldspar-rich, if the decorrelation stretch results are applied to regions outside Black Peak that were not observed during the fieldwork. Watanabe and Matsuo (2003) conclude that quartz and 82

glass are prevalent in red pixel regions of their processed imagery of the Ethiopian Rift Valley. Rowan and Mars (2003) also utilized the decorrealtion stretch technique applied to ASTER emissivity data of Mountain Pass region of California and concludes that red regions in the imagery correspond to quartzite, sandstone, silicified rocks and granitic gneiss. Consistent with the findings at Black Peak presented here, and by others, there is the correlation between framework and sheet silicate abundances and red pixel color. The blue pixel regions appear to be more complex in terms of the corresponding sample mineralogies. In general, most samples collected from blue pixel regions of processed Black Peak ASTER imagery yield laboratory spectra which reflect significant amounts of amphibole. Specifically, the surface spectra collected from all samples from the blue pixel regions have up to 32% amphibole area fractions. The laboratory spectra from the interiors of those same samples reveal only up to 8% amphibole and the surface spectra appear to yield a greater proportion of amphibole than the interior spectra, when both should be approximately equal. This may be due to crystal orientation and fractured surface variations between the two surfaces. It is important to note that although both red and blue pixels samples have lichen adhering to their top surfaces, this is the case for all of the blue pixel samples discussed in this study. In addition, the laboratory emissivity spectra of samples from blue pixel regions appears different from the rest of the laboratory spectra collected from the top surfaces of the other samples examined in this study. The samples from blue pixel regions have two equally wide emissivity lows centered at —9.1)tm and —9.8pm (Fig. 14c: Fig. 14g), as opposed to the emissivity lows of the red pixel spectra at —8.8)im and —9.1 µm. The difference in the emissivity low doublets from blue pixel region samples could indicate that the lichen covering has affected those spectra, and does not reflect amphibole contents only, or that this doublet is a reflection of the amphibole content. Watanabe and Matsuo (2003) found that olivine rich and andesine poor basalts are recognized as blue pixel regions of the Ethiopian Rift Valley ASTER scene. Rowan and Mars, 2003 concludes that blue regions in decorrelation stretch ASTER imagery of Mountain Pass, California correspond to biotite schist and amphibolite regions. Combing these studies shows a correlation between mafic 83

silicate abundances and blue pixel color. Rothery (1987) also demonstrated that the decorrelation stretch process is useful for visual display of distinct mineralization using Landsat TM data of ophiolites in the Oman Mountains, Arabia. In general, this points more to the possibility that blue pixels, and thus also the red pixels, are more indicative of identifying mafic versus felsic and alteration silicates in a given region, and not just specifically to amphiboles. In essence, the red and blue pixels correspond to a variety of silicate structures, the red pixels correspond with framework and sheet silicates, while the blue pixel correspond with mafic mineral, chain and isolated silicates. At Black Peak, the red pixels appear to correspond well both to higher SiO 2 bulk compositions and to feldspars and the mica and clay mineralogy. This agrees with the bulk composition results because higher SiO 2 lavas generally contain plagioclase, and alter to micas and clays. The red pixels corresponding to clays and micas are also identified for the highly altered regions that are red-orange around the caldera walls, where alteration products were noted in the field. Therefore, the pixel color could be due to mineralogy, bulk composition, or both together. All of the red pixel samples demonstrate <10% amphibole, the predominance of feldspars and sheet silicates and SiO2 of 60-65wt%. The majority of the blue pixel samples have > 10% amphibole identified in the top and/or interior surface spectra and <61wt% SiO2. This suggests that it is a reasonable working hypothesis that the blue and red pixels may correlate to compositional and mineralogic variations within and around the dome complex.

5.3 Implications for ASTER assessment of volcanic regions 5.3.1 Correlations between ASTER and petrologic data: what worked This unique study presents the first application of ASTER TIR remote sensing data to the remote Alaska Peninsula for the purposes of discerning geochemical and mineralogical variations in a complicated and young volcanic dome complex. Despite the lack of pristine conditions, and the use of only a single ASTER satellite scene, this study 84

resulted in valuable and confirmed information regarding composition and mineralogic variations at Black Peak caldera. There is a general agreement found at Black Peak between the pixel colors derived from the decorrelation stretch of the ASTER data, the emissivity spectra, and petrologic data from samples collected from specific locations within the caldera dome region. This indicates that the ASTER TIR emissivity data is useable as a first order approximation to investigate the compositional variation and mineralogies within a young volcanic environment with igneous rock types that are similar in bulk composition and mineralogy, and are in close proximity to one another. Additionally this study shows that ASTER data could be applied to successfully delineate young igneous outcrops from highly altered regions within the same volcanic system. The use of this technique in conjunction with a variety of additional visible and shortwave infrared satellite data sets, pre-existing maps, aerial data sets and historic descriptions of volcanic regions can be used as a powerful tool to assess the general geologic variability in remote, volcanic regions.

5.3.2 Limitations at Black Peak Alaska There are limitations to what ASTER can and cannot provide in terms of surface properties of rocks in regions like Black Peak. For example, the ASTER data did not show variations in relative weathering and alteration among and specifically between the domes within the caldera, nor did it allow for direct identification of their relative ages. The ASTER data also did not provide structural information concerning flow features, creases and spines identified in the field. However the of the use of the DEM did allow for the distinction of the domes with and around the caldera (Fig. 16A). In this imagery the domes did not show abrupt or significant (>10 wt% Si0 2) compositional or mineralogic variations as a function of age. Since the decorrelation stretch results seem to reflect those two aspects best, it is likely that it would have taken a more extreme variation to produce differences from the ASTER data that would have separated the domes by age. 85

Despite relative success in applying ASTER data to discern petrologic and geochemical variations in the Black Peak lava domes, additional ground surface features, such as lichen and snow cover almost certainly contributed to the spectral data acquired by the satellite system. The October 2002 ASTER scene may have been affected by snow and vegetation. For example, the ASTER derived emissivity spectra examined for a few red and blue pixel locations (Fig. 14e, 14g) appear relatively flat and correlate well with the UCSB MODIS laboratory emisisvity spectra of snow and have pixel temperatures indicating some snow within the region. It is important to note that in early October of 2002, the Federal Aviation Administration Automated Weather Observing System in Port Heiden, Alaska (Fig. 1), recorded —71cm of precipitation. The snow was not observable on the October 2002 nighttime scene because it lacks the visible wavelength region data used to determine snow coverage. It is possible that Black Peak was relatively snow covered at the time the October 2002 scene was acquired. However, only few of the emissivity profiles resemble the snow, leading to the conclusion that the ASTER data provides some amount of useful information when applied even to relatively snowy northern latitude volcanic centers. Concurrent, additional satellite imagery (Landsat, MODIS, AVHRR) would have been useful for determining the coverage of snow and vegetation on ground surface at Black Peak caldera at the time of the acquisition of the October 02 scene. The use of a single nighttime ASTER scene was limited in identifying these features. However, this is the first time a routine nighttime data set in the TIR at 90m spatial resolution has been available. Satellite scenes from additional sources, of this area, around the same time as the ASTER scene acquisition, were not found, and thus not used here. A concurrent daytime Landsat scene with a VNIR spatial resolution of 30m and a panchromatic band at 15m spatial resolution may have assisted in the assessment of vegetative and snow cover distribution of the region and in the identification of structural features not observed in the ASTER data. Even the use of the Moderate Resolution Imaging Spectroradiometer (MODIS), with a 250m x 250m pixel size in the VNIR, or the Advanced Very High Resolution Radiometer (AVHRR) with a 1.09km x 1.09km pixel size may have been 86

useful in assessment of snow and vegetation distribution. The masking of these features may have contributed to identifying the effect they had on the ASTER emissivity and thus provided a more refined technique for categorizing the surfaces represented by the satellite obtained spectra. Additional processing techniques such as spectral angle mapping (Kruse et. al., 1993), and SiO 2 mapping (Dmochowski et. al., 2003), of the region and linear deconvolution of the ASTER emissivity spectra may help determine the interconnection between mineralogy and composition identified in the red and blue pixel variations obtained through the decorrelation stretch processing of an ASTER image. However the spatial resolution (90m) of the ASTER TIR data has significant limitations in utilizing these techniques to obtain results in a region of minimal compositional range and combined ground surface covers. In addition, this type of research would benefit from the use of satellite instrumentation with higher spatial resolution in the TIR wavelength region so that the region characterized in a pixel area is less than the 90m x 90m pixel region used here, and from the use of a TIR hand-held field-ready spectrometer, possibly available in the near future. Future studies of this type may also benefit from current laboratory based research on the separation of rock types and lichens (Zhang, et. al., 2004).

5.3.3 Applications along the Alaska Peninsula and Aleutian Arc Despite the uncertainty of obtaining scenes that are simultaneously cloud, snow, and vegetation-free, it is worth applying this technique in conjunction with aerial photographs, topographic maps, historical geologic maps and additional satellite data to other regions in southwestern Alaska, particularly those where vegetation is sparse and the compositional range may be wider than that presented in this study. Examples of these locations include the Valley of Ten Thousand Smokes (VTTS), Aniakchak caldera and the Peulik-Ugashik volcanic complex on the Alaska Peninsula (Fig. 1). Hildreth, (1983) summarizes the distinct mineralogical and compositional features of the VTTS. The VTTS is comprised of three distinctive magmas and is predominately identified by the widespread compositionally zoned ash flow deposit of 1912. The bulk SiO 2 content is 87

—77wt% for the rhyolite, —'65-66wt% for the dacite and —62-59wt% for the andesite. Identified phenocryst minerals dispersed within these units include quartz (rhyolite), augite (in all except rhyolite), plagioclase, orthopyroxene, titanomagnetite, ilmenite, apatite, pyrrhotite, and rare olivine (in andesite only). As described by Miller (1998) Aniakchak caldera just northeast of Black Peak may also be a reasonable target for this type of investigation. The pre-caldera volcanic rocks are comprised of basaltic andesite, two-pyroxene andesite, and dacite. The ash flows of the caldera-forming eruption have a Si02 content as high as 68wt%, and the intracaldera volcanic rocks have a compositional range from 64-67wt% SiO2. The overall mineralogy of Aniakchak includes phenocrysts of plagioclase, orthopyroxene, clinopyroxene, magnetite and olivine. The intermittent un- vegetated, highly exposed, low elevation surfaces and the thorough record of geologic investigation make the VTTS and Aniakchak regions particularly well suited for the application of remote sensing based techniques. Although potentially more snow and vegetation covered, the Ugashik-Mount Peulik region, as described by Miller (2004), includes a calcalkaline suite of rocks ranging from basalt to rhyolite and a compositional variation stemming from fractionation and magma mixing. The 5-km diameter Ugashik caldera encompasses three post caldera eruption dacitic to rhyolitic lava domes of unknown age that overlay possible smaller domes or debris from the dome explosions. This technique is well suited for an initial investigation into the relationships among and between these post caldera forming domes and possible associated debris. This technique is also applicable to the regions of unknown mineralogic and compositional in conjunction with aerial photographs, topographic maps, historical geologic maps and additional satellite data in the western Aleutians and would represent a preliminary, first order study of the area, contributing possibly vast quantities of information in preparation for additional field interpretation (Fig. 1). 88

VI. Conclusions The lava flows and domes within and around the —4,600 year old Black Peak caldera, Alaska can be segregated into three distinct, age-related sections based on weathering, and structural and mineralogic characteristics observed in the field. These sections consist of: 1) a pre-caldera-forming eruption series of domes outside of the caldera, and truncated volcanic necks and domes within the caldera walls, 2) domes in the central caldera with significant weathering and alteration, and a collapsed dome region with soil and vegetative cover along the southeastern portion of the caldera, and 3) young domes and flows with observable flow and structural features along the margins of the central dome complex. Geochemical whole rock analyses reveal a mixing trend indicating a mafic magmatic input into a dacitic reservoir throughout the systems pre- through post- caldera forming eruption activity. The presence of vesicular enclaves throughout all three age sections and the absence of orthopyroxene in the youngest domes and flows also indicate a magma mixing regime. Electron microprobe and x-ray diffraction analyses reveal a compositional suite of minerals comparable to that derived from linear deconvolution of laboratory emissivity spectra. Although there is compositional variability between the results, grouping the identified minerals into the categories of plagioclase, potassium feldspar, pyroxene, amphibole, mica/clay, quartz, oxides, and obsidian allows for the direct and accurate comparison of results from these diverse techniques (Hamilton et. al., 1997). Compositional and mineralogic data obtained through laboratory analyses are compared to the decorrelation stretch image (R=band14, G=bandl 2 and B=band10) generated from the ASTER TIR scene of the Black Peak, AK region acquired in October, 2002. The red pixels of the decorrelation stretch image correspond to regions with <10 aerial % amphibole, the predominance of feldspars and sheet silicates and 60-65wt% SiO2. The blue pixels correspond to regions with >10 aerial % amphibole and <61wt% SiO2. Combined with the results of Watanabe and Matsuo (2003) and Rowan and Mars (2003) it is determined that the use of decorrelation stretch as applied here to thermal 89

remote sensing data can be used to assess the relative wt% Si0 2 and mineralogy of a given, specific target. ASTER TIR decorrelation stretch imagery can be applied to both well-studied volcanic centers along the Alaska Peninsula and also regions of unknown volcanic and geologic variability in the western Aleutians in conjunction with aerial photographs, topographic maps, historical geologic maps and additional satellite data. This technique could be used for the prioritization of field work by providing a basis by which compositional and mineralogically variable regions can be discernable prior to entering the field. Additional, concurrent visible wavelength region satellite remote sensing data can also be utilized to determine the extent of snow and vegetative cover in order to assist in the resolution of compositional and mineralogic variability of the region under study. 90

