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Micro-analytical geochemical and spectroscopic investigations of the original context and condition of… McMillan, Rhylan 2020

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 MICRO-ANALYTICAL GEOCHEMICAL AND SPECTROSCOPIC INVESTIGATIONS OF THE ORIGINAL CONTEXT AND CONDITION OF ARCHAEOLOGICAL BIOMINERALS AND MINERALOIDS  by  Rhylan McMillan  B.A., Vancouver Island University, 2013  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Geological Sciences)  THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver)  March 2020 © Rhylan McMillan, 2020 ii   The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: Micro-analytical geochemical and spectroscopic investigations of the original context and condition of archaeological biominerals and mineraloids  submitted by Rhylan McMillan in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Geological Sciences  Examining Committee: Dr. Dominique Weis, Professor, Department of EOAS, UBC Supervisor  Dr. Marghaleray Amini, Research Associate, Department of EOAS, UBC Supervisory Committee Member  Dr. Stuart Sutherland, Professor of Teaching, Department of EOAS, UBC Supervisory Committee Member Dr. Les Lavkulich, Professor Emeritus, Faculty of Land and Food Systems, UBC University Examiner Dr. Tara Ivanochko, Senior Instructor, Department of EOAS, UBC University Examiner   iii  Abstract  Detailed written records only exist for a very small amount of human history. Researchers must therefore combine Indigenous traditional knowledge with scientific evidence, often collected with geochemical and spectroscopic techniques, to investigate ancient human biology, behaviour, and culture. However, acquiring meaningful scientific information about rare and culturally-sensitive materials without destroying or modifying them is extremely challenging. The four research chapters in this dissertation adapt and develop analytical frameworks for appropriately acquiring key data from archaeological biominerals and mineraloids to address the fundamental question:   ‘What was the original context and condition of the archaeological materials we find?’  The first two research chapters focus on investigating the post-mortem histories and diagenetic alteration of archaeological bone using our novel ‘Perio-spot’ technique. In Chapter 2, we evaluate the depositional histories, stratigraphic provenance, and thus age of megafauna and Neandertal bones at Scladina Cave (Belgium). In Chapter 3, we assess the taphonomic state of archaeological bones and the effectiveness of acetic acid pre-treatment procedure used to remove diagenetic alteration, documenting that it may actually concentrate post-mortem signals in recrystallized, intensively-altered bones.  The last two research chapters focus on enhancing the traditional techniques for sourcing obsidian (volcanic glass) stone tools in the Pacific Northwest. Our step-wise ‘Splitting Obsidian’ approach (Chapter 4) involves non-destructively investigating all artifacts in an assemblage for elemental concentrations and structural characteristics, then analyzing a subset of representative iv  artifacts for lead (Pb) isotope compositions and more precise trace element concentrations using minimally-invasive techniques. In Chapter 5, we apply this approach to a suite of rare archaeological belongings in partnership with xʷməθkʷəy̓əm (Musqueam), an Indigenous community near Vancouver (Canada), and suggest ancient transport of obsidian over distances exceeding 1000 km in western North America. This supports the oral history and continuity of intricate xʷməθkʷəy̓əm social and material networks, providing additional key lines of evidence for how and from where people procured resources in ancient North America. In summary, the contributions made in this dissertation research provide unique and robust scientific techniques and data that support investigations of ancient human history while minimizing the destruction and alteration of valuable archaeological materials and contexts.   v  Lay Summary  The archaeological record is the body of physical evidence of past human activity. Archaeologists study this evidence and are experts in investigating human history; however, they can never directly observe their subjects and must therefore use indirect evidence to interpret ancient human behaviour. This requires the collection of meaningful scientific data from archaeological materials, which is challenging, especially when such materials should not be altered or destroyed. This dissertation research adapts and enhances traditional chemical and molecular approaches to investigations of the archaeological record to better address the key question:   “From where did the ancient bones, teeth, artifacts, and belongings we find originate, and how have they changed since antiquity?”  The breadth of the studies presented herein include a vast range of human history on two continents, and the resulting analytical approaches provide key information required to solve common archaeological challenges and address modern questions about the human journey. vi  Preface  This dissertation is composed of six chapters, four of which have been written as scholarly journal articles on which I am primary and corresponding author. Three of these chapters have been published in international journals (McMillan et al., 2017, 2019a, and 2019b) and the fourth, which involves data from xʷməθkʷəy̓əm (Musqueam) archaeological belongings, has gone through internal review by community representatives, has been presented at an international conference (the American Geophysical Union Fall Meeting, 2019; McMillan et al., 2019c), and will be submitted to an international scholarly journal in 2020.  Chapter 1 is an introduction to the research. Chapters 2 through 5 are each stand-alone studies. Chapters 2 and 3 focus on archaeological bones from the European Pleistocene, and Chapters 4 and 5 focus on archaeological obsidian from the Holocene Pacific Northwest. Chapters 2 and 4 each provide the conceptual framework and method development required to address applied challenges in Chapter 3 and 5. Chapter 6 is a summary and conclusion of all work presented in this dissertation. All research presented herein is the original work of the author, Rhy McMillan. The content of Chapters 2 through 5 have for the most part not been modified from that which has been published or will be submitted. As a result, the reader will note several repeated components among chapters, mostly background, framing, and methodological information.  Chapter 2 is based on work I conducted at Scladina Cave Archaeological Research Centre with Dominique Bonjean via a series of internships, directed studies, and senior projects supervised by Cheryl Roy and Steven Earle at Vancouver Island University (VIU, Nanaimo, Canada) during my Bachelor of Arts degree program. Mr. Bonjean facilitated the framing of the archaeological challenge in the context of Scladina Cave archaeology, and I was responsible for vii  collecting and preparing all samples, developing the analytical approach, and interpreting the results. A version of Chapter 2 has been published. McMillan, R., Weis, D., Amini, M., & Bonjean, D. (2017). Identifying the reworking and stratigraphic provenance of bones by exploring multivariate geochemical relationships with the “Perio-spot” technique. Journal of Archaeological Science, 88, 1–13. I conducted all testing with Dr. Marghaleray Amini, and I wrote most of the manuscript with the supervisory guidance of Dr. Dominique Weis. The section on the LA-ICP-MS method was originally drafted by Dr. Amini.   