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Isotopic systematics of the early Mauna Kea shield phase and insight into the deep mantle beneath the… Nobre Silva, Ines G; Weis, Dominique; Scoates, James S. Mar 27, 2013

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 1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.   1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  Nobre Silva et al. (2012) Figure A1.Depth (mbsl)207Pb/204Pb208Pb/204Pb 143Nd/144Nd206Pb/204Pb3050310031503200325033003350340034503500355018.20 18.30 18.40 18.50 18.60 18.70 18.803050310031503200325033003350340034503500355015.45 15.46 15.47 15.48 15.49 15.50 15.513050310031503200325033003350340034503500355037.80 37.90 38.00 38.10 38.20 38.30305031003150320032503300335034003450350035500.51296 0.51298 0.51300 0.51302Depth (mbsl)Depth (mbsl)Depth (mbsl)HSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]a bc d2SEHSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]  1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  Nobre Silva et al. (2012) Figure A1.Depth (mbsl)207Pb/204Pb208Pb/204Pb 143Nd/144Nd206Pb/204Pb3050310031503200325033003350340034503500355018.20 18.30 18.40 18.50 18.60 18.70 18.803050310031503200325033003350340034503500355015.45 15.46 15.47 15.48 15.49 15.50 15.513050310031503200325033003350340034503500355037.80 37.90 38.00 38.10 38.20 38.30305031003150320032503300335034003450350035500.51296 0.51298 0.51300 0.51302Depth (mbsl)Depth (mbsl)Depth (mbsl)HSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]a bc d2SEHSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009] 206Pb/204Pb18.2518.3518.4518.5518.6518.7518.25 18.35 18.45 18.55 18.65 18.75207Pb/204Pb15.45515.46515.47515.48515.49515.50515.455 15.465 15.475 15.485 15.495 15.505208Pb/204Pb37.8537.9538.0538.1538.2537.85 37.95 38.05 38.15 38.25143Nd/144Nd0.512980.512990.513000.513010.513020.51298 0.51299 0.51300 0.51301 0.51302This StudyThis StudyBlichert-Toft and Albar?de [2009] Blichert-Toft and Albar?de [2009]1:11:11:11:1y = 0.92x + 3.02R2 = 0.94y = 0.95x + 0.98R2 = 0.96 a bc dNobre Silva et al. (2012) Figure A2.   1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  Nobre Silva et al. (2012) Figure A1.Depth (mbsl)207Pb/204Pb208Pb/204Pb 143Nd/144Nd206Pb/204Pb3050310031503200325033003350340034503500355018.20 18.30 18.40 18.50 18.60 18.70 18.803050310031503200325033003350340034503500355015.45 15.46 15.47 15.48 15.49 15.50 15.513050310031503200325033003350340034503500355037.80 37.90 38.00 38.10 38.20 38.30305031003150320032503300335034003450350035500.51296 0.51298 0.51300 0.51302Depth (mbsl)Depth (mbsl)Depth (mbsl)HSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]a bc d2SEHSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009] 206Pb/204Pb18.2518.3518.4518.5518.6518.7518.25 18.35 18.45 18.55 18.65 18.75207Pb/204Pb15.45515.46515.47515.48515.49515.50515.455 15.465 15.475 15.485 15.495 15.505208Pb/204Pb37.8537.9538.0538.1538.2537.85 37.95 38.05 38.15 38.25143Nd/144Nd0.512980.512990.513000.513010.513020.51298 0.51299 0.51300 0.51301 0.51302This StudyThis StudyBlichert-Toft and Albar?de [2009] Blichert-Toft and Albar?de [2009]1:11:11:11:1y = 0.92x + 3.02R2 = 0.94y = 0.95x + 0.98R2 = 0.96 a bc dNobre Silva et al. (2012) Figure A2.  15.4515.4715.4915.5115.5315.5518.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb207Pb/204Pb37.8537.9037.9538.0038.0538.1038.1538.2038.2538.3018.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb208Pb/204Pb0.512960.512970.512980.512990.513000.513010.5130218.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb143Nd/144NdBHVO-2 leachedMean BHVO-2 unleachedMean BHVO-2 leachedThis StudyBlichert-Toft and Albar?de [2009]a bcNobre Silva et al. (2012) Figure A3.   1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  Nobre Silva et al. (2012) Figure A1.Depth (mbsl)207Pb/204Pb208Pb/204Pb 143Nd/144Nd206Pb/204Pb3050310031503200325033003350340034503500355018.20 18.30 18.40 18.50 18.60 18.70 18.803050310031503200325033003350340034503500355015.45 15.46 15.47 15.48 15.49 15.50 15.513050310031503200325033003350340034503500355037.80 37.90 38.00 38.10 38.20 38.30305031003150320032503300335034003450350035500.51296 0.51298 0.51300 0.51302Depth (mbsl)Depth (mbsl)Depth (mbsl)HSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]a bc d2SEHSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009] 206Pb/204Pb18.2518.3518.4518.5518.6518.7518.25 18.35 18.45 18.55 18.65 18.75207Pb/204Pb15.45515.46515.47515.48515.49515.50515.455 15.465 15.475 15.485 15.495 15.505208Pb/204Pb37.8537.9538.0538.1538.2537.85 37.95 38.05 38.15 38.25143Nd/144Nd0.512980.512990.513000.513010.513020.51298 0.51299 0.51300 0.51301 0.51302This StudyThis StudyBlichert-Toft and Albar?de [2009] Blichert-Toft and Albar?de [2009]1:11:11:11:1y = 0.92x + 3.02R2 = 0.94y = 0.95x + 0.98R2 = 0.96 a bc dNobre Silva et al. (2012) Figure A2.  15.4515.4715.4915.5115.5315.5518.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb207Pb/204Pb37.8537.9037.9538.0038.0538.1038.1538.2038.2538.3018.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb208Pb/204Pb0.512960.512970.512980.512990.513000.513010.5130218.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb143Nd/144NdBHVO-2 leachedMean BHVO-2 unleachedMean BHVO-2 leachedThis StudyBlichert-Toft and Albar?de [2009]a bcNobre Silva et al. (2012) Figure A3.  file:///C|/Documents%20and%20Settings/tkstephe/Desktop/ggge20047-sup-0005-readme.txt[3/27/2014 3:11:16 PM]Auxiliary Material Submission for Paper # 2012GC004373Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Oceanhttp://dx.doi.org/10.1029/2012GC004373Authors: Ines Garcia Nobre Silva, Dominique Weis, and James S. ScoatesPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, CanadaAuxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.List of Figures of Auxiliary MaterialFigure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars.Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference.Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  1 Auxiliary Material Submission for Paper # 2012GC004373 Auxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.  Paper: Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Ocean Authors: In?s Garcia Nobre Silva, Dominique Weis, and James S. Scoates Pacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, Canada   Appendix A: Analytical Precision and Accuracy  Precision of the HSDP2?B and ?C isotopic dataset was assessed by the external reproducibility of replicate analyses of freshly prepared Pb, Sr and Nd standard solutions analyzed during the measurement sessions, and that of several sets of complete procedural duplicates and replicate analyses of the same sample solution (Table 1). Accuracy was evaluated by analysis of rock reference material solutions of known isotopic composition, such as BHVO-2 and Kil-93 (Table 1; Weis et al. [2005; 2006]). The HSDP2?B and ?C Pb and Nd isotopic results have also been compared to the values of Blichert-Toft and Albar?de [2009] for the same samples (Figures A1 to A3). For accurate and direct comparison between the two datasets, the data from Blichert-Toft and Albar?de [2009] was renormalized to the same accepted values of the NBS 981 and Rennes standard solutions used in this study [Abouchami et al.,  2 2000; Weis et al., 2006]. The agreement between the two datasets is excellent for 206Pb/204Pb and for 208Pb/204Pb, for which the linear correlations are ~0.97. For 207Pb/204Pb and 143Nd/144Nd, the agreement is not as close. Our values of 207Pb/204Pb and 143Nd/144Nd are systematically higher and lower, respectively, compared to those of Blichert-Toft and Albar?de [2009]. Even so, the 143Nd/144Nd of both research groups are within error of each other (Figures A1 and A3). Our Nd isotopic compositions were obtained during two analytical sessions, one on the TIMS and the other on the MC-ICP-MC, and are in good agreement with each other. The Pb, Nd, and Sr isotopic compositions of BHVO-2 acquired during this study are in good agreement with the literature values for this reference material [e.g., Woodhead and Hergt, 2000; Raczek et al., 2003; Baker et al., 2004; Weis et al., 2005; 2006; Chauvel et al., 2010]. Given our careful sample treatment protocol prior to analysis, we have therefore no explanation for the differences between the two datasets. Additional References in Appendix A: Analytical Precision and Accuracy Baker, J., D. Peate, T. Waight, and C. Meysen (2004), Pb isotopic analysis of standards and samples using a 207Pb-204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS, Chem. Geol., 211, 275?303. Raczek, I., K. P. Jochum, and A. W. Hofmann (2003), Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses, Geostand. Newsl., 27(2), 173?179. Woodhead, J. D., and J. M. Hergt (2000), Pb-isotope analysis of USGS reference materials, Geostand. Newsl., 24(1), 33?38.  3 Chauvel, C., S. Bureau, and C. Poggi (2010), Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials, Geostand. Geoanal. Res., 35(1), 125?143.  List of Figures of Auxiliary Material Figure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars. Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference. Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown.  Nobre Silva et al. (2012) Figure A1.Depth (mbsl)207Pb/204Pb208Pb/204Pb 143Nd/144Nd206Pb/204Pb3050310031503200325033003350340034503500355018.20 18.30 18.40 18.50 18.60 18.70 18.803050310031503200325033003350340034503500355015.45 15.46 15.47 15.48 15.49 15.50 15.513050310031503200325033003350340034503500355037.80 37.90 38.00 38.10 38.20 38.30305031003150320032503300335034003450350035500.51296 0.51298 0.51300 0.51302Depth (mbsl)Depth (mbsl)Depth (mbsl)HSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009]a bc d2SEHSDP2?B & CThis StudyBlichert-Toft andAlbar?de [2009] 206Pb/204Pb18.2518.3518.4518.5518.6518.7518.25 18.35 18.45 18.55 18.65 18.75207Pb/204Pb15.45515.46515.47515.48515.49515.50515.455 15.465 15.475 15.485 15.495 15.505208Pb/204Pb37.8537.9538.0538.1538.2537.85 37.95 38.05 38.15 38.25143Nd/144Nd0.512980.512990.513000.513010.513020.51298 0.51299 0.51300 0.51301 0.51302This StudyThis StudyBlichert-Toft and Albar?de [2009] Blichert-Toft and Albar?de [2009]1:11:11:11:1y = 0.92x + 3.02R2 = 0.94y = 0.95x + 0.98R2 = 0.96 a bc dNobre Silva et al. (2012) Figure A2.  15.4515.4715.4915.5115.5315.5518.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb207Pb/204Pb37.8537.9037.9538.0038.0538.1038.1538.2038.2538.3018.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb208Pb/204Pb0.512960.512970.512980.512990.513000.513010.5130218.25 18.35 18.45 18.55 18.65 18.75206Pb/204Pb143Nd/144NdBHVO-2 leachedMean BHVO-2 unleachedMean BHVO-2 leachedThis StudyBlichert-Toft and Albar?de [2009]a bcNobre Silva et al. (2012) Figure A3.  file:///C|/Documents%20and%20Settings/tkstephe/Desktop/ggge20047-sup-0005-readme.txt[3/27/2014 3:11:16 PM]Auxiliary Material Submission for Paper # 2012GC004373Isotopic Systematics of the Early Mauna Kea Shield Phase and Insight Into the Deep Mantle Beneath the Pacific Oceanhttp://dx.doi.org/10.1029/2012GC004373Authors: Ines Garcia Nobre Silva, Dominique Weis, and James S. ScoatesPacific Centre for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Road, Vancouver, BC V6T 1Z4, CanadaAuxiliary material for this article contains four supplementary files including one text file and three figures regarding the assessment of analytical precision and accuracy of the dataset.List of Figures of Auxiliary MaterialFigure A1. Down-hole comparison of the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for the same set of samples recovered during the HSDP2-B and ?C. Analytical uncertainty (2 SE) is smaller than the symbol size except when