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Table Al. Section 1 additional field sample descriptions

1, CNB03_4 dome dome sample CNB035 lava flow coulee/flow? surface near "Gates" 03Mc_20 lava pre-caldera lava flow on ridge extending NW of caldera

Section 2 additional field sample descriptions

, , i.t mPleID I le I YR °I!ieldNotes 03JABP_03 dome "red pixel" dome "rind" half-way down the flank 03JAB13_05 dome on dome slope above Purple Lake 03JL13P03 dome sampling in-place lava hbl, plag spine, hbl+ plag CNB03_2 dome dome sample 03Mc_04 dome top of dome SW of hbl and plag Mc_03; more lichen covered than Mc 03 03Mc 12 dome conical dome hbl= hornblende, plag=plagioclase 99

Table A2. XRF Normalized Mar or Elements (weight %) J$npieID 111ii it:1102 a iI**ii psnp a1011 IthJi dila; 4(1 'iPra!! 01Mc_01 60.89 0.527 17.34 5.15 0.155 3.91 7.30 3.47 1.13 0.139 01Mc_02 60.44 0.583 17.77 5.49 0.154 3.27 7.52 3.50 1.13 0.145 01Mc_03 62.70 0.493 17.76 4.39 0.133 2.48 6.88 3.65 L36 0.150 0lMc_04 62.66 0.486 17.48 4.49 0.151 3.11 6.77 3.55 1.17 0.143 01Mc-_06 65.35 0.427 17.34 4.01 0.149 1.76 5.78 3.69 1.35 0.140 01Mc_07 60.79 0.564 17.78 5.44 0.154 3.12 7.38 3.48 1.14 0.145 01Mc_08 60.74 0.553 17.87 5.41 0.156 3.04 7.41 3.55 1.14 0.143 01Mc_13 60.59 0.577 17.61 5.58 0.146 3.56 7.34 3.28 1.18 0.123 01Mc_17 64.43 0A62 17.41 4.18 0.154 2.24 6.10 3.64 1.23 0.157 01Mc_17 64.08 0.428 17.67 4.07 0.153 2.25 6.31 3.70 1.20 0.147 0 IMe_20 61.42 0.527 17.60 5.54 0.160 3.04 6.98 3.49 1.08 0.159 03JABP_02 63.28 0.499 18.30 5.71 0.137 2.19 5.06 3.56 1.11 0.151 03JABP_03 61.53 0.504 18.84 5.83 0.147 2.51 5.87 3.56 1.07 0.136 03JABP_04rr 61.11 0.527 17.57 5.78 0.163 2.94 7.19 3.47 1.08 0.163 03JABP_04g 61.91 0.487 17.67 5.22 0.154 2.71 7.02 3.56 1.11 0.153 03JABP_05 59.58 0.557 18.00 5.99 0.162 3.37 7.77 3.39 1.01 0.163 03JABP_06 58.88 0.652 18.14 5.92 0.147 3.59 8.10 3.52 0.91 0.141 03JABP_08 60.49 0.569 17.43 5.85 0.168 3.52 7.42 3.27 1.17 0.123 03JABP_09 61.45 0.505 17.67 5.49 0.159 2.82 7.11 3.54 1.10 0.158 03JABP_10 62.11 0.479 17.55 5.19 0.157 2.79 6.92 3.54 1.13 0.147 03JABP_11 63.56 0.464 17.29 4.76 0.156 2.33 6.42 3.69 1.17 0.155 03JLBP_0 1 61.21 0.504 17.96 5.51 0.158 2.87 7.05 3.51 1.08 0.150 03.1LBP_03 60.17 0.579 17.70 6.04 0.163 3.13 7.52 3.45 1.10 0.155 03.1LBP_04 59.62 0.583 17.95 6.04 0.170 3.30 7.68 3.42 1.07 0.154 031LBP_06 61.65 0.496 17.90 5.42 0.154 2.77 6.87 3.48 1.10 0.162 03JLBP_07 60.68 0.531 17.87 5.66 0.159 3.05 7.41 3.42 1.07 0.156 03Mc_1 0 61.38 0.550 17.79 5.44 0.143 2.97 7.00 3.42 1.24 0.135 03Mc_ 1 1 57.92 0.663 18.22 6.41 0.149 3.90 8.23 3.43 0.95 0.141 03Mc_12 61.49 0.518 18.02 5.15 0.143 2.61 7.18 3.66 1.08 0.144 03Mc_16 60.99 0.524 17.63 5.82 0.157 2.95 7.22 3.469 1.07 0.155 03Mc_18 62.48 0.525 17.98 5.00 0.081 1.99 6.94 3.58 1.31 0.127 03Mc_19 61.33 0.529 17.52 5.61 0.146 2.91 7.10 3.48 1.24 0.125 03Mc_20 59.91 0.563 18.43 5.87 0.135 2.99 7.80 3.37 0.79 0.136 03Mc_02 63.99 0.463 17.34 4.78 0.153 2.11 6.12 3.59 1.31 0.139 03Mc_03 61.36 0.523 17.79 5.43 0.146 2.69 7.17 3.57 1.15 0.149 03Mc_04 61.94 0.489 17.78 5.24 0.152 2.58 6.94 3.60 1.13 0.155 03Mc_05 58.64 0.586 18.25 6.41 0.161 3.56 7.94 3.33 0.96 0.160 03Mc_06 57.84 0.591 18.42 6.56 0.163 3.80 8.26 3.27 0.93 0.169 03Mc_07 63.11 0.492 17.27 5.20 0.157 2.34 6.47 3.65 1.15 0.155 CNB03_1 60.56 0.557 17.91 5.75 0.149 2.85 7.40 3.54 1.14 0.149 CNB03_2 59.91 0.588 17.98 6.05 0.151 2.99 7.55 3.52 1.12 0.150 CNB03_4 60.78 0.531 17.63 5.72 0.148 3.04 7.27 3.49 1.25 0.135 CNB035 58.68 0.599 17.99 6.49 0.165 3.69 7.96 3.26 0.99 0.169 CNB03_8 63.82 0.459 17.30 4.93 0.151 2.04 6.28 3.69 1.18 0.150 CN1303_9 61.08 0.579 17.37 6.03 0.156 3.02 6.99 3.35 1.28 0.140 CNB03 9L 62.74 0.522 17.38 5.59 0.163 2.31 6.37 3.56 1.22 0.149 100

Table A3. XRF Unnormalized Trace Elements ( pm Sample ID V,' Cu 01Mc_01 27 67 127 505 428 94 3.3 19 63 01Mc_02 7 18 151 473 439 91 2.7 29 64 01Mc_133 3 8 126 552 546 95 2.2 25 54 01Mc_04 17 40 116 506 418 98 3.5 13 61 01 Mc-_06 4 4 85 626 464 103 4.1 14 59 01Mc_07 5 14 148 480 442 94 3.2 23 62 01Mc_08 2 12 144 471 441 92 3.0 19 63 01Mci 3 18 54 148 490 358 85 3.1 36 60 01Mc_17 1 6 98 527 419 103 3.2 9 64 01Mc_17 4 7 88 521 433 101 2.8 7 62 01Mc_20 5 13 121 485 430 101 2.7 20 70 03JAB13_02 7 8 119 516 508 113 2.4 25 63 03JABP_03 9 9 116 488 510 110 2.0 31 96 03JAB13_04rr 8 8 115 465 440 97 3.0 25 68 03JABP_O4g 7 13 119 491 442 96 2.9 14 63 03JABP_05 9 14 140 437 467 91 2.6 27 63 03JABP_06 12 21 175 378 484 87 3.5 38 60 03JAB13_08 19 51 158 503 365 83 2.8 34 66 03JABP_09 5 10 115 488 446 96 3.1 18 63 03JABP _10 9 10 113 496 438 96 3.1 16 59 03JABP_11 7 9 89 514 441 104 3.6 6 62 03JLBP_01 7 12 116 477 451 96 3.3 15 63 0311,BP_03 8 13 154 459 448 94 3.3 24 65 03JLBP_04 7 12 155 448 453 91 2.6 25 67 03JLBP_06 11 14 115 483 444 101 3.3 20 65 03MBP_07 7 10 127 464 453 95 2.5 25 63 03Mci 0 101 13 139 504 460 105 3.9 30 60 03Mc_11 16 22 200 382 468 92 3.7 48 67 03Mc_12 10 8 131 466 471 98 3.1 34 59 03Mc_16 12 12 128 471 449 101 3.8 18 68 03Mc_l 8 9 6 138 533 425 93 3.6 33 56 03Mc_19 12 18 148 525 393 89 3.6 30 64 03Mc_20 10 13 142 392 466 89 1.9 27 67 03Mc_02 8 6 94 569 455 114 4.0 12 64 03Mc_03 9 9, 141 488 463 100 3.6 22 62 03Mc_04 10 8 132 500 461 103 3.2 18 62 03Mc_05 13 9 148 408 479 91 3.4 30 72 03Mc_06 13 11 160 393 487 89 3.1 34 73 03Mc_07 7 10 108 510 455 113 4.0 11 67 CNB03_1 10 10 154 475 467 100 3.3 30 65 CNB03_2 10 10 165 460 463 103 4.1 23 68 CNB03_4 12 16 147 511 449 97 3.6 40 61 CNB035 13 10 161 410 474 93 3.7 34 71 CNB03_8 7 6 96 518 460 111 4.1 5 64 CNB03_9 9 8 159 511 431 105 4.0 14 65 CNB03 9L 8 8 120 501 461 120 4.5 25 66 101

Table A4. ICP-MS Trace Elements ra 1 Pm? pi sit-kr ta 4 e I PiH MA' IA, 01Mc_01 11.30 21.63 2.61 11.25 2.78 0.97 2.82 0,47 2.94 0.61 1.74 0.27 01Mc_02 10.77 20.83 2.55 11.17 2.86 0.96 2.80 0.47 2.99 0.63 1.76 0.27 01Mc_03 12.65 23.26 2.86 11.88 2.83 0.95 2.66 0.45 2.73 0.57 1.61 0.24 01Mc_04 10.69 20.16 2.47 10.63 2.62 0.91 2.61 0.45 2.82 0.59 1.73 0.26 01Mc-_06 14.16 25.83 3.16 13.11 3.14 0.95 3.00 0.49 3.05 0.65 1.81 0.28 01Mc_07 10.91 20.72 2.57 11.18 2.89 0.96 2.81 0.49 3.07 0.63 1.82 0.278 01Mc_08 11.07 20.18 2.45 10.87 2.83 0.97 2.77 0.48 3.09 0.64 1.84 0.27 01Mc_13 9.25 17.43 2.10 9.01 2.39 0.86 2.48 0.43 2.75 0.56 1.61 0.24 01Mc_17 11.35 21.53 2.58 10.92 2.68 0.88 2.53 0.44 2.78 0.58 1.64 0.26 01Mc_17 11.63 21.83 2.63 11.04 2.72 0.92 2.71 0.45 2.85 0.61 1.74 0.26 01Mc_20 10.08 19.16 2.40 10.43 2.69 0.94 2.67 0.47 2.96 0.62 1.80 0.27 03JABP_02 9.53 17.92 2.08 8.24 1.93 0.74 1.87 0.31 1.95 0.43 1.22 0.19 03JABP_03 9.68 18.45 2.18 9.23 2.32 0.86 2.18 0.36 2.23 0.47 1.34 0.21 03JABP_O4rr 10.52 21.07 2.57 11.23 2.81 1.00 2.81 0.48 2.94 0.63 1.73 0.27 03JABP_04g 10.58 20.90 2.56 11.14 2.71 0.94 2.73 0.46 2.94 0.61 1.74 0.26 03JABP_05 10.42 20.76 2.59 11.48 2.97 1.01 2.92 0.50 3.12 0.66 1.87 0.28 03JABP_06 9.26 18.75 2.34 10.51 2.85 0.96 2.95 0.50 3.11 0.65 1.83 0.27 03JABP_08 10.67 21.15 2.69 11.57 3.15 0.94 3.33 0.56 3.58 0.73 2.05 0.31 03JABP_09 10.43 20.50 2.54 10.83 2.75 0.94 2.76 0.46 2.89 0.61 1.71 0.26 03JABP_10 10.27 20.07 2.44 10.51 2.62 0.89 2.54 0.44 2.70 0.57 1.62 0.25 03JABP_11 11.16 21.86 2.61 11.00 2.70 0.88 2.64 0.44 2.75 0.59 1.62 0.26 03JLBP_0 1 12.06 22.33 2.48 9.67 2.35 0.94 2.32 0.40 2.47 0.53 1.53 0.24 03JLBP_03 10.53 20.84 2.58 11.21 2.90 0.98 2.87 0.45 3.11 0.65 1.79 0.28 03JLBP_04 10.55 21.24 2.61 11.46 2.95 0.98 2.94 0.51 3.15 0.67 1.88 0.29 03JLBP_06 11.38 22.33 2.70 11.43 2.90 0.92 2.72 0.48 2.93 0.63 1.76 0.27 03.MBP_07 10.25 20.19 2.49 10.87 2.80 0.97 2.79 0.47 3.04 0.63 1.77 0.28 03Mc_l 0 9.83 18.96 2.31 9.99 2.54 0.90 2.68 0.44 2.74 0.60 1.67 0.24 03Mc_l I 8.79 17.66 2.23 9.99 2.73 1.00 2.88 0.48 3.07 0.65 1.80 0.27 03Mc_12 10.16 20.01 2.42 10.28 2.62 0.92 2.60 0.44 2.75 0.59 1.67 0.25 03Mc_16 10.14 20.06 2.44 10.74 2.74 0.95 2.76 0.46 2.93 0.63 1.78 0.27 03Mc_18 9.95 18.82 2.25 9.52 2.45 0.86 2.53 0.41 2.63 0.55 1.51 0.23 03Mc_19 9.88 18.98 2.28 9.63 2.59 0.86 2.58 0.46 2.80 0.60 1.68 0.26 03Mc_20 8.91 16.28 2.23 9.72 2.57 0.92 2.69 0.45 2.80 0.59 1.66 0.25 03Mc_02 10.73 20.74 2.48 10.39 2.57 0.87 2.53 0.42 2.62 0.58 1.62 0.25 03Mc_03 10.59 20.53 2.48 10.72 2.67 0.92 2.66 0.44 2.81 0.59 1.63 0.25 03Mc_04 10.91 20.98 2.52 10.71 2.66 0.92 2.59 0.43 2.70 0.58 1.66 0.25 03Mc_05 9.62 19.19 2.45 10.68 2.83 0.96 2.90 0.48 2.97 0.64 1.79 0.28 03Mc_06 9.45 19.09 2.40 10.82 2.91 1.00 2.95 0.50 3.10 0.66 1.87 0.28 03Mc_07 11.10 21.64 2.62 11.16 2.76 0.94 2.75 0.46 2.89 0.62 1.74 0.27 CNB03_1 10.72 21.45 2.61 11.08 2.79 0.96 2.74 0.46 2.87 0.62 1.72 0.27 CNB03_2 10.31 20.28 2.50 10.93 2.75 0.95 2.77 0.46 2.89 0.62 1.75 0.26 CNB03_4 10.60 20.55 2.47 10.65 2.74 0.93 2.76 0.45 2.80 0.60 1.69 0.26 CNB035 9.81 19.74 2.53 11.19 2.93 0.99 3.01 0.49 3.23 0.67 1.90 0.29 CNB03_8 10.76 20.81 2.51 10.48 2.57 0.89 2.53 0.42 2.66 0.56 1.59 0.25 CNB039 10.77 20.99 2.59 11.09 2.84 0.95 2.86 0.48 3.03 0.65 1.78 0.27 CNB03 9L 9.91 19.07 2.32 9.78 2.56 0.86 2.57 0.43 2.80 0.59 1.70 0.25 102