The research questions posed in Chapter 3 is based on discussions between Dr. Christophe Snoeck and me. Dr. Snoeck facilitated the framing of the project and provided access to the cremated remains, and I was responsible for collecting all Scladina Cave bone samples, preparing all bone samples, analyzing the samples with Raman spectroscopy and LA-ICP-MS, and interpreting all results. A version of Chapter 3 has also been published. McMillan, R., Snoeck, C., de Winter, N. J., Claeys, P., & Weis, D. (2019). Evaluating the impact of acetic acid chemical pre-treatment on ‘old’ and cremated bone with the ‘Perio-spot’ technique and ‘Perios-endos’ profiles. Palaeogeography, Palaeoclimatology, Palaeoecology 530, 330-344. I conducted all the LA-ICP-MS and Raman analysis. Dr. Niels de Winter conducted the µXRF analyses, and Dr. Snoeck conducted the FTIR analysis. I was responsible for compiling and interpreting all of the results (including the µXRF and FTIR results), and I wrote most of the manuscript with the supervisory guidance of Dr. Dominique Weis. The methods section for the µXRF was originally drafted by Dr. de Winter, and the paragraph on cremated bone in the introduction and the methods section for the FTIR was was originally drafted by Dr. Snoeck.   A version of chapter 4 has also been published. McMillan, R., Amini, M., Weis, D. 2019. Splitting obsidian: Assessing a multiproxy approach for sourcing obsidian artifacts in British viii  Columbia. Journal of Archaeological Science: Reports 28, 102040. I conducted all the SS-LA-ICP-MS, pXRF, MC-ICP-MS, and Raman analyses. Dr. Amini provided valuable assistance during the SS-LA-ICP-MS and MC-ICP-MS analyses. I was responsible for collecting all samples as well as compiling and interpreting all of the results, and I wrote most of the manuscript with the supervisory guidance of Dr. Dominique Weis. The methods section for the MC-ICP-MS was originally drafted by Dr. Amini and they also facilitated the dissolution and chromatography of the obsidian source samples in preparation for MC-ICP-MS analyses.   Chapter 5 is based on Indigenous-led research questions and was framed during discussions with xʷməθkʷəy̓əm (Musqueam) community members at Musqueam 101 as well as with Musqueam Indian Band senior archaeologist Aviva Rathbone. My partnership with xʷməθkʷəy̓əm was facilitated by my involvement in the UBC Indigenous/Science Research Excellence Cluster. The research was conducted under permit MIB-2019-020-Research, co-held by me and Aviva Rathbone in the spirit of collaborative practice. The unique specimens analysed for this study were discovered during initial investigations of archeological stone beads carried out by Léa Brunswic, with whom I also collaborated via the UBC Indigenous/Science Research Excellence Cluster. I was responsible for interacting with xʷməθkʷəy̓əm community members and representatives, obtaining a research permit and permission for minimally-invasive analyses, sample preparation, conducting all analyses, carrying out all data interpretation, and I wrote all of the manuscript with the supervisory guidance of Dr. Dominique Weis. This work is in preparation for publication after further consultation with the community, and it will be submitted sometime in 2020 after we have gone through due process out of respect for the community’ interests. ix  Table of Contents Abstract ....................................................................................................................................iii Lay Summary ............................................................................................................................ v Preface ...................................................................................................................................... vi Table of Contents ..................................................................................................................... ix List of Tables ........................................................................................................................... xv List of Figures ...................................................................................................................... xviii List of Abbreviations ............................................................................................................. xxi Glossary ................................................................................................................................ xxiii Acknowledgements .............................................................................................................. xxvi Dedication............................................................................................................................. xxix Chapter 1: Introduction............................................................................................................ 1 1.1 Context and motivation ................................................................................................ 1 1.2 Study scope ................................................................................................................. 3 1.3 Geochemical characteristics and their origins in archaeological materials .................... 6 1.3.1 Bioapatite chemistry, structure, and morphology .................................................. 7 1.3.2 Bone diagenesis and taphonomy .......................................................................... 9 1.3.3 The geochemical investigation of archaeological bone ....................................... 13 1.3.4 Obsidian artifact and belonging provenance ....................................................... 16 1.4 Techniques used for investigating rare and culturally-sensitive archaeological materials in this dissertation research ................................................................................................... 25 1.4.1 Raman spectroscopy (non-destructive) ............................................................... 26 1.4.2 X-ray fluorescence (non-destructive) ................................................................. 26 1.4.3 Laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS; minimally-invasive) .......................................................................................................... 28 1.5 Overview of this dissertation ..................................................................................... 29 1.6 Research, training, teaching, fieldwork, and networking opportunities related to this research ................................................................................................................................. 34 1.6.1 Meetings and conferences .................................................................................. 34 1.6.2 MAGNET .......................................................................................................... 34 x  1.6.3 Indigenous partnerships ..................................................................................... 36 1.6.3.1 Indigenous/Science UBC Research Excellence Cluster .................................. 