shown by the error bars.Figure A2. Binary diagrams comparing the Pb and Nd isotopic compositions determined in this study and by Blichert-Toft and Albar?de [2009] for samples recovered during the HSDP2-B and ?C. Slopes of unity are shown for reference.Figure A3. Pb-Pb and Nd-Pb isotope diagrams comparing the isotopic compositions determined in this study and those by Blichert-Toft and Albar?de [2009]. For reference, the compositions of USGS reference material BHVO-2 analyzed by Weis et al. [2005, 2006] and in this study are also shown. ArticleVolume 14, Number 327 March 2013doi:10.1002/ggge.20047ISSN: 1525-2027Isotopic systematics of the early Mauna Kea shield phase andinsight into the deep mantle beneath the Pacific OceanIn?s G. Nobre Silva, Dominique Weis, and James S. ScoatesPacific Center for Isotopic and Geochemical Research, Department of Earth and Ocean Sciences,University of British Columbia, Vancouver, British Columbia, Canada (inobre@eos.ubc.ca)[1] The 3500m deep Hawai`i Scientific Drilling Project core provides a ~680 kyr record of the magmatichistory and source components ofMaunaKea volcano.We report high-precision Pb-Sr-Nd isotopic compositionsof 40 basalts from the last 408 m of the final drilling phase (HSDP2-B and HSDP2-C) and show that theselowermost basalts represent the early shield stage of Mauna Kea?s growth history. Two sample groups aredistinguished based on their isotopic variability compared to the rest of the core. Over a depth interval of210 m (3098.2?3308.2 mbsl), the basalts show very restricted isotopic variation and represent sampling of arelatively homogeneous source. Samples from the bottom 192 m record the largest range of 206Pb/204Pb and208Pb/204Pb in the core, reflecting the greater isotopic variability of the earlier stages of volcanism comparedto subsequent stages. The heterogeneity of Mauna Kea lavas is explained by mixing variable proportions offour distinct components intrinsic to the Hawaiian mantle plume. One of these components, Kea, is a prevalentand long-lived composition within the Hawaiian plume, whereas the other three components are involved atdifferent stages of the volcano?s history and contribute to the short-term isotopic variability of Mauna Kea.The compositional similarity of the Kea component to ?C? and to the super-chondritic bulk-silicate Earthsuggests that Kea may be part of the primitive mantle of a non-chondritic Earth. Other Pacific oceanic islandbasalts share Kea-like compositions, indicating that the Kea component is a common, widespread compositionwithin the Pacific deep mantle.Components: 11,700 words, 8 figures, 1 table.Keywords: HSDP2; Mauna Kea; Hawaiian mantle plume; ocean island basalts; Pb-Sr-Nd isotope systematics;mantle heterogeneities.Index Terms: 1025 Geochemistry: Composition of the mantle; 1040 Geochemistry: Radiogenic isotopegeochemistry.Received 8 September 2012; Revised 3 December 2012; Accepted 16 December 2012; Published 27 March 2013.Nobre Silva, I. G., D.Weis, and J. S. Scoates (2013), Isotopic systematics of the earlyMaunaKea shield phase and insightinto the deep mantle beneath the Pacific Ocean, Geochem. Geophys. Geosyst. 14, 659?676, doi:10.1002/ggge.20047.1. Introduction[2] The age-progressive Hawaiian-Emperor volcanicchain in the Pacific Ocean is the classic example ofintraplate hotspot volcanism attributed to a deep-seated mantle plume [e.g., Morgan, 1971; Courtillotet al., 2003;DePaolo andWeis, 2007]. This simple tec-tonic setting, together with the distant location fromplate margins and large rates of magma flux, makesHawaiian volcanoes one of the best places to studythe chemical evolution and structure of mantle plumesand of the deep mantle [e.g., Staudigel et al., 1984;?2013. American Geophysical Union. All Rights Reserved. 659Sleep, 1990; Campbell and Griffiths, 1991; Hauriet al., 1994; DePaolo et al., 2001; Bryce et al., 2005;Farnetani and Hofmann, 2009; Weis et al., 2011].As the Pacific plate moves across the Hawaiianmantleplume, at a velocity of 9?10 cm/yr, individual volca-noes grow and evolve through several stages (pre-shield, shield, post-shield, and a much later one,rejuvenated) as they sample different areas ofthe plume?s melting region [e.g., Clague andDalrymple, 1987]. The geochemistry of continuouseruptive sequences of individual volcanoes hence pro-vides a record of the geochemical time series of theplume?smelting region [e.g.,Hauri et al., 1996;Lassiteret al., 1996;DePaolo et al., 2001; Bryce et al., 2005].[3] Compositional variations occur over various timescales during the eruptive life of a Hawaiian volcano.Both short-term (decadal to centennial) and long-term(millennial) isotopic variations are recognized inshield lavas of Hawaiian volcanoes [e.g., Pietruszkaand Garcia, 1999; Marske et al., 2007; 2008; MaunaLoa, Kurz and Kammer, 1991; Kurz et al., 1995;Rhodes and Hart, 1995;DePaolo et al., 2001; MaunaKea, Blichert-Toft et al., 2003; Eisele et al., 2003;Kurz et al., 2004, Kauai, Salters et al., 2006;Fekiacovaet al., 2007], all within the larger time scale (?1 Ma)of volcano growth and compositional evolution [e.g.,Frey et al., 1990; Garcia et al., 2006]. The ~3500 mdeep core recovered by the Hawai`i Scientific Dril-ling Project (HSDP) constitutes the longest stratigra-phically controlled record of the magmatic output ofa single volcano sampled thus far. The analysis ofthe temporal isotopic covariations within the first~3100m of core allowed the identification of compo-sitional heterogeneities within the Hawaiian plumeas well as their maximum and minimum sizes[e.g., Blichert-Toft et al., 2003; Eisele et al., 2003;Abouchami et al., 2005; Bryce et al., 2005]. Addi-tionally, direct comparison with lavas from otherHawaiian volcanoes erupted at equivalent stages ofvolcano growth led to the formulation of newmodelsfor the chemical structure of the Hawaiian plumeand its deep mantle source [e.g., DePaolo et al.,2001; Blichert-Toft et al., 2003; Kurz et al., 2004;Abouchami et al., 2005; Bryce et al., 2005;Farnetaniand Hofmann, 2010, Weis et al., 2011].