Table A4. ICP-MS Trace Elements ppm) (cont ltib 'Y {I; '" 01Mc_01 1.80 0.30 489 3.64 2.64 17.29 2.55 0.19 1.51 6.48 27.3 2.05 01Mc_02 1.77 0.29 468 3.35 2.59 17.43 2.69 0.20 1.43 6.14 25.0 1.65 01Mc_03 1.59 0.27 534 3.28 3.01 15.59 2.66 0.23 1.25 6.28 32.0 2.92 01Mc_04 1.72 0.28 517 3.33 2.82 16.02 2.69 0.21 1.34 5.45 27.5 1.81 01Mc-_06 1.79 0.30 616 3.38 3.45 18.56 2.67 0.27 1.34 7.52 32.9 1.30 01Mc_07 1.81 0.30 462 3.25 2.53 17.15 2.64 0.19 1.39 6.03 24.9 1.83 01Mc_08 1.78 0.30 471 3.32 2.59 17.23 2.56 0.20 1.38 6.25 25.4 1.88 01Mc_13 1.56 0.26 484 3.08 2.48 15.68 2.34 0.20 1.19 5.54 27.4 1.13 01Mc_17 1.71 0.29 519 3.19 3.01 16.27 2.82 0.23 1.31 7.01 28.3 2.05 01Mc_17 1.75 0.30 525 3.17 3.00 16.78 2.77 0.22 1.31 7.05 28.9 2.08 01Mc_20 1.78 0.30 473 3.13 2.71 16.81 2.62 0.20 1.29 5.80 25.9 1.97 03JABP_02 1.26 0.22 490 2.72 2.73 11.58 2.55 0.20 0.89 15.83 24.4 1.79 03JABP_03 1.38 0.23 465 2.79 2.62 12.79 2.54 0.19 1.04 7.85 22.5 1.58 03JABP_O4rr 1.79 0.29 475 3.01 2.63 17.17 2.53 0.20 1.21 5.50 25.1 1.88 03JABP_045 1.78 0.29 500 3.11 2.78 16.79 2.63 0.20 1.31 5.43 27.0 2.00 03JABP_05 1.84 0.30 432 2.81 2.50 17.92 2.53 0.18 1.16 5.52 22.9 1.65 03JABP_06 1.78 0.29 387 2.14 2.60 17.61 2.33 0.19 0.88 4.81 19.1 1.36 03JABP_08 2.05 0.33 486 2.99 2.51 19.88 2.34 0.20 1.18 5.06 26.4 1.26 03JABP_09 1.77 0.29 469 2.99 2.92 16.81 2.64 0.20 1.25 5.08 25.9 1.94 03JABP10 1.68 0.28 467 2.96 2.73 15.85 2.50 0.20 1.22 5.02 25.9 2.15 03JABP_I I 1.71 0.28 506 3.08 2.95 16.38 2.79 0.22 1.28 6.85 27.5 1.96 03.1LBP_0 1 1.62 0.28 468 3.13 2.70 14.52 2.65 0.20 1.26 5.77 25.5 1.92 03JLBP_03 1.88 0.31 450 3.28 2.68 17.85 2.57 0.19 1.35 6.42 25.4 1.96 03ILBP_04 1.90 0.31 440 3.20 2.59 18.29 2.45 0.19 1.32 5.64 23.7 1.83 03JLBP_06 1.79 0.30 475 3.13 2.79 17.17 2.55 0.21 1.35 6.70 26.8 1.97 03.1LBP_07 1.79 0.29 457 2.96 2.63 17.45 2.46 0.19 1.21 6.00 25.1 1.75 03Mc_1 0 1.60 0.26 470 2.90 2.50 16.25 2.65 0.20 1.17 5.21 26.7 1.09 03Mc_11 1.75 0.29 374 2.24 2.27 17.60 2.38 0.16 0.90 5.86 20.0 1.41 03Mc_12 1.65 0.27 453 2.76 2.60 16.42 2.48 0.19 1.13 4.56 22.7 0.75 03Mc_16 1.74 0.29 459 2.97 2.66 17.28 2.65 0.19 1.30 5.22 25.4 1.86 03Mc_18 1.48 0.24 509 3.02 2.65 15.14 2.40 0.21 1.22 5.06 30.9 2.43 03Mc_19 1.69 0.28 511 3.18 2.59 17.02 2.33 0.21 1.23 6.69 29.4 2.04 03Mc_20 1.56 0.26 379 2.00 2.45 16.88 2.26 0.18 0.81 6.31 17.8 0.34 03Mc_02 1.64 0.28 547 3.06 2.89 15.78 2.88 0.21 1.29 6.42 28.1 2.03 03Mc_03 1.68 0.27 469 3.17 2.50 16.24 2.53 0.19 1.31 5.90 25.4 1.84 03Mc_04 1.69 0.28 479 3.06 2.68 16.01 2.68 020 1.31 5.40 25.9 2.01 03Mc_05 1.80 0.29 398 2.63 2.34 17.47 2.35 0.17 1.07 5.39 21.2 1.51 03Mc_06 1.79 0.30 379 2.52 2.23 18.14 2.31 0.15 1.05 6.75 20.0 1.41 03Mc_07 1.76 0.30 490 3.06 2.85 17.12 2.85 0.20 1.30 6.88 26.5 1.91 CNB03_1 1.73 0.29 457 3.15 2.47 16.57 2.61 0.18 1.32 6.43 24.5 1.84 CNB03_2 1.71 0.28 446 3.16 2.42 16.72 2.63 0.18 1.26 6.38 23.9 1.78 CNB03_4 1.68 0.28 493 3.49 2.34 16.49 2.58 0.18 1.39 7.36 27.6 2.02 CNB03_5 1.84 0.31 395 2.64 2.39 18.24 2.43 0.17 1.07 5.15 21.4 1.53 CNB03_8 1.63 0.28 494 2.95 2.83 15.74 2.73 0.21 1.22 6.47 26.6 1.95 CNB03_9 1.76 029 497 3.51 2.56 17.51 2.70 0.21 1.38 6.63 29.0 2.07 CNB03 9L 1.70 0.29 481 2.91 2.81 16.31 2.96 0.20 1.23 4.77 26.2 1.88 103

Table A4. ICP-MS Trace Elements ( m) (cont.) OP 01Mc_01 443 20.3 89.1 01Mc_02 466 21.0 95.5 01Mc_03 546 14.9 89.1 01Mc_04 415 15.3 92.2 01Mc-_06 466 9.5 93.1 01Mc_07 457 19.7 91.2 01Mc08 450 19.3 85.0 01Mc_13 369 18.8 77.3 01Mc_17 428 10.9 99.2 01Mc_17 449 10.9 95.9 01Mc_20 437 14.3 89.4 03JABP_02 444 12.0 87.5 03JABP_03 455 13.1 88.9 03JABP_O4n 456 13.5 86.0 03JABP_04g 447 12.9 89.8 03JABP_05 471 15.9 84.7 03JABP_06 495 22.3 81.6 03JABP_08 373 17.7 77.0 03.1ABP_09 463 13.9 90.8 03JABP_10 444 12.5 85.5 03JABP11 446 11.1 98.1 03JLBP_0 1 453 14.6 91.1 03JLBP_03 467 19.2 87.4 031LBP_04 467 19.3 83.5 03JLBP_06 451 14.3 87.9 031LBP07 467 16.0 82.0 03Mc_10 426 15.3 90.9 03Mci 1 474 24.3 80.7 03Mc_12 474 15.7 87.1 03Mc_16 457 14.7 92.2 03Mc18 412 14.1 80.6 03Mc_19 392 15.8 78.6 03Mc_20 462 15.5 79.3 03Mc_02 430 10.9 99.1 03Mc_03 455 16.8 87.7 03Mc_04 454 13.1 92.4 03Mc_05 476 17.8 80.6 03Mc_06 487 19.1 78.1 03Mc_07 445 11.7 100.3 CNB03_1 455 18.4 88.8 CNB 03_2 459 20.0 92.6 CNB03_4 437 17.8 85.2 CNB035 466 18.9 81.9 CNB03_8 436 10.5 95.8 CNB03_9 419 17.3 93.3 CNB03 9L 438 11.7 105.5 104

Table A5. Probe analyses ofpyroxene lb RI's ItI Ai 04

F 0.31 0.24 0.28 0.54 Na2O 0.55 0.42 0.00 0.27 MgO 15.67 15.47 23.33 15.41 Al203 3.71 2.66 1.15 1.77 SiO2 51.08 51.87 52.60 52.31 1C20 0.01 0 0.01 0.05 CaO 18.42 18.76 0.83 19.65 TiO2 0 1.44 0 0.32 MnO 0.69 0.64 1.63 0.64 FeO 8.57 8.02 20.08 9.37 Total 99.01 99.52 99.91 100.33 En 45 44 65 43 Wo 38 39 2 40

robe' n , F 0 0.07 Na2O 0.01 0 MgO 24.54 23.78 Al203 0.47 0.81 SiO2 54.19 53.47 1(20 0.03 0.02 CaO 0.62 1.25 TiO2 0.32 0.96 MnO 1.53 1.40 FeO 18.50 18.39 Total 100.21 100.15 En 68 44 Wo 1 3 105

Table A5. Probe analyses of pyroxene cont.

T F 0.09 0 0.07 0.10 0.17 0 Na2O 0.25 0.64 0.97 0.62 0.42 0.38 MgO 17.05 15.51 16.40 16.13 15.21 15.87 Al203 3.44 4.53 3.54 1.94 2.51 2.75 S102 52.12 50.20 50.89 52.42 51.50 51.78 1{20 0.02 0 0.02 0 0.03 0.01 CaO 17.01 18.03 18.32 19.11 18.57 18.86 TiO2 0.74 80 1.12 0.54 0.64 0.79 MnO 0.50 0.71 0.66 0.64 0.71 0.62 FeO 9.10 8.01 6.60 7.28 8.92 7.72 Total 100.32 98.42 98.58 98.79 98.68 98.78 En 49 45 47 46 44 46 Wo 35 38 38 39 39 39

2 , 1 F 0 0 0.36 0.36 Na2O 0.09 0.05 0 0 MgO 24.45 23.35 23.39 23.40 Al203 1.30 0.83 0.48 0.65 SiO2 52.46 51.86 52.63 52.71 1{20 0.01 0.01 0.01 0 CaO 1.28 0.48 0.66 0.44 TiO2 0.19 0.82 0 0.22 MnO 1.59 1.55 1.63 1.96 FeO 17.72 19.68 19.51 18.71 Total 99.06 98.64 98.66 98.47 En 67 65 66 66 Wo 3 1 1 1 106

Table A5. Probe analyses of pyroxene cont. sa fil n P F 0 0.11 0.09 0 Na20 0.03 0.01 0.02 0 MgO 23.65 22.79 23.87 23.50 Al203 1.16 1.09 1.21 1.13 5102 52.97 53.04 52.51 52.99 K20 0 0 0 0 CaO 0.47 0.72 0.43 0.51 TiO2 0.11 0.18 0.03 0.14 MnO 1.95 1.67 1.86 1.82 FeO 19.48 20.90 19.23 20.33 Total 99.82 100.50 99.27 100.40 En 66 63 66 65 Wo 1 1 1 1

F 0 0 0.03 Na20 0.00 0.05 0.08 MgO 24.37 25.05 . 24.02 Al203 1.16 1.54 1.12 5102 53.44 53.39 53.76 1(20 0.02 0.03 0.01 CaO 1.44 1.23 1.18 TiO2 0.13 0.19 0.21 MnO 1.76 1.85 1.51 FeO 17.84 17.93 19.32 Total 100.15 101.28 101.29 En 67 68 66 Wo 3 3 2 107