37 1.6.4 Workshops attended ........................................................................................... 38 1.6.5 Workshops organized and facilitated .................................................................. 39 1.6.6 Teaching and learning opportunities and certificate programs ............................ 39 1.6.7 Awards granted .................................................................................................. 42 Chapter 2: Identifying the reworking and stratigraphic provenance of bones by exploring multivariate geochemical relationships with the ‘Perio-spot’ technique .............................. 43 2.1 Introduction ............................................................................................................... 43 2.2 Scladina Cave: Geographical, geological, and archaeological context ........................ 45 2.3 Materials and methods ............................................................................................... 49 2.3.1 Sample collection............................................................................................... 49 2.3.2 The ‘Perio-spot’ technique ................................................................................. 50 2.3.3 Laser ablation - inductively coupled plasma - mass spectrometry ....................... 50 2.3.4 Raman spectroscopy .......................................................................................... 52 2.3.5 Statistical analyses ............................................................................................. 53 2.3.5.1 Predictor variables ......................................................................................... 55 2.3.5.2 Identifying reworking and stratigraphic provenance ....................................... 56 2.4 Results ....................................................................................................................... 56 2.4.1 LA-ICP-MS and Raman analyses ....................................................................... 56 2.4.2 Statistical analyses ............................................................................................. 58 2.5 Discussion ................................................................................................................. 59 2.5.1 Trace element and Raman structural characteristics: stratigraphic trends ............ 59 2.5.2 Reworking in the Scladina sequence .................................................................. 63 2.5.3 Implications for Neandertal occupation at Scladina Cave: reworking and original context of Scladina Child .................................................................................................. 65 2.5.4 Extent of reworking, diagenetic periods, and climate.......................................... 66 2.5.5 Limitations and advantages of identifying reworking and the stratigraphic provenance of bones with the ‘Perio-spot’ technique ......................................................... 68 2.6 Future work ............................................................................................................... 70 xi  2.7 Conclusions ............................................................................................................... 71 Chapter 3: Evaluating the impact of acetic acid chemical pre-treatment on ‘old’ and cremated bone with the ‘Perio-spot’ technique and ‘Perios-endos’ profiles ........................ 73 3.1 Introduction ............................................................................................................... 73 3.2 Materials: sample types, collection, and context......................................................... 76 3.3 Methods .................................................................................................................... 78 3.3.1 Sample preparation and acetic acid pre-treatment ............................................... 78 3.3.2 The ‘Perio-spot’ technique and ‘Perios-endos’ profiles ...................................... 79 3.3.3 Laser ablation - inductively coupled plasma - mass spectrometry  ...................... 80 3.3.4 Micro X-ray fluorescence (µXRF) ..................................................................... 81 3.3.5 Raman spectroscopy .......................................................................................... 82 3.3.6 Fourier transform infrared spectroscopy (FTIR) ................................................. 83 3.4 Results ....................................................................................................................... 84 3.4.1 Trace element characteristics before and after pre-treatment .............................. 84 3.4.1.1 LA-ICP-MS ‘Perio-spots’ .............................................................................. 84 3.4.1.2 LA-ICP-MS ‘Perio-endos’ profiles................................................................. 87 3.4.1.3 µXRF ‘Perios-endos’ profiles ......................................................................... 87 3.4.2 Structural characteristics before and after pre-treatment ..................................... 90 3.4.2.1 Raman structural characteristics of ‘Perio-spots’ ............................................ 90 3.4.2.2 Fourier transform infrared spectroscopy (FTIR) ............................................. 94 3.4.3 Leachate weights ............................................................................................... 95 3.5 Discussion ................................................................................................................. 95 3.5.1 Characterizing diagenetic alteration of the trace element content and structural characteristics of bone at high spatial resolution ................................................................ 95 3.5.2 Impact of acetic acid pre-treatment on the trace element and structural characteristics of cremated and ‘old’ bones...................................................................... 101 3.5.3 Identifying the diagenetic state of bones via chemical leaching ........................ 106 3.5.4 Comparison of LA-ICP-MS, µXRF, Raman spectroscopy, and FTIR for evaluating the diagenetic alteration of bone ..................................................................... 107 3.5.4.1 Trace element analysis by LA-ICP-MS and µXRF ....................................... 107 xii  3.5.4.2 Structural analysis by Raman spectroscopy and FTIR .................................. 107 3.5.5 Future work ..................................................................................................... 108 3.6 Conclusions ............................................................................................................. 109 Chapter 4: Splitting Obsidian: Assessing a multiproxy approach for sourcing obsidian artifacts in British Columbia ................................................................................................ 111 4.1 Introduction ............................................................................................................. 111 4.2 Methods .................................................................................................................. 114 4.2.1 Samples ........................................................................................................... 