[4] Hawaiian volcanoes younger than 5Ma form twosub-parallel chains, termed Kea and Loa [Dana,1849; Jackson et al., 1972], that are systematicallydistinct chemically and isotopically [e.g., Tatsumoto,1978; Frey and Rhodes, 1993; Abouchami et al.,2005]. The geochemical differences between volca-noes along the two chains reflect mixing of variableproportions of at least three distinct components[e.g., Staudigel et al., 1984; Stille et al., 1986; Eileret al., 1996; Tanaka et al., 2008]. The distributionof these components is a matter of considerable de-bate with two main models of plume structure beinginvoked to explain such long-term geochemical dif-ferences: a concentrically zoned plume [e.g., Hauriet al., 1994, 1996; Lassiter et al., 1996; DePaoloet al., 2001] and a bilaterally asymmetrical plume[Abouchami et al., 2005; Weis et al., 2011; Huanget al., 2011]. Both purely concentrically and bilater-ally zoned plume models are, however, unable tofully explain all the geochemical variability amongstHawaiian basalts. As a result, numerous variationsof these plume structure models incorporating verticalheterogeneities within the upwelling plume have beenproposed [e.g., Frey and Rhodes, 1993; Blichert-Toftet al., 2003; Kurz et al., 2004; Abouchami et al.,2005; Bryce et al., 2005; Huang et al., 2005, 2009;Marske et al., 2007; Xu et al., 2007; Blichert-Toftand Albar?de, 2009; Hanano et al., 2010; Farnetaniand Hofmann, 2010].[5] Any model for the Hawaiian mantle plume struc-ture must account for the longevity of the HawaiianKea component. Kea-like compositions have beenrecognized in lavas from the Hawaiian-Emperorseamount chain back to >85 Ma [Regelous et al.,2003; Abouchami et al., 2005; Tanaka et al., 2008]and in mid-Cretaceous basalts preserved in Kamchatka[Portnyagin et al., 2008]. Recently, Weis et al.[2011] showed that Loa-like isotopic compositionsextend back at least 5 myr along the Hawaiian chain.Based on their comparative study of Loa and Keashield lavas, Weis et al. [2011] argued that thegeochemical differences between Kea and Loa trendvolcanoes can be traced to the core mantle boundary.The more variable and enriched compositions of Loavolcanoes are explained by sampling of the heteroge-neous Pacific ultra low velocity zone (ULVZ) by theLoa side of the Hawaiian mantle plume, whereas the?average,? less heterogeneous compositions of Keavolcanoes are explained by sampling of deep Pacificmantle [Weis et al., 2011].[6] The last 408 m of the HSDP sampled a series ofsubmarine tholeiitic basalts that erupted in the earlyshield-building stage of Mauna Kea volcano. In thisstudy, we use the Pb, Sr, and Nd isotopic composi-tions of 40 whole-rock samples to identify short-term isotopic fluctuations that reflect compositionalheterogeneities sampled in the early phase of growthof Mauna Kea. We examine the >680 kyr isotopicrecord of Mauna Kea?s magmatic history to evaluateboth the short- and long-term isotopic variationswithin the drill core and provide constraints on thechemical structure of the Hawaiian mantle plumeand deep Pacific mantle.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.200476602. Hawai`i Scientific Drilling Project:Geological Setting and Core Stratigraphy[7] The Hawai`i Scientific Drilling Project was amultidisciplinary international scientific effort totest the models of growth and chemical evolutionof Hawaiian volcanoes by systematically samplinga continuous stratigraphic sequence of lavas froma large Hawaiian volcano [Stolper et al., 1996;DePaolo et al., 2001]. Mauna Kea was chosensince it is the youngest Hawaiian volcano that hascompleted its life cycle of major growth stages(pre-shield, shield, post-shield) [e.g., Clague andDalrymple, 1987; Frey et al., 1990; 1991; Stolperet al., 1996; Garcia et al., 2007; Stolper et al.,2009]. The HSDP drill sites were located on thenortheast side of the island of Hawai`i, on the eastflank of Mauna Kea volcano, in an abandonedrock quarry adjacent to Hilo International Airport(Figure 1). Almost 250 m of Mauna Loa lavasoverlies Mauna Kea lavas at this location, whichallowed for comparative studies between the twoconsecutive volcanoes.[8] The success of the first phase of the project (?pi-lot hole?HSDP1) [e.g., Stolper et al., 1996] led to thedeep drilling of the HSDP2, a ~3500m deep core thatwas recovered in two phases over a total period of al-most 5 years. The main drilling phase of the HSDP2was carried throughout 1999, during which time thehole reached 3110 meters below sea level (mbsl)[Garcia et al., 2007]. The second drilling phasewas accomplished in two stages. Starting in 2003with the enlargement of the hole?s diameter, coringbegan in late 2004 and proceeded until early 2005(phase B). Coring restarted in late 2006 and reachedcompletion in early 2007 at 3508 mbsl (phase C)[Stolper et al., 2009].[9] On the basis of observed contacts and variationsin mineralogical, lithological, and structural features,a total of 389 lithological units were identifiedwithin the HSDP2 core [Garcia et al., 2007; Stolperet al., 2009] and five depth zones were recognized(Figure 1c): (1) sub-aerial Mauna Loa lavas (surfaceto 246 mbsl), (2) sub-aerial Mauna Kea lavas (246to 1079 mbsl), (3) shallow submarine Mauna Kealavas (1079 to 1984 mbsl), (4) deep submarineMauna Kea lavas (1984 to 3098 mbsl), and (5) deepsubmarine Mauna Kea lavas from the final drillingphase (3098 to 3508 mbsl) [Rhodes and Vollinger,2004;Garcia et al., 2007, Stolper et al., 2009]. In thisfinal phase of drilling (HSDP2-B and HSDP2-C), 44flow and intrusive units were identified, consistingprimarily of submarine pillow lavas (~60%), withlesser amounts of hyaloclastites (~17%), massivevolcanic units (~12%), pillow breccias (~10%), andintrusive units (~1%) [Stolper et al., 2009; Rhodeset al., 2012].