Table A6. Probe analyses of amphibole S P_ 07 2 F 0 0 0.51 0.87 0.14 0 Na2O 2.74 3.02 1.01 1.21 2.37 2.057 MgO 18.57 13.01 16.15 16.45 15.48 18.57 Al203 7.71 7,50 6.53 7.22 8,12 6.725 SiO2 46.91 45.07 49.80 48.64 47.61 47.808 K2O 0.61 0.54 0.14 0.20 0.25 0.165 CaO 8.46 9.82 9.4 9.82 9.56 10.502 TiO2 3.31 1.85 2.94 2.36 0.88 1.114 MnO 0.84 0.77 0.66 0.61 0.74 0.517 FeO 10.30 19.66 12.94 12.78 13.19 11.132 Total 99.47 101.24 100.11 100.16 98.45 98.78 Amphibole barroisite ednite barroisite mag-hbl barroisite mag-hbl

c c SSP 3 1 F 0 0 0.37 0 0.15 0.54 Na2O 1.38 1.37 1.49 1.44 1.34 1.41 MgO 18.41 17.30 15.06 16.14 16.74 14.45 Al203 5.37 7.20 6.96 7.16 6.67 8.20 SiO2 48.19 49.73 46.64 47.55 45.72 46.85 K2O 0.20 0.19 0.47 0.40 0.12 0.25 CaO 10.40 10.28 10.84 10.84 9.09 9.66 TiO2 0.49 2.31 0.65 0.66 0.95 4.09 MnO 0.77 0.57 0.77 0.61 0.72 0.71 FeO 14.76 11.23 16.21 14.25 17.49 13.38 Total 99.97 100.17 99.47 99.05 99.05 99.53 Amphibole mag-hbl mag-hbl mag-hbl mag-hbl barroisite barroisite mag-hbl = magnesio-hornblende 108

Table A6. Probe analyses of amphibole Ccont

F 0.30 0 0.077 0 Na2O 2.32 1.10 1.15 1.40 MgO 14.32 15.33 16.01 15.14 Al203 8.21 7.71 6.99 8.25 SiO2 48.10 48.11 48.29 46.90 1C20 0.41 0.23 0.22 0.27 CaO 10.38 9.79 9.47 9.61 TiO2 1.97 2.29 3.28 0.99 MnO 0.73 0.50 0.62 0.61 FeO 13.16 13.72 13.14 15.36 Total 99.89 98.79 99.243 98.54 Amphibole mag-hbl mag-hbl mag-hbl barroisite

F 0.06 0.13 0.33 Na2O 1.77 2.35 3.42 MgO 14.95 16.8 15.31 Al203 10.82 7.44 7.58 SiO2 46.62 49.90 48.27 1C20 0.24 0.19 0.29 CaO 9.58 9.61 9.46 TiO2 1.48 0.98 1.03 MnO 0.54 0.70 0.68 FeO 13.71 12.38 12.52 Total 99.88 100.559 98.89 Amphibole barroisite barroisite barroisite 109

Table A6. Probe analyses of amphibole (cont)

F 0 0.45 0 0.30 0.23 Na20 3.63 3.94 2.23 4.28 3.12 Mg0 15.40 14.29 18.74 13.98 15.77 Al203 7.88 8.44 4.55 7.97 7.81 8102 49.49 47.69 48.38 47.94 47.22 K20 0.28 0.53 0.05 0.26 0.52 Ca0 9.58 8.39 9.82 9.40 9.51 T102 2.00 0.17 1.50 1.83 2.50 Mn0 0.53 0.48 0.63 0.63 0.52 Fe0 11.23 13.63 12.56 12.98 12.48 Total 100.02 98.01 98.45 99.58 99.66 Amphibole banoisite mag.-kato mag.-hbl mag.-kato barroisite mag.-kato = magnesio-katophorite 110

Table A7 Probe analyses of plasioclase

Na20 4.17 5.20 4.46 5.12 5.12 5.12 3.79 4.03 5.31 5.33 Al203 30.71 28.78 30.01 29.03 29.59 28.66 31.18 30.85 28.77 28.63 Si02 53.00 55.12 53.54 54.55 55.16 55.39 52.07 52.32 55.00 55.98 K20 0.14 0.20 0.13 0.13 0.18 0.22 0.09 0.10 0.18 0.19 Ca0 12.69 10.92 11.93 10.88 10.55 10.70 13.14 13.31 10.57 10.07 FeO 0.28 0.21 0.22 0.26 0.21 0.23 0.19 0.41 0.24 0.24 100.99 100.42 100.28 99.96 100.80 100.33 100.46 101.02 100.07 100.43 An 62.21 53.08 59.21 53.63 52.67 52.88 65.34 64.22 51.83 50.49

B Peas , 47§ G 0 52 Na20 2.86 3.41 2.63 5.12 2.53 3.42 2.72 Al203 32.53 32.06 32.80 29.17 32.32 31.96 32.03 Si02 49.62 50.85 48.75 54.47 48.93 50.46 49.43 K20 0.06 0.12 0.08 0.16 0.28 0.10 0.21 CaO 15.53 14.05 15.24 10.97 15.35 14.35 14.24 FeO 0.37 0.26 0.27 0.28 0.82 0.47 0.75 Total 100.97 100.75 99.77 100.17 100.22 100.77 99.37 An 74.73 68.98 75.80 53.70 69.09 69.46 73.39 a G hl Na20 4.25 5.14 3.97 4.82 Al203 30.28 29.07 30.43 29.79 Si02 53.17 55.39 52.25 54.89 K20 0.21 0.17 0.14 0.18 CaO 12.75 10.91 12.75 11.05 Fe0 0.30 0.13 0.21 0.12 Total 100.95 100.81 99.76 100.85 An 61.62 53.45 63.41 55.31

6'

Na20 4.36 4.60 5.32 5.58 5.16 5.01 5.19 Al203 30.22 29.25 28.58 28.15 28.56 29.65 28.50 8102 53.39 54.17 55.90 56.93 54.97 54.57 54.70 K20 0.11 0.14 0.16 0.21 0.15 0.16 0.18 CaO 12.26 11.76 10.78 9.64 10.54 11.00 10.61 FeO 0.28 0.30 0.28 0.16 0.30 0.28 0.14 Total 100.63 100.22 101.01 100.69 99.68 100.67 99.32 An 60.42 58.07 52.34 48.21 52.52 54.31 52.49 Grouped by crystal. All above points are from rim to core in each crystal. 111

Table A7. Probe analyses of plagioclase cont.

G i Na2O 5.24 5.71 4.43 6.02 4.36 2.93 5.20 5.79 Al2 O3 28.98 28.35 30.30 27.59 30.02 32.67 29.09 27.62 SiO2 55.21 56.38 53.69 57.15 53.68 49.72 55.28 56.71 K2O 0.12 0.20 0.15 0.39 0.10 0.14 0.11 0.23 CaO 10.85 9.97 11.15 8.67 12.06 14.75 10.97 9.54 FeO 0.26 0.19 0.20 0.19 0.06 0.30 0.30 0.28 Total 100.66 100.80 99.91 100.01 100.28 100.51 100.95 100.16 An 52.96 48.51 57.66 43.30 60.13 72.99 53.50 47.01

7 0 P 3 Na2O 5.49 5.71 4.82 5.43 5.44 5.38 5.53 5.49 5.95 5.35 Al203 28.20 28.37 29.80 28.51 28.17 28.20 28.50 28.50 27.47 28.70 SiO2 56.46 56.25 53.97 56.01 55.77 55.57 56.14 55.61 56.48 55.43 1(20 0.21 0.16 0.14 0.20 0.19 0.22 0.19 0.15 0.17 0.20 CaO 9.81 9.87 11.84 10.22 10.28 9.95 9.67 10.21 9.25 10.19 FeO 0.29 0.12 0.25 0.25 0.25 0.32 0.20 0.17 0.27 0.19 Total 100.45 100.48 100.81 100.61 100.11 99.64 100.23 100.12 99.58 100.05 An 49.01 48.41 57.11 50.39 50.34 49.91 48.57 50.26 45.77 50.71

Na2O 4.61 3.87 5.01 5.85 5.77 Al203 29.42 30.94 29.73 28.00 28.31 SiO2 53.47 52.30 54.90 55.91 56.62 K2O 0.20 0.09 0.18 0.23 0.24 CaO 11.67 13.16 10.92 9.29 9.90 FeO 0.09 0.26 0.27 0.20 0.22 Total 99.45 100.61 101.01 99.47 101.06 An 57.67 64.91 54.08 46.13 47.98 Grouped by crystal. All above points are from rim to core in each crystal.

3'

Na2O 5.42 5.16 3.94 3.62 5.28 5.07 4.61 Al203 28.23 28.89 31.56 31.48 28.51 29.16 29.66 SiO2 56.64 55.25 51.46 51.42 55.40 55.03 54.12 1(20 0.17 0.21 0.11 0.09 0.17 0.13 0.14 CaO 10.26 11.08 13.60 13.56 10.82 11.16 11.39 FeO 0.32 0.32 0.21 0.28 0.22 0.20 0.46 Total 01.05 100.90 100.87 100.44 100.41 100.74 100.39 An 50.61 53.63 65.18 67.10 52.56 54.48 57.23 Grouped by crystal. All above points are core in each crystal. 112

Table A7. Probe analyses of plagioclase cont.) Sampl

Na20 5.36 5.80 5.00 5.53 5.13 4.94 3.11 3.05 5.73 2.49 Al203 28.76 27.67 29.08 28.39 28.60 28.94 31.72 31.23 27.92 33.23 Si02 56.16 57.64 55.66 56.68 55.66 55.37 50.41 51.14 56.53 49.30 1{20 0.18 0.23 0.13 0.18 0.16 0.16 0.14 0.22 0.24 0.08 CaO 10.10 9.21 10.97 9.82 10.71 10.81 13.50 13.69 9.29 15.18 FeO 0.25 0.12 0.20 0.13 0.30 0.24 0.45 0.60 0.27 0.33 Total 100.81 100.67 101.03 100.73 100.55 100.45 99.33 99.93 99.98 100.61 An 50.45 46.08 54,40 49.01 53.08 54.23 70.01 70.34 46.59 76.72 Grouped by crystal. All above points are core in each crystal.

. CNB03 I IIII,151PrriaG, Na20 3.32 5.36 5.32 4.92 4.94 5.39 Al203 31.26 28.56 29.12 29.28 29.22 28.74 Si02 50.53 55.81 55.00 55.34 54.83 55.67 1{20 0.14 0.18 0.13 0.21 0.17 0.13 CaO 13.41 10.21 10.50 10.76 10.62 10.28 FeO 0.46 0.28 0.29 0.20 0.23 0.31 Total 99.13 100.39 100.35 100.71 100.00 100.51 An 68.50 50.77 51.79 54.02 53.76 50.92

G' 183G 18441' ' 1860 Na20 3.37 3.81 2.50 1.92 1.60 1.88 Al203 31.83 30.87 32.77 34.22 33.15 33.70 Si02 50.20 51.75 49.45 47.61 47.60 48.18 1(20 0.06 0.09 0.05 0.07 0.05 0.08 CaO 14.46 13.17 15.51 16.41 16.83 16.24 FeO 0.63 0.54 0.83 0.65 1.03 0.68 Total 100.56 100.22 101.10 100.88 100.25 100.76 An 70.07 65.28 77.21 82.20 85.10 82.29 Grouped by crystal. All above points are from rim to core in each crystal.

003 1 200 0 2010 2020 203G 2 Na20 4.76 5 51 5.49 4.97 4.90 5.24 5.66 5.49 4.93 5.34 Al203 28.59 28 45 28.27 28.98 29.32 28.56 28.32 27.61 28.68 28.70 Si02 54.20 55 13 55.07 55.43 54.21 55.44 55.48 55.66 55.21 55.53 1{20 0.20 019 0.27 0.20 0.12 0.17 0.14 0.15 0.16 0.18 CaO 11.57 10 74 9.94 11.00 11.23 10.13 10.51 10.12 9.56 10.62 FeO 0.22 0 22 0.18 0.35 0.28 0.19 0.31 0.24 0.16 0.29 Total 99.53 100.23 99.21 100.93 100.06 99.72 100.42 99.27 98.70 100.64 An 56.69 51,31 49.24 54.39 55.51 51.13 50.25 50.03 51.17 51.84 Grouped by crystal. All above points are from core to rim in each crystal. 113

Table A7. Probe analyses of plagioclase(cont.)

120 Na2O 3.87 5.15 5.3b 4.80 5.30 Al203 30.38 28.96 28.21 28.86 28.73 8102 52.08 55.46 55.20 54.31 55.06 K2O 0.17 0,13 0.23 0.18 0.17 CaO 12.54 9.23 9.95 10.58 10.64 FeO 0.25 0.22 0.30 0.19 0.48 Total 99.30 99.13 99.17 98.91 100.39 An 63.49 49.36 50.22 54.31 52.06

I

Na2O 5.77 5.47 5.47 4.87 3.79 3.49 2.64 M203 27.40 28.87 27.87 28.88 30.52 31.57 32.63 8102 56.36 55.35 56.05 54.41 51.81 51.20 49.24 K2O 0.26 0.18 0.19 0.17 0.15 0.08 0.09 CaO 9.73 10.15 9.68 10.97 13.30 13.38 15.20 FeO 0.33 0.12 0.24 0.19 0.73 0.49 0.55 Total 99.85 100.15 99.49 99.48 100.30 100.22 100.34 An 47.51 50.07 48.89 54.87 65.40 67.58 75.69

Na2O 5.76 6.09 5.44 5.70 5.57 5.09 Al203 27.49 27.64 28.02 28.15 27.97 28.17 8102 57.17 56.68 55.79 56.77 56.34 55.65 1(20 0.22 0.22 0.17 0.18 0.25 0.19 CaO 9.63 9.39 10.51 9.79 9.35 10.37 FeO 0.30 0.32 0.27 0.31 0.34 0.12 Total 100.58 100.35 100.21 100.90 99.82 99.59 An 47.39 45.42 51.12 48.19 47.41 52.36

11=4251 ' 5.40 5.89 5.13 5.25 5.38 5.18 Al203 28.26 28.25 28.74 28.28 27.89 28.53 8102 56.22 56.36 54.68 55.29 55.71 54.92 1(20 0.25 0.15 0.16 0.19 0.15 0.17 CaO 9.73 9.80 10.64 9.94 9.99 10.82 FeO 0.29 0.24 0.33 0.31 0.29 0.27 Total 100.15 100.69 99.66 99.25 99.40 99.89 An 49.14 49.14 52.91 50.56 50.20 53.03 Grouped by rystal. All above points are from core to rim in each crystal. 114

Table A7. Probe analyses of plagioclase cont.