114 4.2.2 Step 1: Non-destructive .................................................................................... 116 4.2.2.1 Portable X-ray fluorescence (pXRF) ............................................................ 116 4.2.2.2 Raman spectroscopy .................................................................................... 117 4.2.3 Step 2: Minimally-invasive .............................................................................. 118 4.2.3.1 Trace element concentrations and Pb isotope ratios by SS-LA-ICP-MS ....... 118 4.2.4 High-precision Pb isotope analyses by MC-ICP-MS ........................................ 119 4.3 Results ..................................................................................................................... 120 4.4 Discussion ............................................................................................................... 131 4.4.1 Provenance hypothesis and sourcing outcomes ................................................ 131 4.4.1.1 Trace element ratios ..................................................................................... 131 4.4.1.2 Structural characteristics .............................................................................. 132 4.4.1.3 Pb isotope ratios ........................................................................................... 132 4.4.2 Artifact provenance .......................................................................................... 133 4.4.3 Challenges and limitations ............................................................................... 134 4.5 Conclusions ............................................................................................................. 137 Chapter 5: Obsidian Among the Beads: Identifying long-distance transport of obsidian across the North American landscape in antiquity .............................................................. 138 5.1 Introduction ............................................................................................................. 138 5.2 Materials and methods ............................................................................................. 139 5.2.1 Raman spectroscopy ........................................................................................ 144 5.2.2 SS-LA-ICP-MS ............................................................................................... 145 5.3 Results ..................................................................................................................... 147 xiii  5.3.1 Structural characteristics by Raman spectroscopy ............................................ 147 5.3.2 Trace element concentrations by SS-LA-ICP-MS ............................................ 147 5.3.3 Pb isotope ratios by SS-LA-ICP-MS ................................................................ 150 5.4 Discussion ............................................................................................................... 152 5.4.1 Provenance hypothesis and sourcing outcomes ................................................ 152 5.4.1.1 Structural characteristics .............................................................................. 152 5.4.1.2 Trace elements and Pb isotope ratios ............................................................ 153 5.4.1.3 Belonging provenance summary .................................................................. 159 5.4.2 Raman structural characteristics of Group A and Group B belongings.............. 160 5.4.3 Implications of obsidian provenance for xʷməθkʷəy̓əm .................................... 161 5.4.4 Analysis of micro-belongings with the ‘Splitting Obsidian’ procedure ............. 163 5.4.4.1 Community outreach and future work .......................................................... 165 5.5 Conclusions ............................................................................................................. 165 Chapter 6: Conclusions ......................................................................................................... 167 6.1 Summary of the dissertation and key research findings ............................................ 167 6.1.1 Biominerals, stratigraphic provenance, diagenetic facies, and post-mortem alteration  ........................................................................................................................ 168 6.1.2 The structural characteristics, chemical composition, and radiogenic isotope ratios of volcanic glasses from the Pacific Northwest ................................................................ 174 6.1.3 Multidisciplinary approaches and the role of partnership development in archaeological research ................................................................................................... 177 6.1.4 Remaining challenges and works in progress ................................................... 180 6.1.5 Future work and next steps ............................................................................... 182 6.1.6 Concluding remarks ......................................................................................... 184 Bibliography .......................................................................................................................... 185 Appendices ............................................................................................................................ 202 Appendix A......................................................................................................................... 202 A.1 Complex T ....................................................................................................... 204 A.2 Complex 1A/Z-INF.......................................................................................... 208 A.3 Complex 1B ..................................................................................................... 219 xiv  A.4 Complex 2A .................................................................................................... 226 A.5 Complex 2B ..................................................................................................... 232 A.6 Unit 3-SUP ...................................................................................................... 236 A.7 Unit 3-INF ....................................................................................................... 245 A.8 Complex 4A .................................................................................................... 250 A.9 Complex 5 ....................................................................................................... 259 A.10 Complex 6A .................................................................................................... 263 A.11 Complexes below 6A ....................................................................................... 268 Appendix B ......................................................................................................................... 276 Appendix C ......................................................................................................................... 288 C.1 MAPS-4 digestion method ............................................................................... 289 C.2 ICP-OES analysis of MAPS-4.......................................................................... 