[10] The youngest dated Mauna Kea sample fromthe main phase of the HSDP2, an alkalic basalt at~277 mbsl, has a 40Ar/39Ar age of 236  16 ka,and the deepest dated sample, at a depth of 2789mbsl, has an age of 683  82 ka [Sharp and Renne,2005]. Assuming a linear fit to the 40Ar/39Ar ages,Sharp and Renne [2005] determined mean accumu-lation rates of ~9 m/kyr and ~0.9 m/kyr for theshield and post-shield sequences, respectively, overthe 400 kyr of volcanism recorded by the ~2.7 kmthick section of Mauna Kea basalts. Recently,Jourdan et al. [2012] refined the age-depth rela-tions in the deeper part of the HSDP2 core. Afterobtaining indistinguishable mean 40Ar/39Ar agesof 683  130 ka for two tholeiitic basalts recoveredfrom depths of 3278 and 3321 mbsl during HSDP2-B,these authors proposed that these ~3.3 km deeplava flows erupted at 681  120 ka. No age hasbeen determined on samples from the deepest200 m of core (phase C). Assuming the 8.4 m/kyrshield lava accumulation rate of Jourdan et al.[2012], modeled regression ages for samples fromthese deeper 200 m are inferred to range between~668 and ~688 kyr.3. Samples and Analytical Methods[11] Forty Mauna Kea basalts from the whole-rockreference suite of the HSDP2-B and HSDP2-C wereanalyzed for Pb-Sr-Nd isotope compositions. Themajor and trace element compositions of thesesamples are reported in Rhodes et al. [2012], andHf-Pb-Nd isotope compositions were previouslyreported by Blichert-Toft and Albar?de [2009]. Allbasalts are tholeiitic and cover a wide range ofMgO contents (6.6?25.4 wt%). Most samples havehigh SiO2 contents (>50 wt%) and based on theirtrace element concentrations belong to type-1 (highSiO2, high Zr/Nb) and type-4 (high SiO2, lowZr/Nb) magma groups [Rhodes and Vollinger,2004; Rhodes et al., 2012]. Exceptions are samplesR6-2.15-3.0 and R184-1.15-2.1, two intrusive unitsat 3098.2 and 3400.9 mbsl, respectively, which aremost similar to type-3 (low SiO2, low Zr/Nb) lavas;and samples R210-3.3-3.95 and R219-5.55-6.2,7.25-7.7, at 3472.2 and 3500.9 mbsl, respectively,which have compositions most similar to those ofMauna Loa volcano [Rhodes and Vollinger, 2004;Rhodes et al., 2012].GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047661LoaKeaMauna Loa Subaerial tholeiiteMauna Kea Subaerial(including alkalic lavas)Mauna Kea Subaerial tholeiiteash or soilSubaerialSubmarinerotary drilled intervalsmassivehyaloclastite1st intrusive1st pillowpillowintrusiveMKMLh t p e Dbm(s) l0500100015002000300025003500HSDP2-B & C(2003-2007)246 m1079 madapted from Stolper et al. [2009]1984 m3098 mHSDP2 (1999)HSDP1 (1993)Figure 1. Location maps of the Hawaiian Islands and HSDP2 drill site. (a) Overview map of the Hawaiian Islandsand the Kea and Loa volcano trends. (b) Enlarged view of the topography and bathymetry (500 m interval contours) ofthe Big Island of Hawai`i (maps drawn using GeoMapApp: http://www.geomapapp.org). The boundaries of thefive volcanoes (Ko, Kohala; Hu, Hualalai; MK, Mauna Kea; ML, Mauna Loa; and Ki, Kilauea) and the submergedshoreline of Mauna Kea are shown. The red star indicates the location of the HSDP2 deep hole drilled during 1999and 2004?2007. The Loihi seamount (Lo) occurs to the southeast of the Big Island. (c) Simplified lithologic columnof the HSDP2 drill core (adapted from Stolper et al. [2009]). The lithologies are represented by different patterns asindicated. The depth scale is meters below sea level (mbsl), and key depths are identified: boundary betweenMauna Loa (ML) and Mauna Kea (MK) lavas, transition between sub-aerial and submarine MK lavas, and firstoccurrence of intrusive rocks and pillow lavas. The dashed box highlights the stratigraphic levels drilled duringHSDP2 phases B and C.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047662[12] All isotopic analyses were performed on whole-rock powders (except for sample 26-102-R163-2.1-2.6that was in glass chip form) that were prepared,rinsed, and pulverized following the procedures ofRhodes [1996] and Rhodes and Vollinger [2004].Given the time gap between the two sample recoveryphases of the last 408 m of the HSDP2 core, theisotopic measurements presented in this study wereobtained in two analytical sessions (mid-2006 forthe 22 samples from phase B and early 2008 forthe 18 samples from phase C). All chemical purifica-tion and mass spectrometric analyses were carriedout in Class 100 and Class 10,000 clean laboratories,respectively, at the Pacific Center for Isotopic andGeochemical Research (PCIGR) at the Universityof British Columbia. For all samples, the Pb, Sr,and Nd isotopic compositions were determined onthe same sample dissolution. All sample solutionswere passed twice through Pb anion exchangecolumns for Pb purification. The fractions washedout from the Pb columns, containing all other samplematrix elements, were then processed through otherchromatographic ion exchange columns for Sr andNd purification, following the sequential chromato-graphic purification methods described in Weiset al. [2006]. Given the importance of efficiently re-moving alteration phases and any extraneous Pb con-taminant to get accurate and reproducible Pb isotopiccompositions of oceanic basalts [Hanano et al.,2009, Nobre Silva et al., 2009], all samples werethoroughly acid-leached prior to digestionand isotopic analysis following the sequential acidleaching procedure of Weis et al. [2005] and NobreSilva et al. [2009; 2010]. All mass spectrometricanalyses by MC-ICP-MS and TIMS followed theprocedures detailed inWeis et al. [2006], and standardvalues measured during the analytical sessions arereported in the footnote of Table 1. Total proceduralblanks were ~50, 180, and 45 pg for Pb, Sr, and Nd,respectively, which are