Na2O 5.58 5.52 5.68 5.31 5.39 5.57 5.47 Al203 28.58 28.27 28.24 28.52 26.88 28.68 28.61 S102 55.61 55.60 56.01 55.09 58.25 55.51 55.72 1(20 0.20 0.26 0.21 0.14 0.63 0.16 0.15 CaO 10.20 10.15 9.78 10.73 9.10 10.10 10.63 FeO 0.26 0.30 0.45 0.17 0.44 0.19 0.23 100.44 100.10 100.36 99.96 100.69 100.21 100.81 Total 6 An 49.66 49.63 48.18 52.31 46.42 49.59 51.34

244

Na2O 5.43 5.06 4.99 4.94 5.31 5.44 5.23 Al203 28.35 29.14 29.37 28.82 28.66 28.16 28.98 SiO2 55.38 54.84 54.64 55.46 55.68 55.90 54.93 1020 0.19 0.16 0.10 0.16 0.16 0.27 0.19 CaO 10.03 11.47 10.87 10.20 10.52 10.03 11.07 FeO 0.42 0.18 0.23 0.28 0.37 0.24 0.30 Total 99.80 100.84 100.20 99.86 100.69 100.03 100.70 An 49.98 55.09. 54.29 52.76 51.80 49.70 53.35

110 2 G 56 2 Na2O 3.24 5.02 5.34 5.31 5.19 5.12 4.82 5.22 4.81 Al203 32.12 29.04 28.64 28.34 29.10 29.05 29.59 28.93 29.75 8102 50.91 55.32 55.46 55.86 55.18 54.85 53.81 54.91 54.33 1(20 0.10 0.13 0.13 0.17 0.13 0.18 0.14 0.13 0.16 CaO 14.09 10.68 9.93 10.68 10.63 10.98 11.54 10.98 11.34 FeO 0.21 0.21 0.00 0.30 0.24 0.13 0.18 0.21 0.19 Total 100.67 100.39 99.50 100.65 100.47 100.30 100.07 100.37 100.57 An 70.17 53.64 50.28 52.14 52,67 53.67 56.49 53.36 56.04

Na2O 5.05 5.13 5.15 5.50 4.98 4.97 3.93 4.93 Al203 29.32 29.04 28.59 28.39 28.71 28.58 29.89 29.34 SiO2 54.91 54.72 54.92 55.93 54.67 54.94 51.14 54.47 1(20 0.17 0.08 0.16 0.18 0.18 0.15 0.11 0.16 CaO 10.74 10.68 10.32 10.22 10.92 10.83 13.71 11.07 FeO 0.37 0.28 0.47 0.29 0.14 0.10 0.23 0.34 Total 100.57 99.93 99.61 100.51 99.61 99.56 99.00 100.31 An 53.46 53.23 52.04 50.12 54.20 54.19 65.45 54.87 Grouped by crystal. All above points are from core to rim in each crystal. 115

Table A7. Probe analyses of plagioclase (cont.)

,40 27 %'I,,G Na2O 2 07 2.24 2.12 2.46 Al203 32 21 31.75 33.56 31.44 SiO2 49 10 49.60 47.42 50.60 K2O 0 33 0.39 0.08 0.35 CaO 16 04 14.73 15.54 14.70 FeO 0 60 0.83 0.74 0.72 Total 100 34 99.53 99.45 100.27 An 79.51 76.52 79.84 75.14

Na2O 4.95 5.27 5.33 5.37 5.13 4.94 3.36 3.75 Al203 28.58 27.97 28.30 28.50 29.05 29.77 31.54 31.08 5102 54.81 55.94 55.24 55.10 54.14 53.80 50.68 50.92 IC20 0.16 0.24 0.21 0.25 0.22 0.18 0.09 0.10 CaO 10.67 9.96 9.88 10.29 11.10 11.59 13.78 13.19 FeO 0.24 0.18 0.22 0.26 0.09 0.13 0.25 0.32 Total 99.40 99.56 99.17 99.76 99.73 100.41 99.70 99.35 An 53.85 50.35 49.94 50.66 53.75 55.89 69.03 65.67

Na2O 5.61 4.94 5.65 5.44 4.77 4.66 4.50 5.19 Al203 28.17 28.07 28.18 27.98 29.39 29.36 29.76 28.56 SiO2 55.93 54.96 56.19 56.05 54.28 53.77 54.44 55.37 K2O 0.18 0.17 0.20 0.19 0.10 0.13 0.15 0.23 CaO 10.30 10.52 10.29 9.95 11.17 11.19 11.91 10.35 FeO 0.28 0.28 0.32 0.33 0.18 0.33 0.27 0.50 Total 100.46 98.94 100.81 99.94 99.89 99.45 101.02 100.20 An _ 49.86 53.51 49.59 49.69 56.06 56.58 58.87 51.68

G 9 340 Na2O 3.30 4.84 3.33 3.68 3.57 4.66 5.19 Al203 28.47 28.81 31.90 31.64 31.51 29.47 28.29 SiO2 57.48 54.92 50.67 50.47 50.56 53.53 55.02 K2O 0.74 0.17 0.07 0.10 0.10 0.13 0.17 CaO 12.06 10.05 14.18 13.49 14.45 11.70 10.76 FeO 0.51 0.18 0.43 0.36 0.50 0.22 0.31 Total 102.55 98.97 100.58 99.73 100.70 99.71 99.74 An 63.75 52.88 69.85 66.58 68.70 57.67 52.861 Grouped by crystal. All above points are from core to rim in each crystal. 116

Table A7. Probe analyses of plagioclase cont. _

Na2O 5.10 5.42 5.20 3.28 2.43 Al203 28.67 27.91 28.48 31.70 33.10 SiO2 54.69 56.51 54.77 51.16 48.36 1020 0.19 0.21 0.19 0.10 0.07 CaO 10.75 10.06 10.62 14.17 15.81 FeO 0.19 0.34 0.28 0.66 0.53 Total 99.58 100.44 99.53 101.07 100.28 An 53.20 50.04 52.44 70.06 77.95

Na2O 5.58 4.46 5.22 4.94 5.19 4.43 4.11 Al203 27.86 30.41 28.60 29.50 28.01 30.02 30.40 SiO2 55.90 52.95 55.00 54.70 57.12 53.97 52.82 1020 0.21 0.11 0.17 0.22 0.23 0.13 0.11 CaO 10.08 12.50 10.96 11.19 9.74 12.03 12.73 FeO 0.05 0.21 0.12 0.31 0.27 0.30 0.41 Total 99.68 100.62 100.07 100.86 100.56 100.88 100.58 An 49.37 60.41 53.16 54.87 50.20 59.52 62.73 Both above are core

4.39 5.16 5.36 4.94 5.13 4.87 3.95 4.46 29.89 29.14 29.05 29.19 28.95 29.29 30.92 29.76 54.21 55.98 55.16 55.20 55.96 54.55 52,55 54.35 0.19 0.16 0.15 0.19 0.14 0.16 0.13 0.14 12.18 10.65 10.68 10.58 10.51 11.66 12.72 11.83 0.29 0.10 0.32 0.27 0.32 0.42 0.53 0.37 101.15 101.19 100.72 100.36 101.00 100.95 100.80 100.91 An 59.85 52.81 51.96 53.60 52.66 56.43 63.55 58.94

Na2O 5.20 5.15 5.58 5.01 4.98 5.30 5.38 Al203 28.80 29.07 28.14 29.30 28.84 28.66 28.98 SiO2 55.50 55.34 56.43 55.36 55.86 56.11 55.76 1020 0.15 0.16 0.18 0.16 0.15 0.19 0.21 CaO 10.44 10.56 9.80 10.79 10.63 10.70 9.99 FeO 0.18 0.25 0.20 0.22 0.19 0.19 0.14 Total 100.27 100.52 100.33 100.83 100.65 101.14 100.47 An 52.13 52.62 48.74 53.83 53.61 52.14 50.00 Grouped by crystal. All above points are from core to rim in each crystal except where noted otherwise. 117

Table A7. Probe analyses of plagioclase cont.

Na2O 3.33 3.12 2.95 5.46 5.19 4.29 3.66 3.31 3.29 Al203 32.51 32.30 32.54 28.08 29.22 30.03 31.39 32.51 29.73 SiO2 50.64 50.59 49.86 55.76 55.45 52.71 51.66 50.89 51.55 K2O 0.09 0.07 0.07 0.27 0.17 0.10 0.10 0.10 0.41 CaO 14.42 14.61 13.85 9.86 10.50 12.47 12.89 13.99 13.17 FeO 0.26 0.29 0.31 0.23 0.22 0.37 0.16 0.22 0.35 Total 101.26 100.98 99.58 99.65 100.75 99.97 99.86 101.02 98.49 An 70.14 71.86 71.82 49.15 52.28 61.30 65.64 69.60 67.18

0 ;'"3 $7 88I0^d "I0 Na2O 4.87 5.28 5.37 5.12 5.34 4.60 5.13 5.23 Al203 29.51 28.41 28.50 28.66 28.60 29.58 29.12 28.80 SiO2 54.24 54.96 55.19 55.48 55.71 53.61 55.20 54.68 K2O 0.19 0.26 0.14 0.15 0.19 0.15 0.15 0.20 CaO 11.58 9.38 10.59 10.84 9.82 11.41 11.12 10.34 FeO 0.24 0.19 0.26 0.19 0.35 0.19 0.20 0.26 Total 100.63 98.47 100.04 100.43 100.01 99.54 100.91 99.51 An 56.17 48.78 51.71 53.42 49.82 57.30 54.06 51.56

t, h 3901 9 G Na2O 3.29 4.34 5.11 4.84 5.23 3.14 5.11 Al203 31.60 29.38 29.33 28.97 28.93 31.64 28.57 8102 50.58 52.79 54.67 54.36 54.10 50.10 54.12 K2O 0.12 0.21 0.19 0.13 0.16 0.07 0.11 CaO 13.56 12.05 10.77 10.96 10.89 13.82 9.98 FeO 0.21 0.30 0.39 0.49 0.44 0.34 0.30 Total 99.36 99.07 100.46 99.74 99.75 99.11 98.20 An 69.01 59.82 53.20 55.15 53.03 70.58 51.55

Na2O 3.41 2.73 2.17 4.47 2.64 2.41 3.28 3.67 2.80 Al203 31.78 32.45 33.79 30.90 32.57 32.64 31.21 31.00 32.50 SiO2 50.17 49.02 47.68 51.76 49.64 48.73 51.33 51.76 49.38 1(20 0.15 0.15 0.12 0.22 0.19 0.14 0.22 0.20 0.14 CaO 13.50 15.11 15.21 12.62 14.55 15.18 13.48 13.20 15.19 FeO 0.19 0.32 0.31 0.37 0.61 0.46 0.75 0.39 0.18 Total 99.19 99.79 99.27 100.34 100.20 99.55 100.27 100.22 100.17 An 68.01 74.70 78.89 60.20 74.45 77.02 68.48 65.77 74.40 Grouped by crystal. All above points are from core to rim in each crystal. 118

Table A7. Probe analyses ofplagioclase (cont)

Na20 2.04 2.51 2.06 2.89 3.34 3.13 4.13 3.35 5.15 4.98 Al203 33.41 33.43 33.49 31.86 31.26 32.13 29.98 31.62 28.81 28.90 Si02 48.34 48.35 47.80 50.28 51.09 50.05 53.20 50.19 55.56 53.96 K.20 0.06 0.19 0.08 0.25 0.19 0.18 0.18 0.21 0.33 0.30 CaO 15.95 15.48 16.29 14.45 13.59 14.50 12.38 13.94 10.93 11.25 FeO 0.54 0.76 0.37 0.51 0.50 0.53 0.53 0.35 0.30 0.26 Total 100.33 100.71 100.09 100.24 99.96 100.51 100.40 99.66 101.07 99.64 An 80.91 76.49 80.97 72.30 68.45 71.19 61.67 68.81 52.97 54,59

84m" G, Na20 4.99 5.02 1.82 3.89 2.00 Al203 29.30 28.95 33.82 30.83 33.81 Si02 54.77 55.25 46.93 52.12 47.59 K20 0.28 0.30 0.06 0.16 0.11 CaO 10.64 10.76 16.68 13.04 16.81 FeO 0.20 0.26 0.57 0.71 0.73 Total 100.18 100.53 99.88 100.75 101.04 An 53.20 53.28 83.21 64.31 81.81

4 '428 0 Na20 3.15 4.77 4.68 4.05 Al203 32.00 29.64 29.92 30.41 Si02 49.20 53.28 53.46 53.03 1(20 0.11 012 0.17 0.26 CaO 14.91 11.04 11.92 12.11 FeO 0.45 0.30 0.20 0.35 Total 99.82 99.24 100.36 100.20 An 71.90 55.41 57.88 61.34