290 C.3 Impact of laser light on Raman measurements and the relationship among trace elements, Raman crystallinity, and diagenetic periods ..................................................... 292 C.4 Description of diagenetic periods established at Scladina Cave ........................ 295 C.5 Supplementary tabulated data for Chapter 2 ..................................................... 298 Appendix D......................................................................................................................... 308 D.1 ‘Perios-endos’ profiles collected by µXRF for Chapter 3 ................................. 309 Appendix E ......................................................................................................................... 316 E.1 PCA of Raman spectra ..................................................................................... 317 E.2 SS-LA-ICP-MS Spot analyses and outlier Removal ......................................... 318 E.3 SS-LA-ICP-MS data reduction ......................................................................... 319 E.4 pXRF concentration data collected for Chapter 4 ............................................. 322 E.5 Raman data collected for Chapter 4 .................................................................. 325 E.6 All ICP-MS data collected for Chapter 4 .......................................................... 351 Appendix F ......................................................................................................................... 364 F.1 All SS-LA-ICP-MS data collected for Chapter 5 .............................................. 365 F.2 Raman data collected for Chapter 5 .................................................................. 373  xv  List of Tables Table 1.1 Select presentations at conferences and meetings and relevant dissertation chapters or opportunities. ............................................................................................................................ 35 Table 1.2 Industrial partners, dates, durations, locations, and descriptions of MAGNET internships participated in during this dissertation research ....................................................... 37 Table 1.3 Titles, location, dates, and description of the main workshops I attended during my dissertation research .................................................................................................................. 38 Table 1.4 Titles, location, dates, and description of the main workshops I co-developed and/or facilitated during my dissertation research. ................................................................................ 39 Table 1.5 Titles, issuers, and dates issued for awards received during dissertation research ...... 42 Table 2.1 Palaeoenvironment, palaeoclimate, marine isotopic stages, and radiocarbon ages for the Scladina Cave sedimentary sequence ................................................................................... 48 Table 2.2 The number of bones and ‘Perio-spots’ from each sedimentary complex analyzed in this study. ................................................................................................................................. 50 Table 2.3 Wilk's lambda and f-to-remove statistics from all 27 LDA conducted in this study.... 60 Table 2.4 Average Mahalanobis squared distances among the ‘Perio-spot’ data for cave bear femora (‘Ursus’) and the context each femur was exhumed from as well as two subjacent complexes ................................................................................................................................. 61 Table 2.5 Average Mahalanobis squared distances among the two taphonomic proxies for the Scladina Child and the ‘Perio-spot’ analyses from Complex 4A, Unit 5, and Unit 6A ............... 63 Table 3.1 All ‘Perio-spot’ data collected by LA-ICP-MS and Raman spectroscopy .................. 86 Table 3.2 Trace element concentrations for each ‘Perios-endos’ profile collected with LA-ICP-MS ............................................................................................................................................ 89 Table 3.3 Treated / untreated trace element concentrations for each ‘Perios-endos’ profile collected with LA-ICP-MS ..................................................................................................... 103 Table 3.4 FTIR results averaged per bone ............................................................................... 103 Table 3.5 Measured weights of untreated bones and leachates from each pre-treatment step ... 104 Table 4.1 The sample type, collection type, geographic location, and analyses conducted on source materials and artifacts analysed in this study ................................................................ 115 xvi  Table 4.2 Average trace element concentrations and ratios as well as Raman peak characteristics for all geologic source samples and artifacts analysed in this study ......................................... 121 Table 4.3 Mean Pb isotope ratios collected by both SS-LA-ICP-MS and solution MC-ICP-MS  for all geologic source samples and artifacts analysed in this study ......................................... 130 Table 5.1 The sample type, collection type, geographic location, and analyses conducted on source materials and belongings analysed in this study ............................................................ 142 Table 5.2 Average trace element concentrations and ratios for all geologic source samples and belongings analysed in this study ............................................................................................ 149 Table 5.3 Mean Pb isotope ratios collected by both SS-LA-ICP-MS and solution MC-ICP-MS for all geologic source samples and belongings analysed in this study ..................................... 151 Table 6.1 Contextual details, research questions, and relationships among the four research chapters in this dissertation. .................................................................................................... 169 Table C.1 All ‘Perio-spot’ analyses for Chapter 2 ................................................................... 298 Table D.1 µXRF 'Perio-endos' results for each bone analysed in Chapter 3 ............................. 309 Table E.1 Elemental concentration data collected by pXRF for both source materials and artifacts analysed in Chapter 4 used to create the averaged values reported in tables in text ..... 322 Table E.2 Background-subtracted, normalized, and averaged Raman spectra for geologic source materials investigated in Chapter 4 .......................................................................................... 325 Table E.3 Calculated characteristics on Q0 peaks fitted with Gaussian curves. ........................ 346 Table E.4 All trace element concentrations for source materials and artifacts collected by SS-LA-ICP-MS for Chapter 4. ...................................................................................................... 351 Table E.5 All Pb isotope ratios for source materials and artifacts collected by SS-LA-ICP-MS for Chapter 4. .......................................................................................................................... 357 Table E.6 All MC-ICP-MS data collected for both Chapters 4 and 5. ..................................... 