negligible compared to the el-emental concentrations in the samples. Two rock ref-erence materials (USGS BHVO-2 and Hawaiian rockKil-93) were also processed together with the sampleset. Their values are reported in Table 1, together withthe sample results.4. Results4.1. Stratigraphic Variations in Pb-Sr-NdIsotope Compositions[13] Basalts from the last 408 m (phases B and C)of the HSDP2 core yield 206Pb/204Pb = 18.3033?18.6936, 207Pb/204Pb = 15.4707?15.4993, 208Pb/204Pb = 37.924?38.271, 87Sr/86Sr = 0.703513?0.703631,and 143Nd/144Nd = 0.512968?0.513011 (Table 1and Figure 2). The Pb and Nd isotopic values aremostly similar to those of the overlying, youngerlavas (above ~3098 mbsl; Figure 2) [e.g., Eiseleet al., 2003; Blichert-Toft et al., 2003; Bryce et al.,2005] and are in good agreement with those ofBlichert-Toft and Albar?de [2009] (Appendix A inthe Supporting Information).1[14] Between 3097.7 and 3308.2 mbsl, the isotopicvariability of these older basalts is very restricted(206Pb/204Pb = 18.4953?18.5960, 208Pb/204Pb = 38.187?38.204, 87Sr/86Sr = 0.703595?0.703631, and 143Nd/144Nd = 0.512968?0.512990). Type-1 basalts are themost abundant in this interval, and the observedrange of isotopic compositions correlates with theirlimited variation in major element oxide and trace el-ement contents [Rhodes et al., 2012]. These 210.5 mrepresent the longest interval (~10 kyr) of restrictedgeochemical variation observed in the HSDP2 core;the relative variations in 206Pb/204Pb, 86Sr/87Sr, and143Nd/144Nd are ~11, ~4, and ~3, respectively,smaller than those observed for younger basalts (Fig-ure 2). The exception is sample R6-2.15-3.0, a mas-sive intrusive rock at 3098.2 mbsl with low SiO2and Zr/Nb [Rhodes et al., 2012] that has isotopiccompositions identical to other type-3 samples re-covered higher in the core stratigraphy during themain phase of the HSDP2 [Blichert-Toft et al.,2003; Eisele et al., 2003; Bryce et al., 2005].[15] Basalts from the last 192 m of drill core (3313.5to 3505.7 mbsl) are most similar to type-4 basalts andshow significantly greater Pb isotopic variations(Figure 2 and Table 1). As also noted by Blichert-Toft and Albar?de [2009], this group of 19 samplesyields the largest range of Pb isotopic compositions(206Pb/204Pb = 18.3033?18.6936, 208Pb/204Pb = 37.924?38.291) compared to basalts from the entire~3200 m of core above (Figure 2). These deeperbasalts extend the Pb isotopic range (206Pb/204Pband 208Pb/204Pb) of Mauna Kea to compositions thatare both significantly more and less radiogenic thanpreviously observed for this volcano [e.g.,Abouchamiet al., 2000; Eisele et al., 2003; Blichert-Toft et al.,2003]. This distinction is less obvious in Sr and Ndisotopic compositions (Figure 2). Collectively, thelowermost 192 m of basalts in the core display ~2smaller Sr and Nd isotopic variations in comparisonto the younger samples [Bryce et al., 2005] and showa systematic progression of increasing 87Sr/86Sr andincreasing eNd with depth (Figure 2). In this deeper1All Supporting Information may be found in the online version ofthis article.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047663Table1.Pb,Sr,andNdIsotopicCompositionsbyMC-ICP-MSandTIMSofMaunaKeaSamplesFromtheLastDrillingPhases(BandC)oftheHSDP2CoreSample[RunandCoreInterval]Depth(mbsl)a206Pb/204Pbb2SEb207Pb/204Pbb2SEb208Pb/204Pbb2SE87Sr/86Src2s143Nd/144Ndd2se NdeHSDP2-BR6-0.85-1.23097.718.59130.000915.48540.000938.19050.00260.7035820.0000100.5129840.0000076.7R6-2.15-3.03098.218.49530.000615.47280.000638.18690.00190.7035950.0000070.5129680.0000066.4R8-0.15-0.73102.418.59340.000915.48710.000838.19620.00230.7035770.0000060.5129830.0000056.7R10-4.35-4.73109.418.59490.000615.48820.000538.20170.00130.7035730.0000060.5129800.0000076.7repf-18.59200.001015.48500.000938.19030.0026-----R11-5.3-5.73111.518.58530.000815.48710.000838.18850.00240.7035650.0000070.5129770.0000066.6dupg-------0.7035710.0000080.5129770.0000066.6R13-0.1-0.53115.218.58680.000715.48810.000838.19390.00250.7035510.0000070.5129720.0000056.5R16-5.2-6.03122.518.58660.000915.48880.000938.19400.00240.7035640.0000070.5129740.0000066.5dup3122.518.58570.001215.48800.001138.19340.0033-----R30-4.25-5.23141.218.59120.000515.48590.000538.19390.00160.7035910.0000080.5129900.0000066.9R51-2.4-3.63160.818.59360.001215.48830.001438.20050.00450.7035680.0000060.5129820.0000086.7R56-1.0-1.53171.118.58650.001015.48750.001138.19260.00310.7035640.0000080.5129750.0000056.6dup3171.118.58880.001015.48380.000738.18690.0024-----R57-5.0-5.93173.418.59310.000715.48830.000838.20030.00190.7035720.0000060.5129820.0000076.7R60-7.6-8.43181.218.58110.001215.48810.001338.18670.00400.7035750.0000070.5129870.0000076.8dup3181.218.57960.001015.48660.001138.18240.0036-----R80-2.8-3.53215.518.58330.001115.48940.001238.19390.00360.7035740.0000060.5129830.0000066.7rep3215.518.58150.003015.48850.003838.19140.0126-----R93-1.4-2.03234.718.58190.001015.48790.001138.19000.00310.7035720.0000090.5129800.0000076.7R101-4.4-4.93244.818.58530.000815.48540.000638.18910.00160.7035870.0000080.5129800.0000076.7R108-0.0-0.73263.918.59350.000715.48640.000738.19540.00180.7035690.0000090.5129720.0000056.5rep3263.918.59380.000715.48680.000738.19590.0020-----R112-7.1-7.73277.018.58450.001015.48530.000938.18830.00220.7035610.0000100.5129780.0000056.6R116-6.25-7.23285.818.57650.001015.48760.001138.18580.00370.7035800.0000100.5129690.0000086.5dup------0.7035790.0000080.5129720.0000066.5R122-1.85-2.653300.118.59600.000915.48870.000838.20200.00220.7035650.0000080.5129840.0000066.7R125-4.9-5.33305.918.59200.001215.48820.001338.19890.00410.7035850.0000060.5129800.0000056.7R127-1.4-2.23308.218.59070.000915.49850.000738.20180.00180.7035880.0000060.5129880.0000066.8rep18.59100.000815.49930.000738.20420.0021-----R129-5.8-6.53313.518.42860.000715.47250.000738.06850.00190.7036310.0000070.5129710.0000086.5HSDP2-CR149-1.2-1.63333.318.63050.000715.49060.000738.22330.00170.7035590.0000080.5129830.0000086.7R154-2.1-2.953339.518.50350.000715.47800.000638.12960.00300.7035510.0000070.5129960.0000057.0R155-2.7-3.53341.418.54880.001015.48030.001038.15010.00300.7035640.0000070.5129810.0000056.7R158-1.75-2.103348.318.62960.000715.49110.000738.22420.00240.7035660.0000070.5129790.0000096.6rep--------0.5129800.0000086.7R162-1.55-2.33353.918.62920.000715.48970.000638.21950.00200.7035600.0000080.5129860.0000076.8R163-2.1-2.63357.018.68850.000915.49410.001138.25880.00330.7036040.0000080.5129790.0000076.6GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047664Table1.