Na20 5.13 5.07 5.79 3.00 3.06 4.53 4.12 Al203 28.41 28.66 27.58 31.98 31.99 30.49 29.18 S102 55.47 54.86 56.03 49.12 49.71 53.12 54.35 K20 0.13 0.21 0.22 0.10 0.13 0.18 0.53 CaO 10.42 10.62 9.42 14.32 14.41 12.53 11.58 FeO 0.20 0.16 0.25 0.54 0.53 0.19 0.55 Total 99.76 99.57 99/8 99.05 99.82 101.03 100.31 An 52.48 52.99 46.74 72.12 71.71 59.85 58.89 Grouped by crystal. All above points are from core to rim in each crystal. 119

Table AS. X-ray diffraction analyses $111$1. . '4 n , * n n P"4" I 4 1 " " Pn 'I"444 . ' srr , 444 4* 4 jat.4444 03Mc_03 3.17 100.00 Albite, Enstatite, Magnesio-hornblende 4.03 23.60 Anorthite, Albite 2.65 19.20 Bytownite, Albite 2.53 12.90 Magnetite 2.52 12.00 Bytownite, Enstatite, Albite 3.20 10.00 Anorthite, Albite 03JLBP_03 4.04 100.00 Albite, Anorthite 8.27 80.10 Gedrite, Anthophyllite 3.74 71.00 Albite, Anorthite, Sanidine 3.17 68.80 Albite, Anorthite 3.25 33.60 Gedrite, Anthophyllite, Sanidine 3.35 30.40 Gedrite 03JABP_O4g 3.32 100.00 Muscovite 3.17 94.10 Enstatite, Bytownite, Oligoclase, Anthophyllite, Magnesio-homblende 4.03 58.70 Albite, Bytownite, Oligoclase 2.58 17.80 Muscovite 4.99 3.00 Muscovite 3.21 3.00 Bytownite 3.40 2.80 Magnesio-hornblende 03.1ABP_05 3.20 100.00 Albite, Anorthite 4.03 92.30 Albite, Anorthite 3.74 41.90 Albite, Anorthite 2.50 33.00 Enstatite 03JABP_08 4.03 100.00 Albite, Anorthite 3.75 43.60 Albite, Anorthite 3.21 54.00 Albite, Anorthite 2.84 10.40 Anthophyllite 03JABP_09 3.31 42.00 Lepidolite 3.23 38.00 Sanidine 4.22 10.00 Orthoclase 1.98 5.60 Lepidolite 4.49 4.50 Illite 1.99 2.00 Illite CNB03_1 4.03 100.00 Albite, Anorthite, Bytownite 3.34 33.90 Augite 2.53 30.60 Magnetite 2.95 26.00 Augite, Magnetite 3.21 20.60 Anorthoclase 3.75 14.40 Albite, Anorthite, Bytownite 8.51 11.30 Magnesio-homblende 3.13 7.60 Magnesio-homblende 2.16 5.60 Anorthoclase 120

Table A8. X-ray diffraction analyses cont be 03JLBP_04 3.22 100.00 Albite, Sanidine 4.04 77.10 Anorthite 2.88 7.70 Enstatite 2.54 7.20 Enstatite 3.75 3.75 Anorthite, Sanidine CNB03_2 3.19 100.00 Albite, Anorthite 4.04 36.30 Anorthite 2.54 10.20 Anthophyllite 3.36 5.70 Anthophyllite 03JLBP_07 4.03 100.00 Albite, Anorthite 3.19 63.20 Albite, Anorthite 2.13 23.20 Augite 2.99 16.60 Augite 3.34 12.60 Montmorillionite 03Mc_1 1 2.00 100.00 Muscovite, Phlogopite, Illite 3.21 96.20 Anorthite, Illite, Albite, Sanidine, Pigeonite 2 25 46.20 Phlogopite, Augite 30.00 39.60 Montmorillionite 10.41 26.90 Illite 1.93 10.10 Illite 03Mc_16 3.32 100.00 Lepidolite, Muscovite, Sanidine, Augite 3.19 69.50 Albite, Muscovite 2.91 69.00 Diopside 2.50 44.20 Enstatite 3.00 39.50 Anorthite, Diopside 2.53 31.50 Augite 2.54 31.50 Enstatite, Ilmenite 03Mc_12 4.03 15.60 Albite, Anorthite, Andesine, Bytownite 2.51 9.50 Phlogopite 3.18 15.00 Andesine, Bytownite 3.21 2.00 Oligoclase 03Mc_10 3.33 100.00 Muscovite, Sanidine, Orthoclase 4.03 46.90 Albite, Anorthite 3.20 46.20 Albite, Anorthite 3.75 18.90 Anorthite 03JABP_02 4.03 100.00 Albite, Anorthite 3.34 11.80 Augite, Montmorillionite, Illite, Muscovite 2.01 7.50 Illite 03JABP_06 3.17 100.00 Enstatite, Albite, Anorthite 3.75 45.00 Albite 3.34 44.60 Augite, Montmorillionite, Illite, Muscovite 4.04 25.60 Anorthite 2.00 25.50 Illite, Phlogopite 121

Table A9a. Linear deconvolution results for section 1, interior surface results on left, top surface results on right OP :04,110.glOiX Chlorite BUR-1340 12-29-95 5.6 13.3 Obsidian Glass 7.2 15.5 Augite (Wo44 En28 Fs28) 2.0 4.8 Chlorite BUR-1340 12-29-95 6.8 14.6 NMNH-9780 Ilmenite WAR-4119 12-15-97 14.6 34.3 Augite (Wo44 En28 Fs28) 10.2 21.9 NMNH-9780 Illite (granular) 20.2 47.7 Ilmenite WAR-411912-15-97 20.2 43.6

blackbody 57.7 0.0 Illite (granular) 2.6 5.6 Total 100 100 blackbody 54.2 0.0 Spectral nns(%) = 1.111 Total 101 101 Endmember vectors = 17, 25, 40, 44, 45 Spectral rms(%) = 1.636 Endmember vectors = 9, 17, 25, 40, 44, 45

004014411, ," . , .11 .. , Bytownite WAR-5859 25.6 46.6 Bytownite WAR-5859 9.1 40.2 Quartz 6.7 12.1 Albite WAR-0235 8-16-95 0 1.4 Augite (Wo44 En28 Fs28) 4.0 7.3 Biotite flakes (oxides from 3.3 14.8 NMNH-9780 BUR-840) Anorthoclase WAR-0579 1-2- 12.3 22.3 Obsidian Glass 2.6 11.6 96 Gedrite (Amphibole) BUR- 1.5 2.8 Oligoclase (Peristerite) BUR- 0.9 4.1 1700 060D Perthite WAR-5802 1-3-96 4.6 8.3 Diopside (Di50) NMNH- 2.3 10.3 107497 Ilmenite WAR-41I9 12-15-97 0.4 0.7 Clinochlore (Chlorite) WAR- 0.9 4.0 1924 blackbody 45.2 0.0 Elite (granular) 3.1 13.8 Total 100 100 blackbody 77.5 0.0 Spectral rms(%) = 0.433 Total 100.1 100.1 Endmember vectors = 3, 6, 25, 27, 30, 37, 40, Spectral rms(%) = 0.400 45 Endmember vectors = 3, 4, 8, 9, 10, 23, 38, 44, 45 122

Table A9a. Linear deconvolution results for section 1 (cont.) interior surface results on left, top surface results on right 19010#0 8.6 18.4 Quartz 2.4 4.9 Biotite flakes (oxides from 3.4 7.4 Hornblende WAR-0404 5.3 10.9 BUR-840) 12/27/1995 Anorthite WAR-5759 6.3 13.6 Biotite flakes (oxides from 1.3 2.7 BUR-840) Albite WAR-5851 4.3 9.2 Obsidian Glass 4.2 8.6 Diopside (Di50) NMNH- 3.6 7.8 Andesine BUR-240 8-4-95 8.5 17.3 107497 Sanidine WAR-RGSANOI 6- 20.3 43.6 Albite WAR-5851 9.0 18.4 12-97 blackbody 53.4 0.0 Diopside (Di50) NMNH- 2.1 4.4 107497 Total 100.0 100.0 Gedrite (Amphibole) BUR- 9.3 18.9 1700 Spectral rms(%) = 0.514 Magnetite WAR-0384 2.8 5.7 12/15/1997 Endmember vectors = 6, 8, 12, 19, 23, 41, 45 Ilmenite WAR-4119 12-15-97 4.0 8.2

blackbody 51.1 0.0 Total 100.0 100.0 Spectral rms(%) = 0.532 Endmember vectors = 6, 7, 8, 9, 18, 19, 23, 30, 39, 40, 45

.„. Bytownite WAR-5859 12.7 34.0 Quartz 4.0 10.7 Biotite flakes (oxides from 3.2 8.6 BUR-840) Obsidian Glass 3.7 9.8 Oligoclase (Peristerite) BUR- 8.7 23.1 060D Albite WAR-5851 0.5 1.4 Diopside (Di50)NMNH- 4.6 12.4 107497 blackbody 62.5 0.0 Total 100.0 100.0 Spectral rms(%) - 0.386 Endmember vectors = 3, 6, 8, 9, 10, 19, 23, 45 123

Table A9b. Linear deconvolution results for section 2 interior surface results on left, top surface results on right . , 4 740 0040111intle , Bytownite WAR-5859 33.7 35.5 Bytownite WAR-5859 24.8 58.0 Quartz 9.1 9.6 Quartz 8.5 19.8 Oligoclase (Peristerite) BUR- 18.9 19.9 Biotite flakes (oxides from 2.1 4.9 060D BUR-840) Andesine BUR-240 8-4-95 23.4 24.7 Perthite WAR-5802 1-3-96 2.7 6.4 Albite WAR-5851 6.0 6.3 Sanidine WAR-RGSANO1 6- 4.8 11.2 12-97 Enstatite (En93)NMNH-34669 2.4 2.5 blackbody 57.4 0.0

Magnetite WAR-0384 12-15- 1.4 1.5 Total 100.3 100.3 97 blackbody 5.1 0.0 Spectral mis(%) = 0.452 Total 100.1 100.1 Endmember vectors = 3, 6, 8, 37 41, 45 Spectral tms(%) = 0.477 Endmember vectors = 3, 6, 10, 18, 19, 21, 39, 45 lot :00, Bytownite WAR-5859 28.9 47.5 Bytownite WAR-5859 3.7 77.8 Quart 11.7 19.2 Biotite flakes (oxides from 1.0 22.0 BUR-840) Oligoclase (Peristerite) BUR- 16.6 27.4 blackbody 95.1 0.0 060D Perthite WAR-5802 1-3-96 3.7 6.1 Total 99.8 99.8 blackbody 39.3 0.0 Spectral rms(%) = 0.375 Total 100.2 100.2 Endmember vectors = 3, 8, 45 Spectral rms(%) = 0.780 Endmember vectors = 3, 6, 10, 37, 45

Bytownite WAR-5859 62.2 64.3 Bytownite WAR-5859 12.8 33.3 Quartz 13.8 14.3 Quartz 8.3 21.5 Anorthoclase WAR-0579 1-2- 5.9 6.2 Gedrite (Amphibole) BUR- 4.8 12.5 96 1700 Anthophyllite (Amphibole) 0.6 0.6 Perthite WAR-5802 1-3-96 10.1 26.3 BUR-476 Perthite WAR-5802 1-3-96 8.4 8.6 Sanidine WAR-ROSANO1 6- 2.5 6.5 12-97 Sanidine WAR-RGSANOI 6- 5.8 6.0 blackbody 61.6 0.0 12-97 blackbody 3.3 0.0 Total 100.1 100.1 Total 99.9 99.9 Spectral rms(%) = 0.536 Spectral rms(%) = 0.656 Endmember vectors = 3, 6, 30, 37, 41, 45 Endmember vectors = 3, 6, 27, 35, 37, 41, 45 124

Table A9b. Linear deconvolution results for section 2 (cont.) interior surface results on left, ton surface results on right 400+ thiirs Bytownite WAR-5859 24.9 49.6 Bytownite WAR-5859 18.0 42.9 Quartz 9.9 19.6 Quartz 5.6 13.3 Katophorite (Amphibole) 3.5 7.0 Oligoclase (Peristerite) BUR- 5.0 11.8 BUR-2660 060D Anorthoclase WAR-0579 1-2- 4.8 9.5 Augite (Wo44 En28 Fs28) 3.5 8.4 96 NMNH-9780 Perthite WAR-5802 1-3-96 7.4 14.7 Perthite WAR-5802 1-3-96 0.9 2.2 blackbody 49.9 0.0 Illite (granular) 9.1 21.6 Total 100.4 100.4 blackbody 58.1 0.0 Spectral rms(%) = 0.674 Total 100.2 100.2 Endmember vectors = 3, 6, 14, 27, 37, 45 Spectral rms(%) = 0.545 Endmember vectors - 3, 6, 10, 25, 37, 44, 45

ittlIA41:::04irt Bytownite WAR-5859 32.6 60.4 Bytownite WAR-5859 21.7 60.9 Quartz 11.5 21.4 Quartz 7.7 21.6 Perthite WAR-5802 1-3-96 10.0 18.6 Perthite WAR-5802 1-3-96 6.3 17.7 blackbody 46.1 0.0 blackbody 64.5 0.0 Total 100.3 100.3 Total 100.2 100.2 Spectral rrns(%) = 0.744 Spectral rms(%) = 0.580 Endmember vectors = 3, 6, 37, 45 Endmember vectors = 3, 6, 37, 45