363 Table F.1 All trace element concentrations for source materials and belongings collected by SS-LA-ICP-MS for Chapter 5. ...................................................................................................... 365 Table F.2 All Pb isotope ratios for source materials and belongings collected by SS-LA-ICP-MS for Chapter 5. .......................................................................................................................... 369 Table F.3 Background subtracted, normalized, and averaged Raman spectra for source materials from Glass Buttes ('GLAB') and for Group A belongings (CES-D, E, F, and G) ...................... 373 xvii  Table F.4 Background subtracted, normalized, and averaged Raman spectra for Group B belongings (CES-A, B, C, H, J, K, L, M, and N) ..................................................................... 402  xviii  List of Figures  Figure 1.1 Map showing the location and time periods of the culture areas addressed in this dissertation research .................................................................................................................... 4 Figure 1.2 Map showing the Indigenous languages of British Columbia ..................................... 5 Figure 1.3 The main skeletal elements and their respective abundances of water, organic, and biomineral constituents by both weight % and volume %. ........................................................... 9 Figure 1.4 The different levels of structural organization in bone ............................................. 10 Figure 1.5 Diagram showing some of the main contributors to life history signals and measured signals in archaeological bone ................................................................................................... 12 Figure 1.6 REE systematics and laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) analysis locations of bones from Scladina Cave, Belgium.............. 15 Figure 1.7 Photographs of obsidian (volcanic glass) ................................................................. 17 Figure 1.8 Zr/Rb and Nb/Y of obsidian source materials in British Columbia ........................... 20 Figure 1.9 Averaged, normalized, and background-subtracted Raman spectra for obsidian source samples from British Columbia ................................................................................................. 22 Figure 1.10 Volcano locations (coloured stars) and 207Pb/206Pb of geologic obsidian samples plotted geographically in British Columbia ............................................................................... 23 Figure 1.11 Instrumentation used during the course of this dissertation research ....................... 41 Figure 2.1 Scladina Cave location, stratigraphy, and sedimentary dynamics ............................. 46 Figure 2.2 The ‘Perio-spot’ technique and diffusion profiles in bones from Scladina Cave ....... 51 Figure 2.3 Stratigraphic trends of all nine predictor variables used during linear discriminant analyses .................................................................................................................................... 57 Figure 2.4 Stratigraphic provenancing outcomes and the Scladina stratigraphic sequence ......... 62 Figure 2.5 Canonical scores and Cu and U concentrations of the Neandertal proxies ................ 67 Figure 3.1 The ‘Perio-spot’ technique and ‘Perios-endos’ profiles ............................................ 80 Figure 3.2 Box plots of trace element concentrations in ‘Perio-spots’ collected by LA-ICP-MS for bones from Scladina Cave ................................................................................................... 85 Figure 3.3 ‘Perios-endos’ concentration profiles for the treated/untreated concentrations of Cu, Sr, La, Ce, Pb, and U collected by LA-ICP-MS ......................................................................... 88 xix  Figure 3.4 Treated/untreated La concentration ‘Perios-endos’ profiles collected with LA-ICP-MS in three bones from Scladina Cave (Pleistocene) and one cremated bone (Early Medieval; two profiles were obtained from this bone)................................................................................ 90 Figure 3.5 The Fe/Ca, Mn/Ca, Sr/Ca, and Pb/Ca for treated/untreated ‘Perios-endos’ profiles collected by µXRF of treated/untreated aliquots of in three bones from Scladina Cave (Pleistocene) and one cremated bone (Early Medieval) ............................................................. 91 Figure 3.6 Averaged Raman v1-(PO4) PCMI and v1-(PO4) FWHM for bone samples analyzed before and after chemical pre-treatment .................................................................................... 92 Figure 3.7 Baseline-subtracted, normalized, and averaged Raman spectra of the v1-(PO4) peak from bones analyzed in this study before and after chemical pre-treatment. ............................... 93 Figure 3.8 FTIR carbonate/phosphate (BPI*) and the organic matter and water content (WAMPI*) for bone samples analyzed before and after chemical pre-treatment ........................ 94 Figure 3.9 The amount of material (% total bone weight) removed by each pre-treatment step plotted down the Scladina Cave stratigraphy ............................................................................. 96 Figure 3.10 The Raman v1-(PO4) Peak Centre at Maximum Intensity (PCMI) and the v1-(PO4) Full Width at Half Maximum (FWHM) plotted against Sr/Ca, La/Ca, and Pb/Ca collected by LA-ICP-MS for each ‘Perio-spot’ analysis from the untreated halves of each bone analyzed in this study .................................................................................................................................. 98 Figure 4.1 Volcano locations (coloured stars) and 207Pb/206Pb of geologic obsidian samples plotted geographically in British Columbia ............................................................................. 113 Figure 4.2 Zr/Rb and Nb/Y of geologic source materials and artifacts analyzed in this study. . 124 Figure 4.3 Averaged, normalized, and background-subtracted Raman spectra for geologic source samples analysed in this study, arranged from most northern (Mount Edziza, top) to most southern (Mount Garibaldi, bottom) ........................................................................................ 126 Figure 4.4 Calculated characteristics of fitted Raman Q0 Peaks of both artifacts and geologic source materials, with peak location (peak centre at maximum intensity; PCMI) on the x-axis and peak width (full width at half maximum; FWHM) on the y-axis .............................................. 127 Figure 4.5 Top left: PCA scores for two principle components calculated from the Raman spectra of geologic source materials, with 95% confidence ellipses and coloured at the volcano resolution ................................................................................................................................ 128 xx  Figure 4.6 Mean 207Pb/206Pb and 208Pb/206Pb measured by MC-ICP-MS and SS-LA-ICP-MS at the specimen resolution and volcano resolution ....................................................................... 129 Figure 5.1 Locations of named places and c̓əsnaʔəm (Marpole) within xʷməθkʷəy̓əm (Musqueam) traditional territory in modern-day Vancouver, British Columbia, Canada .......... 