(continued)Sample[RunandCoreInterval]Depth(mbsl)a206Pb/204Pbb2SEb207Pb/204Pbb2SEb208Pb/204Pbb2SE87Sr/86Src2s143Nd/144Ndd2se NdeR165-0.75-1.453359.818.69220.000815.49470.000938.26510.00260.7035620.0000100.5129870.0000106.8dup3359.818.68980.000815.49330.000638.26010.00180.7035630.0000100.5129810.0000066.7R168-3.7-4.153366.318.69360.000915.49690.000838.27100.00210.7035560.0000080.5129770.0000096.6R176-5.93-6.53381.318.69160.000715.49380.000738.26240.00180.7035570.0000080.5129750.0000066.6R184-1.15-2.13400.918.52890.000615.47880.000638.20580.00170.7035130.0000100.5129930.0000066.9R187-0.9-1.8,2.05-2.53405.318.59290.000715.48690.000738.17560.00200.7035870.0000070.5129680.0000066.4R192-4.4-5.43418.118.64380.001315.48890.001038.21030.00260.7035290.0000090.5129810.0000066.7rep3418.118.64730.000715.49100.000638.21670.0017R198-0.5-1.93435.218.62970.002315.48940.002038.21930.00530.7035590.0000090.5129880.0000076.8R204-1.1-1.83453.418.59350.001615.49840.001438.20430.00350.7035700.0000090.5129840.0000076.7R205-7.5-8.153458.418.64240.000815.49330.000738.23470.00250.7035830.0000070.5129890.0000066.9R210-3.3-3.953472.218.30410.000915.47070.001037.93400.00270.7035540.0000090.5130000.0000077.1dup3472.218.30560.000715.47330.000637.94120.00160.7035670.0000090.5130110.0000097.3duprep3472.218.30330.000615.47120.000737.93410.0019-----R219-5.55-6.2,7.25-7.73500.918.30590.000815.47330.000637.92410.00160.7035960.0000070.5130000.0000077.1R222-8.0-8.83505.718.48360.000815.47290.000838.11720.00270.7035340.0000090.5129940.0000066.9USGSreferencematerialBHVO-2i18.64510.001115.48900.001338.20600.00400.7034620.0000070.5129790.0000076.7Hawaiianrockin-housereferencematerialKil-93h,i18.40660.000815.47150.000738.06100.00200.7035820.0000090.5129720.0000076.5a mbsl=metersbelowsealevel.bPbisotopicratiosbyMC-ICP-MS,normalizedrelativetotheSRM981TS-TIMSreferencevaluesofAbouchamietal.[2000];the2SEistheabsoluteerrorvalueoftheindividualsampleanalysis(internalerror).Duringthetwoanalyticalsessionsoverwhichisotopicmeasurementswereobtained(mid-2006forthe22samplesfromphaseBandearly2008forthe18samplesfromphaseC),analysesoftheSRM981Pbstandard(n=140,and36)yieldedmeanvaluesof206Pb/204Pb=16.94060.0013and16.94200.0016,207Pb/204Pb=15.49640.0025and15.49870.0020,and208Pb/204Pb=36.71380.0084and36.71560.0062,respectively.c SrisotopicratiosmeasuredbyTIMS,normalizedrelativetotheSRM987standardsolutionvalueof87Sr/86 Sr=0.710248[Weisetal.,2006];the2serroristheabsoluteerrorvalueoftheindividualsampleanalysis(internalerror)reportedas106 .Duringthecourseoftheseanalyses,theaverage87Sr/86 SrvalueoftheSRM987Srstandardwas0.7102560.000015(n=10)in2006and0.7102460.000004(n=9)in2008.dNdisotopicratiosmeasuredbyTIMS(HSDP2-Bsamples)andMC-ICP-MS(HSDP2-Csamples),normalizedrelativetotheLaJollastandardsolutionvalueof143Nd/144Nd=0.511858[Weisetal.,2006]andtotheRennesNdstandardvalueof143Nd/144Nd=0.511973[ChauvelandBlichert-Toft,2001],respectively.Duringthecourseofanalyses,theaverage143Nd/144NdvaluesoftheLaJollaNdstandardwas0.5118520.000010(n=10)andtheaveragevaluefortheRennesNdstandardwas0.5120000.000009(n=40).e eNdvaluesarecalculatedusingthe143Nd/144NdCHURvalue=0.512638[JacobsenandWasserburg,1984].f rep=replicateanalysisofthesamesamplesolutionbyMC-ICP-MS.gdup=fullproceduralduplicateanalysisofthesamesample.hSamplefromKilauea?ssummitPu`u`O`oeruptioncollectedin1993byM.O.Garcia,usedasin-housereferencematerial.i IsotopicvaluesforUSGSBHVO-2areingoodagreementwiththepublishedvaluesbyWeisetal.[2006],andthevaluesforKil-93areingoodagreementwiththein-housevaluesforthisHawaiianrock(NobreSilvaetal.,2013).GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047665section of the core, few samples have major and traceelement compositions (e.g., SiO2(13)> 49%; Zr/Nb>13) that trend toward compositions observed atMauna Loa volcano [Rhodes et al., 2012]. Their Pb,Sr, and Nd isotope ratios are however distinct fromthose of Mauna Loa, especially their Nd isotopes,which are most similar to late-shield and post-shieldlavas found in the upper Mauna Kea section of the drillcore [e.g., Bryce et al., 2005; Hanano et al., 2010].4.2. Isotope Correlations[16] The Sr, Nd, and Pb isotopic compositions of thetholeiites from the HSDP2-B and HSDP2-C showsome degree of correlation, consistent with the trendsformed by other Hawaiian volcanoes (Figures 3?6).With respect to Sr-Nd isotopes, these older tholeiiteslie within the compositional range of Mauna Kea, atthe depleted end (low 87Sr/86Sr, high 143Nd/144Nd) ofthe array formed by the Hawaiian Islands (Figure 3).Compared to other Mauna Kea basalts, the 87Sr/86Srand 143Nd/144Nd values of HSDP2-B and HSDP2-Cbasalts are displaced toward the lower and higherlimits, respectively, of the isotopic ranges. In Sr-Pband Nd-Pb isotope diagrams (Figures 4 and 5), thesebasalts extend from the compositional trend definedby other Mauna Kea and Kea-trend shieldbasalts toward slightly lower 87Sr/86Sr and higher143Nd/144Nd values, similar to the compositions ofthe late stage, post-shield lavas from Mauna Keaand Kohala [Holcomb et al., 2000; Eisele et al.,2003; Bryce et al., 2005; Hanano et al., 2010].