C Ini 0310,0 eilv tairii1 Bytownite WAR-5859 43.8 63.0 Bytownite WAR-5859 4.8 28.4 Quartz 11.8 16.9 Quartz 1.2 6.9 Albite WAR-5851 2.1 3.0 Biotite flakes (oxides from 1.6 9.4 BUR-840) Anthophyllite (Amphibole) 2.8 4.0 Obsidian Glass 2.4 13.9 BUR-4760 Perthite WAR-5802 1-3-96 3.1 4.5 Albite WAR-5851 0.9 5.5 Sanidine WAR-RGSANOI 6- 6.3 9.0 Diopside (Di50) NMNH- 0.6 3.8 12-97 107497 blackbody 30.6 0.0 Gedrite (Amphibole) BUR- 5.5 32.2 1700 Total 100.4 100.4 blackbody 3.1 0.0 Spectral rms(%) = 0.567 Total 0.1 100.1 Endmember vectors = 3, 6, 19, 35, 37, 41, 45 Spectral nns(%) - 0.302 Endmember vectors = 3, 6, 8, 9, 9, 23, 30, 45 125

Table A9b Linear deconvolution results for section 2 (cont.) interior surface results on left, ton surface results on right 551511 1101 54431111 511- '11 1 55 Bytownite WAR-5859 42.0 51.3 Bytownite WAR-5859 14.8 57 Quartz 14.0 17.1 Quartz 3.8 14.5 Oligoclase (Peristerite) BUR- 25.0 30.6 Biotite flakes (oxides from 0.8 3.2 060D BUR-840) Anthophyllite (Amphibole) 0.7 0.8 Oligoclase (Peristerite) BUR- 3.6 13.7 BUR-4760 060D blackbody 18.1 0.0 Diopside (D150) NMNH- 2.4 9.1 107497 Total 99.8 99.8 Anorthoclase WAR-0579 1-2- 0.6 2.3 96 Spectral rms(%) = 0.798 blackbody 73.9 0.0 Endmember vectors = 3, 6, 10, 35, 45 Total 99.8 99.8 Spectral rms(%) = 0.363 Endmember vectors - 3, 6, 8, 10 23, 27, 45 ii 'outtliphrtbill ', Bytownite WAR-5859 19.9 28.3 Quartz 15.7 22.4 Oligoclase (Peristerite) BUR- 2.2 3.1 060D Katophorite (Amphibole) 32 4.6 BUR-2660 Andesine BUR-240 84-95 19.8 28.2 Albite WAR-5851 4.9 7.0 Perthite WAR-5802 1-3-96 1.3 1.9 Illite (granular) 3.2 4.6 blackbody 29.7 0.0 Total 100.0 100.0 Spectral rms(%) = 0.581 Endmember vectors = 3, 6, 10, 14, 18,. 19, 37, 44, 45

11014018tr iirli Bytownite WAR-5859 39.9 44.9 Biotite flakes (oxides from 1.2 8.4 BUR-840) Quartz 11.3 12.8 Obsidian Glass 1.8 12.5 Katophorite (Amphibole) 6.5 7.3 Anorthite WAR-5759 8.9 62.9 BUR-2660 Albite WAR-5851 8.0 9.0 Diopside (13150)NMNH- 0.2 1.3 107497 Illite (granular) 23.6 26.6 Anorthoclase WAR-0579 1-2- 2.1 14.9 96 blackbody 11.3 0.0 blackbody 85.9 0.0 Total 100.6 100.6 Total 100.0 100 Spectral rms(%)= 0.543 Spectral rms(%) = 0.387 Endmember vectors = 3, 6, 14, 19, 44, 45 Endmember vectors = 8, 9, 12, 23, 27, 45 126

Table Mb. Linear deconvolution results for section 2 (cont.) interior surface results on left, top surface results on right VW i0 6011ti Obsidian Glass 11.8 23.9 Anorthite WAR-5759 2.1 4.2 Albite WAR-5851 11.9 24.1 Augite (Wo44 En28 Fs28) 11.2 22.7 NMNH-9780 Muscovite WAR-5474 12-15- 3.5 7.1 97 Unknown amphibole WAR- 0.2 0.5 0219 Sanidine WAR-RGSANO1 6- 8.9 18.1 12-97 blackbody 51.0 0.0 Total 100.6 100.6 Spectral rms(%) = 0.425 Endmember vectors = 9, 12, 19, 25, 28, 34, 41, 45

Bytownite WAR-5859 24.1 34.0 Bytownite WAR-5859 23.9 22.7 Quartz 9.9 14.0 Quartz 10.9 10.4 Anorthite WAR-5759 10.5 14.8 Obsidian Glass 12.5 11.9 Katophorite (Amphibole) 0.5 0.7 Oligoclase (Peristerite) BUR- 3.8 3.6 BUR-2660 060D Anorthoclase WAR-0579 1-2- 21.8 30.7 Anorthite WAR-5759 9.1 8.6 96 Tremolite (High Fe) HS- 1.3 1.8 Enstatite (En93) NMNH- 4.1 3.9 315.4b 34669 Perthite WAR-5802 1-3-96 3.0 4.3 Hedenbergite (Wo50 En3 4.2 4.0 Fs47) NMNHO blackbody 29.2 0.0 Ilmenite WAR-4119 2.0 1.9 12/15/1997 Total 100.3 100.3 Sanidine WAR-RGSANO1 20.4 19.4 6/12/1997 Spectral rms(%) = 0.424 ICaohnite (solid) 6.9 6.5 Endmember vectors = 3, 6, 12, 14, 27, 32, 37, 45 Illite (granular) 7.6 7.2 blackbody -5.2 0.0 Total 100.1 100.1 Spectral rms(%) = 0.449 Endmember vectors = 3, 6, 9, 10, 12, 21, 26, 40, 41, 42, 44, 45 127

Table A9b. Linear deconvolution results for section 2 (cont.) interior surface results on left, top surface results on right i l - ate' , 0434.11n ' ' I:" '11PP' I i Bytownite WAR-5859 20.2 41.6 Biotite flakes (oxides from 0.5 3.4 BUR-840) Quartz 8.9 18.4 Obsidian Glass 1.5 10.2 Anorthite WAR-5759 6.2 12.8 Oligoclase (Peristerite) BUR- 7.1 47.9 060D Katophorite (Amphibole) 0.3 0.7 Labradorite BUR-3080A 8-17- 1.6 11.0 BUR-2660 95 Anthophyllite (Amphibole) 1.7 3.6 Diopside (Di50)NMNH- 3.4 22.7 BUR-4760 107497 Perthite WAR-5802 1-3-96 9.3 19.1 Clinochlore (Chlorite) WAR- 0.7 4.5 1924 Dickite (powder; Kaolinite 2.1 4.3 blackbody 84.9 0.0 group) blackbody 51.5 0.0 Total 99.8 99.8 Total 100.4 100.4 Spectral rms(%) = 0.410 Spectral mis(%) = 0.496 Endmember vectors = 8, 9, 10, 11, 23, 38, 45 Endmember vectors = 3, 6, 12, 14, 35, 37, 43, 45

Quartz 3.5 15.2 Bytownite WAR-5859 24.7 72.3 Biotite flakes (oxides from 1.8 8.0 Quartz 1.5 4.3 BUR-840) Anorthite WAR-5759 11.0 48.0 Hornblende WAR-0404 12-27- 0.0 0.1 95 Anorthoclase WAR-0579 1-2- 6.7 29.1 Biotite flakes (oxides from 0.8 2.4 96 BUR-840) blackbody 7.2 0.0 Obsidian Glass 1.4 4.1 Total 100.3 100.3 Labradorite BUR-3080A 8-17- 0.2 0.6 95 Spectral rms(%) = 0.382 Diopside (Di50) NMNH- 1.0 3.1 107497 Endmember vectors - 6, 8, 12, 27, 45 Anorthoclase WAR-0579 1-2- 4.4 12.9 96 Magnesio-homblende HS- 0.1 0.2 115.4b blackbody 5.9 0.0 Total 100.1 100.1 Spectral nris(%) = 0.355 Endmember vectors - 3, 6, 7, 8, 9, 11, 23, 27, 33, 45 128

Table A9b. Linear deconvolution results for section 2 (cont.) interior surface results on left, ton surface results on right 1;0 gOtt4P011 ,111 Bytownite WAR-5859 21.5 25.1 Labradorite WAR-4524 1-2-96 34.6 37.2

Quartz 5.5 6.4 Quartz 2.7 0.0 Obsidian Glass 2.4 0.0 Biotite flakes (oxides from 5.4 5.8 BUR-840) Oligoclase (Peristerite) BUR- 3.5 0.0 Obsidian Glass 15.0 16.1 060D Albite WAR-5851 10.5 12.2 Anorthite WAR-5759 11.5 12.4 Diopside (Di50)NMNH- 8.3 9.7 Broazite (3z72)NMNH- 6.2 6.7 107497 C2368 Hedenbergite (Wo50 En3 4.3 0.0 Diopside (Di50) NMNH- 2.9 0.0 Fs47) NMNH-R11524 107497 Gedrite (Amphibole) BUR- 23.7 27.6 Augite (Wo44 En29 Fs20 Ac8) 5.0 5.4 1700 WAR-6474 Ilmenite WAR-4119 12-15-97 4.1 0.0 Perthite WAR-5802 1-3-96 1.4 0.0

Elite (granular) 16.4 19.1 Dickite (powder; Kaolinite 15.6 16.8 group) Total 100.1 100.1 Total 100.2 1002 Spectral RMS1.329% Spectral RMS=0.276% Endmember vectors NA Endmember vectors NA

Quartz 6.9 7.4 Bytownite WAR-5859 3.8 0.0 Biotite flakes (oxides from 0.5 0.0 Quartz 10.4 11.3 BUR-840) Obsidian Glass 31.1 33.2 Biotite flakes (oxides from 3.9 0.0 BUR-840) Muscovite WAR-5474 12-15- 2.4 0.0 Obsidian Glass 24.1 26.1 97 Anthophyllite (Amphibole) 1.6 0.0 Anorthite WAR-5759 9.8 10.6 BUR-4760 limonite WAR-4119 12-15-97 1.9 0.0 Perthite WAR-5802 1-3-96 6.7 7.3

Illite (granular) 56.5 60.3 Dickite (powder; Kaolinite 10.4 11.3 group) Total 100.8 100.8 Illite (granular) 31.6 34.2 Spectral RMS=0.486% Total 100.7 100.7 Endmember vectors NA Spectral RMS1.369% Endmember vectors NA 129

Table A9b. Linear deconvolution results for section 2 (cont.) interior surface results on left, toD surface results on right ,OTAO o osaseillithmi Bytownite W AR-5859 12.5 19.2 Bytownite WAR-5859 2.9 5.9 Quartz 20.7 31.7 Quartz 7.6 15.3 Oligoclase (Peristerite) BUR- 19.3 29.6 Obsidian Glass 18.1 36.5 060D Richterite (Amphibole) ASU- 1.7 2.6 Perthite WAR-5802 1-3-96 8.2 16.5 03 Albite WAR-5851 6.1 9.4 Illite (granular) 12.5 25.3 Hedenbergite (Wo50 En3 0.9 1.3 blackbody 50.3 0.0 Fs47) NMNHO Anorthoclase WAR-0579 3.5 5.3 Total 99.6 99.6 1/2/1996 Illite (granular) 0.2 0.3 Spectral rms(%) = 0.804 blackbody 34.5 0.0 Endmember vectors = 3, 6, 9, 37 44, 45 Total 99.5 99.5 Spectral nose) = 0.911 Endmember vectors = 3, 6, 10, 13, 19, 26, 27, 44, 45

SW* Bytownite WAR-5859 26.4 42.6 Quartz 6.8 14.8 Quartz 15.3 24.7 Obsidian Glass 3.4 7.3 Albite WAR-5851 8.3 13.3 Anorthite WAR-5759 7.0 15.2 Anorthoclase WAR-0579 1-2- 11.9 19.2 Amazonite WAR-0650 8-17- 2.2 4.7 96 95 blackbody 37.9 0.0 Bronzite (Bz72) NMNH- 1.4 3.0 C2368 Total 99.9 99.9 Anorthoclase WAR-0579 1-2- 13.0 28.0 96 Spectral rms(%) = 0.687 Tremolite (High Fe) HS- 1.2 2.6 315.4b Endmember vectors - 3, 6, 19, 27, 45 Perthite WAR-5802 1-3-96 1.9 4.0 Illite (granular) 9.5 20.6 blackbody 53.9 0.0 Total 100.3 100.3 Spectral rms(%) = 0.450 Endmember vectors = 6, 9, 12, 16, 22, 27, 32, 37, 44,45 130

Table A9c. Linear deconvolution results for section 3 interior surface results on left, top surface results on right *ft 11-0? 11100Ci* Bytownite WAR-5859 14.6 38.5 Obsidian Glass 8.3 22.8 Quartz 6.5 17.2 Anorthite WAR-5759 1.2 3.3 Obsidian Glass 3.3 8.8 Albite WAR-5851 9.8 26.8 Albite (Cleavelandite) WAR- 2.2 5.9 Augite (Wo44 En28 Fs28) 8.8 24.1 0612 12/23/1995 NMNH-9780 Amazonite WAR-0650 1.7 4.5 Mite (granular) 8.6 23.6 8/17/1995 Aught (Wo44 En28 Fs28) 1.4 3.7 blackbody 63.7 0.0 NMNH-9780 Gedrite (Amphibole) BUR- 8.1 21.4 Total 100.5 100.5 1700 blackbody 62.2 0.0 Spectral rms(%) = 0.512 Total 100 100 Endmember vectors = 9, 12, 19, 25, 44, 45 Spectral nms(%) = 0.575 Endmember vectors = 3, 6, 9, 15, 16, 25, 30, 45