140 Figure 5.2 All xʷməθkʷəy̓əm micro-belongings analysed in this study.................................... 143 Figure 5.3 Averaged, normalized, and background-subtracted Raman spectra for belongings and geologic source samples analysed in this study........................................................................ 148 Figure 5.4 PCA scores for principle components calculated from the Raman spectra of all 10 geologic source materials from 5 volcanic centres (separated by colour) and of both the Group A and Group B belongings (differentiated by marker shape) ....................................................... 154 Figure 5.5 Trace element concentrations and ratios for all belongings and source materials analysed in this study .............................................................................................................. 155 Figure 5.6 Mean 207Pb/206Pb and 208Pb/206Pb of belongings and source materials .................... 157 Figure 5.7 PCA of scaled trace element concentrations (Rb, Sr, Y, Zr, Nb) for both belongings and potential geologic sources investigated in this study ......................................................... 158 Figure 5.8 Likely geologic source affiliations in Western North America for the 13 obsidian micro-belongings analysed in this study .................................................................................. 163 Figure 6.1 Overview of this dissertation research ................................................................... 176 Figure 6.2 Networks of investigators, translators, and stakeholders during archaeological research .................................................................................................................................. 180 Figure C.1 The Raman Peak Centre at Maximum Intensity (PCMI) and Full-Width Half-Maximum (FWHM) of the PO4 peak for the 313 first spot analyses from this study ................ 294 Figure C.2 Trace elements and Raman measurements for the whole Scladina sequence and for each diagenetic period ............................................................................................................. 297 Figure E.1 Internal precision of all SS-LA-ICP-MS and HR-ICP-MS only spot analyses for source materials and artifacts analysed in this study ................................................................ 320 Figure E.2 Comparison of different SS-LA-ICP-MS reduction schemes for 208Pb/206Pb and 207Pb/206Pb in obsidian source materials to those measured with high-resolution solution MC-ICP-MS .................................................................................................................................. 321  xxi  List of Abbreviations ANOVA = analysis of variance BP = years before present FTIR = Fourier transform infrared spectroscopy ka = thousands of years before present (kilo annum) kyr = a timespan reported in thousands of years LA-ICP-MS = laser ablation - inductively coupled plasma - mass spectrometry LDA = linear discriminant analysis MIS = marine isotopic stage MC-ICP-MS = multi collector - inductively coupled plasma - mass spectrometry PCA = principal component analysis PNW = Pacific northwest of North America ppb = parts per billion ppm = parts per million pXRF = portable X-ray fluorescence REE = rare earth elements RSD = relative standard deviation (usually in % relative to the mean; can be reported to 1 or 2) RSE = relative standard error (usually in % relative to the mean; can be reported to 1 or 2) s = seconds SD = standard deviation (can be reported to 1 or 2) SE = standard error (can be reported to 1 or 2) SS-LA-ICP-MS = split stream - laser ablation - inductively coupled plasma - mass spectrometry uncalBP = uncalibrated radiocarbon years before present xxii  wt% = weight percent µm = micrometer or micron µXRF = micro X-ray fluorescence xxiii  Glossary archaeological record = analogous to the geologic record, it is the body of physical (not written) evidence of the human past archaeology = the study of the human past through the excavation of archaeological sites and the analysis of physical remains and artifacts artifact = any portable object that has been made or modified by humans belonging = the preferred name for artifacts for some scholars and Indigenous communities bioapatite = a biomineral that is the biological analogue to the apatite minerals commonly found in the earth’s crust and the main constituents of the hard parts of vertebrates (bone, dentine, enamel) biomineral = inorganic mineral substances that are a result of biological processes (i.e., biogenic minerals) and constitute an integral part of biologic structures and processes biostratinomy = the study of processes that impact an individual after it dies and before its final burial bone = composite material composed of bioapatite, organic matter, and water that is used for structural support, a reservoir for important elements, and for protection of soft parts in vertebrates conchoidal fracture = the way brittle materials break when they do not follow any natural planes of separation, often resulting in a shell-shaped fracture surface death history = pertaining to the series of events and processes that occurred after an individual’s death  debitage = the material produced during the production of chipped or ‘knapped’ stone tools xxiv  dentin = composite material composed of bioapatite, organic matter, and water that forms the roots of teeth diagenesis = sum of all processes, primarily chemical, by which changes in a sediment, including its bioclasts (e.g., bone), are brought about after deposition and before lithification enamel = composite material primarily composed of bioapatite and small amounts of organic matter and water that forms the cusps of teeth ex-vivo = after death femur = thigh bone (plural = femora) geochemistry = the study of the chemical composition of the earth and its rocks and minerals sourcing = practice of identifying the origin or ‘source’ of materials and processes Holocene = the current geological epoch that began after the last glacial period approximately 11,700 (calibrated radiocarbon) years before present in-vivo = during life life history = pertaining to the series of events and behaviours that occurred during an individual’s life major element = a chemical element present in concentratrions greater than 1 wt% mandible = lower jaw or jawbone and the strongest bone in the human face maxilla = upper fixed bone of the jaw mineraloid = ‘mineral-like’ material that lacks a long-range crystalline structure and includes amorphous solids and gasses minimally-invasive = results in very little, practically invisible alteration to the analyte minor element = a chemical element present in concentrations between 0.1 and 1.0 wt% non-destructive = does not result in any physical alteration of the analyte xxv  obsidian = a naturally-occuring volcanic glass formed by the rapid quenching of felsic (silica-rich) magmas that fractures conchoidally Palaeolithic = old stone age, a period of human history that spans from the initial manufacture of stone tools more than three million years ago to the end of the Pleistocene, 11,700 years ago, covering ~99% of human history Pleistocene = the geological epoch that lasted between approximately 2,580,000 to 11,700 years ago, preceding the Holocene post-mortem = after death (similar to ex-vivo