Bytownite WAR-5859 8.9 45.6 Bytownite WAR-5859 11.4 63.7 Quartz 3.6 18.7 Obsidian Glass 2.3 13.0 Gedrite (Amphibole) BUR- 1.2 6.0 Oligoclase (Peristerite) BUR- 0.6 3.5 1700 0600 Perthite WAR-5802 1-3-96 4.6 23.8 Augite (Wo44 En28 Fs28) 3.5 19.6 NMNH-9780 Mite (granular) 1.1 5.7 blackbody 81.9 0.0 blackbody 80.4 0.0 Total 99.7 99.7 Total 99.8 99.8 Spectral rms(%) = 0.542 Spectral rms(%) = 0.432 Endmember vectors = 3, 9, 10, 25, 45 Endmember vectors = 3, 6, 30, 37, 44, 45

Bytownite WAR-5859 1.7 7.7 Bytownite WAR-5859 4.7 46.3 Quartz 3.8 17.0 Obsidian Glass 1.7 16.6 Obsidian Glass 7.0 30.9 Augite (Wo44 En29 Fs20 2,1 20.6 Ac8) WAR-6474 Illite (granular) 10.1 44.7 Dickite (powder; Kaolinite 1.6 16.2 group) blackbody 77.7 0.0 blackbody 89.6 0.0 Total 100.3 100.3 Total 99.7 99.7 Spectral rms(%) = 0.436 Spectral rms(%) = 0.385 Endmember vectors = 3, 6, 9, 44, 45 Endmember vectors = 3, 9, 24, 43, 45 131

Table A9c. Linear deconvolution results for section 3 interior surface results on left, top surface results on right

Ofil Bytownite WAR-5859 13.5 56.5 Quartz 1.4 5.9 Obsidian Glass 3.4 14.2 Oligoclase (Peristerite) BUR-060D 0.7 3.0 Bronzite (Bz72) NMNH- C2368 2.0 8.3 Hedenbergite (Wo50 En3 Fs47)NMNHO 2.3 9.4 Kaolinite (solid) 0.5 2.2 Illite (granular) 0.1 0.3 blackbody 75.9 0.0 Total 99.9 99.9 Spectral rms(%) = 0.341 Endmember vectors = 3, 6, 9, 10, 22, 26, 42 44 45

iii Obsidian Glass 3.2 21.1 Perthite WAR-5802 1-3-96 3.5 23.1 Illite (granular) 8.5 55.3 blackbody 84.3 0.0 Total 99.5 99.5 Spectral nns(%) = 0.597 Endmember vectors = 9, 37, 44, 45 132

Table A9d. Additiona linear deconvolution results interior surface results on left, top surfacexmisi* results on right Bytownite WAR-5859 17.2 21.4 Andesine WAR-0024 8-17-95 10.9 11.1 Quartz 10.1 12.6 Microcline AK-01 8-17-95 2.9 13.2 Oligoclase (Peristerite) BUR- 32.6 40.6 Homblende WAR-0404 12- 1.1 1.1 060D 27-95 Bronzite (Bz72) NMNH- 1.5 1.8 Biotite flakes (oxides from 1.5 1.5 C2368 BUR-840) Diopside (Di50) NMNH- 1.7 2.1 Obsidian Glass 12 12.2 107497 Hedenbergite (Wo50 En3 1.2 1.4 Anorthite WAR-5759 12.3 12.5 Fs47) NMNHO Anorthoclase WAR-0579 1-2- 2.3 2.9 Augite (Wo44 En28 Fs28) 14.6 14.8 96 NMNH-9780 Magnetite WAR-0384 9.8 12.3 Magnetite WAR-0384 12-15- 12.6 12.8 12/15/1997 97 Illite (granular) 4.5 5.6 Ilmenite WAR-4119 12-15-97 4.5 4.6

blackbody 19.9 0.0 Kaolinite (solid) 10.6 10.7 Total 100.7 100.7 Illite (granular) 7.2 7.3 Spectral rms(%) - 0.482 blackbody 1.7 0 Endmember vectors = 3, 6, 10, 22, 23, 26, 27, Total 102 102 39, 44, 45 Spectral rms(%) = 0.407 Endmember vectors = 1, 5, 7, 8, 9, 12, 2 , 39, 40, 42, 44, 45

.100f0-4101.C.,' Bytownite WAR-5859 34,9 44.6 Microcline AK-01 8/17/1995 6.4 7.2 Quartz 8.5 10.9 Quartz 5.8 6.6 Obsidian Glass 15.6 20.0 Obsidian Glass 47.4 53.9 Oligoclase (Peristerite) BUR- 10,0 12.8 Hedenbergite (Wo50 En3 3 3.4 060D Fs47) NMNHO Richterite (Amphibole) ASU- 3.0 3.8 Magnetite WAR-0384 19.7 22.4 03 12/15/1997 Bronzite (Bz72) NMNH- 0.8 1.1 Illite (granular) 7.3 8,3 C2368 Hedenbergite (Wo50 En3 0.4 0.5 blackbody 12.3 0.0 Fs47) NMNHO Anorthoclase WAR-0579 1.6 2.1 Total 102 102 1/2/1996 Magnetite WAR-0384 3.5 4.5 Spectral rms(%) = 1.211 12/15/1997 blackbody 21.8 0.0 Endmember vectors - 5, 6, 9, 26, 39, 44, 45 Total 100.2 100.2 Spectral nns(%) = 0.398 Endmember vectors = 3, 6, 9, 10, 13, 22, 26, 27, 39, 45 133

Table A9d. Additional linear deconvolution results (cont.) interior surface results on left, too surface results on right ' al401910 Bytownite WAR-5859 16.1 16.0 Bytownite WAR-5859 12.8 27.7 Quartz 4.6 4.6 Quartz 1.8 3.8 Oligoclase (Peristerite) BUR- 9.5 9.5 Biotite flakes (oxides from 2.0 4.4 060D BUR-840) Richterite (Amphibole) ASU- 0.8 0.8 Obsidian Glass 1.3 2.8 03 Albite WAR-5851 2.7 2.7 Oligoclase (Peristerite) BUR- 6.8 14.7 060D Augite (Wo44 En28 Fs28) 6.0 5.9 Richterite (Amphibole) ASU- 0.4 0.9 NMNH-9780 03 Gedrite (Amphibole) BUR- 5.8 5.8 Hedenbergite (Wo50 En3 2.1 4.6 1700 Fs47) NMNHO Actinolite WAR-0354 2.9 2.9 Magnetite WAR-0384 5.9 12.7 12/15/1997 Magnetite WAR-0384 12-15- 7.0 7.0 Illite (granular) 13.4 28.9 97 Sanidine WAR-RGSANO1 6- 5.2 5.2 blackbody 54.1 0.0 12-97 Kaolinite (solid) 13.6 13.5 Total 101 101 Illite (granular) 27.3 27.1 Spectral rms(%) = 0.327 blackbody -0.7 0.0 Endmember vectors = 3, 6, 8, 9, 10, 13, 26, 39, 44, 45 Total 100.9 100.9 Spectral ruts(%) = 0.413 Endmember vectors = 3, 6, 10, 13, 19, 25, 30, 31, 39, 41, 42, 44, 45

Dickite (powder; Kaolinite 4.8 96.8 group) blackbody 92 0.0 Total 96.8 96.8 Spectral rms(%) = 2.731 Endmember vectors = 43, 45 134

Table A9d. Additional linear deconvolution results (cont.) interior surface results on left, top surface results on right

Bytownite WAR-5859 16.7 43.8 Bytownite WAR-5859 8.8 92.5 Albite WAR-0235 8-16-95 0.9 2.3 Biotite flakes (oxides from 0.7 7.4 BUR-8 Quartz 2.5 6.5 blackbody 0.5 0.0 Obsidian Glass 2.1 5.6 Total 100.0 100.0 Amazonite WAR-0650 8-17- 4.2 11.0 Spectral nns(i) = 0.366 95 Augite (Wo44 En28 Fs28) 1.5 4.0 Endmember vectors = 3, 8, 45 NMNH-9780 Ilmenite WAR-4119 12-15-97 3.0 7.9 Illite (granular) 7.3 19.2 OBISIO blackbody 62.0 0.0 Bytownite WAR-5859 7 44.6 Total 100.3 100.3 Hornblende WAR-0404 1.9 12.3 12/27/1995 Spectral nns(%) = 0.332 Biotite flakes (oxides from 0.4 2.4 BUR-840) Endmember vectors = 3, 4, 6, 9, 16, 25, 40, 44, Obsidian Glass 1.2 7.6 45 Hedenbergite (Wo50 En3 1.2 7.8 Fs47) NMNHO Magnetite WAR-0384 4.0 25.4 12/15/1997 blackbody 84.5 0.0 Total 100.3 100.3 Spectral rms(%) = 0.319 Endmember vectors = 3, 7, 8, 9, 26, 39, 45 135

Table A9d. Additional linear deconvolution results (cont.) interior surface results on left, ton surface results on right 4p Quartz 4.3 10.7 Bytownite WAR-5859 29.4 59.9 Obsidian Glass 11.7 29.3 Quartz 3.9 8.0 Anorthite WAR-5759 11.8 29.5 Hornblende WAR-0404 12-27- 4.2 8.6 95 Katophorite (Amphibole) 1.5 3.8 Obsidian Glass 6.2 12.6 BUR-2660 Diopside (Di50)NMNH- 1.1 2.6 Augite (Wo44 En28 Fs28) 0.9 1.8 107497 NMNH-9780 Anorthoclase WAR-0579 1-2- 7.3 18.4 Anorthoclase WAR-0579 1-2- 4.5 9.3 96 96 Tremolite (High Fe) HS-315.4b 1.6 4.1 blackbody 51.0 0.0

Perthite WAR-5802 1-3-96 0.7 1.7 Total 100 100 blackbody 60.1 0.0 Spectral rms(%) = 0.435 Total 100 100 Endmember vectors = 3, 6, 7, 9, 25, 27, 45 Spectral rms(%) = 0.344 Endmember vectors = 6, 9, 12, 14, 23, 27, 32, 37, 45

136

Table A10. Additional analytical and pixel color results P

03MC_1 9 84.8 7.8 7.4 0 0 100 40.6 34.2 2.7 14 8.6 100 B 61.33 69.2 12.4 8.6 0 9.8 100 Z 031LBP_08 100 0 0 0 0 100 77.8 0 22 0 0 99.8 B NA 03JLBP 01 93.4 7 0 0 0 100 70.2 8.4 21.6 0 0 100 B 61.21 03MC_05 96.4 4 0 0 0 100 40.8 36 9.4 0 14 100 B 58.64 03JLBP_02 90.9 4.6 4.6 0 0 100 87.5 9.1 3.2 0 0 99.8 R NA 99 0.8 0 0 0 99.8 03MC_04 92.3 0 8 0 0 100 89.5 4 2.4 0 4.1 100 R 61.94 03JABP 10 95.2 3.9 0.3 0 0 99.4 37.7 0 25.3 0 37 99.5 R 62.11 03JABP_04rr 100 0 0 0 0 100 100 0 0 0 0 100 R 61.11 0 03MC 06 66.1 25.1 0 0 t 8.8 100 30.1 24.1 23.6 0 23 101 B 57.84 03JABP_07 na na na na na na 65.4 17.7 2.5 0 14 99.8 G NA 23.1 0 55.3 0 21 99.5 CNB03 3 88.1 6 5.7 0 0 99.8 67.2 19.6 0 0 13 99.8 B NA

03MC 09 0 0 96.8 0 0 96.8 na na na na na na 0 NA 03MC 20 77.5 5.3 5.6 12 0 101 36.8 15.9 19.5 17 12 102 NA 59.91 03JABP 14 50.8 5.5 28.9 13 2.8 101 2,3 26.6 60.1 7.1 4.6 101 R NA CNB035 63.6 4 19.2 7.9 5.6 100 44.6 20.1 2.4 2.5 7.6 100 G NA 92.5 0 7.4 0 0 99.9 03MC 07 70.4 5.4 0 4.5 20 100 13.8 3.4 8.3 22 54 102 NA 63.11 CNB03_4 60.3 10.5 0 0 29.3 100 77.2 10.4 0 0 13 100 B 60.78

Fmk =framework 0th. =other GIs =obsidian glass

Pix. =pixel color B=blue, G=green, R=red, 0=orange, NA=not available 137

1 02 03JABP 04a Red

1.00 0.98 0.96 0.94 0.92 0.90 0 88 03JLBP_02 Red 1.01 0.99 Original i 0.97 Reconstructed i 0.95 Original t 0.93 Reconstructed t 0.91 Original i2 Reconstructed i2 0.89 Oct 02 ASTER 0.87 0 85

03JLBP 01 Blue 1.00 0.98 0.96 0.94 0.92 0 90 7 8 9 10 11 12 13 14 15 Wavelength (microns)

Figure Ala. Additional emissivity plots and pixel color of section 2 samples 138

1 01 CNB03 3 Blue 1.00 0.99 -414S4 Original i Reconstructed i 0.98 Original t .1 0.97 , ter Reconstructed t Pit 0.96 — Oct 02 ASTER 0.95 0.94 0 93 7 8 9 10 11 12 13 14 15 Wavelength (microns)

Figure Alb. Additional emissivity plot and pixel colors of section 3 samples. 139

1 02 CNB03_4 Blue

1.00 0.98 0.96 0.94. 0.92. Original i Reconstructed i 0 90 Original t

03Mc 09 Red Reconstructed t 114 1.02 — Oct 02 ASTER 1.00 0.98 0.96 0.94 0.92 0.90 0.88 7 8 9 10 11 12 13 14 15 Wavelength (microns)

Figure Ale. Emissivity plot and pixel color samples outside of age-defined sections.