and contrasting with ante-mortem, or before death) provenance = documentation of an object’s complete history from its earliest known origins to its current state and location provenience = the exact location or discovery spot of an object recorded in three dimensions (x, y, z) Quaternary = the current and most recent of the three periods of the Cenozoic era (2,580,000 years before present to the present), including both the Pleistocene and Holocene epochs taphonomy = the study of all processes that impact an individual between their time of death and their discovery, originally defined by Efremov (1940) trace element = a chemical element present in concentrations less than 0.1 wt%   xxvi  Acknowledgements  I gratefully acknowledge that most of the thinking, investigating, and writing of this dissertation research was conducted in the ancestral, traditional, and unceded territory of the xʷməθkʷəy̓əm people. For this amazing experience, opportunity, and honour, I raise my hands to say: hay ce:p q̓ə  (thank you)  In addition, all of the material analysed for this dissertation work was collected, manipulated, and altered at the request or with the explicit consent of relevant Indigenous and descent communities.  This research would not have been possible without countless inspirations and contributions from many of my colleagues, friends, and family. Though our years of interactions, you have motivated me to continue exploring my unique niche of research and focus on sharing it with the people who value it most.  I am especially grateful to my research supervisors and committee, Drs. Dominique Weis, Marg Amini, and Stuart Sutherland. Dominique, I cannot thank you enough for taking a ‘leap of faith’ and bringing me on board first for an MSc and eventually this dissertation research. It was one of the best things that has ever happened to me, and the impact it has had and will have on my life is beyond measurement; it has been a fantastic journey, I’ve had a tonne of fun, and I am excited for the next steps. Marg, I feel so fortunate to have met you back in 2012 during my first forays into this research and that you have continuously supported me and provided me with guidance since then. Thanks, too, for all of those great chats in the laser lab. Stuart, it has been an absolute pleasure to learn and teach from/with you, both in the context of xxvii  undergraduate courses and my dissertation research. You have been a solid foundation for me throughout the years I have been at UBC, and I am so grateful for your support, kindness, and how you have clearly enjoyed challenging me. I am also eternally grateful for the mentorship and kindness the three of you gave me during some of the biggest challenges I could ever imagine facing, which so happened to coincide with the final stages of this dissertation research.  For financial support, I thank the NSERC CREATE Multidisciplinary Applied Geochemistry Network (MAGNET), the UBC 4YF Program, and the NSERC CGSD Program. Funding for much of the research was provided by an NSERC Discovery Grant to Dominique Weis.  For sample preparation and analytical support, I thank Heather Hughes-Adams, Mary Chung, Hannah, Rachel Maj, Maureen Soon, Kathy Gordon, Vivian Lai, Christophe Snoeck, and Niels deWinter. I thank Agenschap Onroerend erfgoed, Vlaanderen, Belgium, for access to the cremated bone sample from Broechem (Chapter 3), and Dominique Bonjean, Director of Scladina Cave Archaeological Research Centre, as well as Stéphane Pirson, Kevin DiModica, and Gregory Abrams for access and valuable help in collecting the Scladina Cave bone samples (Chapters 2 and 3). I would also like to thank Mollie McDowell, Craig Skinner, David Pokotylo, Andrew Martindale, Alison Wylie, Aviva Rathbone, Morgan Ritchie, Dee Cullon, Heather Pratt, Catherine Chauvel, Kelly Russel, Lucy Gagnon, Alex Wilson, Grant Keddie, Philippe Claeys, Mauray Toutloff, Timothy Allan, RG Matson, Laura Bilenker, Steven Earle, Eric Guiry, Daniel Herwartz, Heather Pratt, Dee Cullon, Cheryl Roy, Matthijs Smit, Diane Hanano, Wade Smith, Jess Metcalfe, Anaïs Fourny, Lauren Harrison, Jamie Cutts, Rhys O'Connor, Holly Pelletier, June Cho, Nicole Williamson, and others from the PCIGR research team and staff for sample collection, additional support, valuable feedback, and guidance. I also thank all of the members xxviii  of the UBC Indigenous/Science Research Excellence Cluster and the VP Research and Innovation (UBC) Dr. Gail Murphy for their support.  xxix  Dedication  To Omi and Opi for all those adventures in the garden. And to Crystal McMillan. Miss ya, momma.  1  Chapter 1: Introduction 1.1 Context and motivation How we, as humans, interpret the biology, behavior, and culture of our ancient ancestors is neither static nor homogenous, and the knowledge systems and frameworks for investigating human history vary drastically in both time and space. Nevertheless, examining the ancient human past is fundamental for understanding where we came from, who we are now, and what the future holds for us.  One way of ‘knowing’ and thus interpreting ancient human history is through the use of Western scientific techniques, the development and refinement of which is the main focus of this dissertation research. Importantly, the outcomes of the research presented herein do not replace nor supersede Indigenous oral history, traditional knowledge, or alternate ways of knowing. Instead, they provide methodological frameworks for obtaining precise, accurate, and reliable complementary lines of evidence during investigations of human history using the ‘archaeological record,’ the body of physical evidence of the human past.  As we learn more about both our modern selves and ancient ancestors, our questions regarding the contents of the archaeological record have become increasingly complex and sophisticated. Addressing such questions can be relatively straightforward in situations where detailed written or oral documentation is available; however, no written record exists for most of human existence, and many Indigenous oral histories have been severed in places recently colonized by Western societies. Therefore, combining available Indigenous knowledge with both inter- and multidisciplinary scientific approaches is key to providing adequate answers to modern archaeological questions, especially in spatiotemporal contexts without extensive documentation. In Canada, this collaborative practice among archaeologists, scientists, and Indigenous peoples is 2  further motivated by the Truth and Reconciliation Commission of Canada’s recommendations (Truth & Reconciliation Commission of Canada, 2015), which include:  “Together, Canadians must do more than just talk about reconciliation; we must learn how to practise reconciliation in our everyday lives—within ourselves and our families, and in our communities, governments, places of worship, schools, and work-places.”  ‘Geochemistry,’ the investigation of the chemical and isotopic compositions of the Earth and its constituents, is a particularly applicable scientific framework for addressing archaeological challenges. For example, a person’s life history (e.g., diet, mobility) alters the chemical and isotopic characteristics of their bones, teeth, and soft tissues. The ways in which ancient people interacted with the landscape can also be informed by comparing the geochemical