[17] The HSDP2-B and HSDP2-C basalts form twodistinct Pb isotope arrays that intersect at theMLMKsubaerialsubmarineMLMKsubaerialsubmarinezone 1zone 2zone 3zone 4zone 1zone 2zone 3zone 40400800120016002000240028003200360018.0 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8206Pb/204PbDepth (mbsl)0400800120016002000240028003200360037.7 37.8 37.9 38.0 38.1 38.2 38.3208Pb/204Pb040080012001600200024002800320036000.925 0.930 0.935 0.940 0.945 0.950 0.955 0.960208Pb*/206Pb*040080012001600200024002800320036000.7034 0.7035 0.7036 0.7037 0.7038 0.703987Sr/86Sr040080012001600200024002800320036005.5 6.0 6.5 7.0 7.5NdDepth (mbsl)Mauna LoaMauna Kea?Kea-lo8??Kea-mid8??Kea-hi8?Mauna KeaHSDP2HSDP2-B & CFigure 2. Pb, Sr, and Nd isotopic variations with depth (meters below sea level, mbsl) in the HSDP2 drill core. Red-filled symbols represent the samples from phases B and C analyzed in this study. Other HSDP2 data sources are asfollows: Open squares?Mauna Loa, DePaolo et al. [2001] and Blichert-Toft et al. [2003]; open circles?Mauna Kea,Blichert-Toft et al. [2003] and Bryce et al. [2005]; and gray-filled circles?distinct Mauna Kea sample groups of Eiseleet al. [2003]. Also indicated are theMauna Loa-Mauna Kea and sub-aerial-submarine boundaries and the four zones iden-tified by Stolper et al. [2004]. Literature data were normalized to the same standard values, i.e., triple spike values of SRM981 [Abouchami et al., 2000], La Jolla 143Nd/144Nd = 0.511858 and SRM 987 = 0.710248 [Weis et al., 2006].GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047666(0.7031, 0.5130)(0.70427, 0.51265)Figure 3. 143Nd/144Nd versus 87Sr/86Sr diagram for the HSDP2 Mauna Kea basalts compared to shield basalts fromother volcanoes on the Big Island of Hawai`i (Kohala, Hualalai, Mauna Loa, Kilauea, and Loihi) and to post-shieldlavas of Mauna Kea and Kohala. The analytical uncertainty (2s error) is smaller than the symbol sizes. For refer-ence, the ?Kea,? depleted Makapuu (DMK), and enriched Makapuu (EMK) end-members from Tanaka et al. [2002]and the ?Loihi? end-member from Tanaka et al. [2008] are shown (open hexagons). Data sources are from the fol-lowing: Mauna Kea, Bryce et al. [2005]; Kilauea, Pietruszka and Garcia [1999], Abouchami et al. [2005], andMarske et al. [2007]; Hilina bench, Chen et al. [1996] and Kimura et al. [2006]; Kohala, Hofmann et al. [1987],M. O. Garcia (unpublished data, 2001), and D. Weis (unpublished data, 2001); Hualalai, Yamasaki et al. [2009];Mauna Loa, DePaolo et al. [2001] and Weis et al. [2011]; Loihi, Garcia et al. [1993]; Mauna Kea post-shield,Bryce et al. [2005] and Hanano et al. [2010]; and Kohala post-shield, Holcomb et al. 2000 and Hanano et al.[2010]. Literature data were normalized to the same standard values as noted in Figure 2.0.70330.70350.70370.70390.70410.70430.704517.70 17.90 18.10 18.30 18.50 18.70 18.90206Pb/204PbMauna LoaHualalaiLoihiLoa VolcanoesHilo RidgeMauna KeaPost-shieldKohalaLate-ShieldKohalaPost-shieldDMKLOIHIKEAKOOLAU(17.78, 0.7031)Hilina BenchKohalaKilaueaKea Volcanoes?Kea-lo8??Kea-mid8??Kea-hi8?HSDP2-B&CMauna KeaFigure 4. 87Sr/86Sr versus 206Pb/204Pb diagram for the HSDP2 Mauna Kea basalts compared to shield basalts fromthe other volcanoes on the Big Island of Hawai`i (Kohala, Hualalai, Mauna Loa, Kilauea, and Loihi) and to post-shield lavas of Mauna Kea and Kohala. Data sources for Pb isotopes are from the following: Mauna Kea,Blichert-Toft et al. [2003] and Eisele et al. [2003]; Kilauea, Pietruszka and Garcia [1999], Abouchami et al.[2005], and Marske et al. [2007]; Hilina bench, Chen et al. [1996], Abouchami et al. [2005], and Kimura et al.[2006]; Kohala, Abouchami et al. [2005], M. O. Garcia (unpublished data, 2001), and D. Weis (unpublished data,2001); Hualalai, Yamasaki et al. [2009]; Mauna Loa, Blichert-Toft et al. [2003] and Weis et al. [2011]; Loihi, Abouchamiet al. [2005]; Mauna Kea post-shield, Hanano et al. [2010]; and Kohala post-shield, Holcomb et al. [2000] and Hananoet al. [2010]. Symbols and standard normalization values are as noted in Figure 3.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047667Figure 6. Diagrams of (a) 208Pb/204Pb versus 206Pb/204Pb and (b) 208Pb/206Pb versus 207Pb/206Pb for the HSDP2Mauna Kea basalts compared to shield basalts from other volcanoes on the Big Island of Hawai`i (Kohala, Hualalai,Mauna Loa, Kilauea, and Loihi) and to post-shield lavas of Mauna Kea and Kohala. The thick black line represents thePb isotopic division for Loa and Kea trend volcanoes as defined by Abouchami et al. [2005]. The thin black lines rep-resent the HSDP2 Pb isotopic arrays ?Kea-hi8,? ?Kea-mid8,? and ?Kea-lo8? defined by Eisele et al. [2003]. Thedashed line represents the linear regression though the ?Kea-mid8? and Mauna Loa Pb isotopic compositions, indicat-ing the involvement of Loa-like compositions, best defined by the EMK component in the Mauna Kea source region.Symbols, data sources, and standard normalization values are as in previous figures.0.51260.51270.51280.51290.51300.513117.70 17.90 18.10 18.30 18.50 18.70 18.90206Pb/204PbKEADMKEMKHilo RidgeMauna KeaPost-shieldKohalaLate-ShieldKohalaPost-shieldMauna LoaHualalaiLoihiLoa VolcanoesHilina BenchKohalaKilaueaKea Volcanoes?Kea-lo8??Kea-mid8??Kea-hi8?HSDP2-B&CMauna KeaFigure 5. 143Nd/144Nd versus 206Pb/204Pb diagram for the HSDP2Mauna Kea basalts compared to shield basalts from theother volcanoes on the Big Island of Hawai`i (Kohala, Hualalai, Mauna Loa, Kilauea, and Loihi) and to post-shield lavas ofMauna Kea and Kohala. Symbols, data sources, and standard normalization values are as in previous figures.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047668radiogenic end (Figure 6), extending the range of206Pb/204Pb and 208Pb/204Pb of Mauna Kea to signifi-cantly more radiogenic values, similar to those of ?an-cestral? Kilauea lavas [Kimura et al., 2006]. One Pbisotope array overlaps with Mauna Kea?s main Pbisotopic compositional field, best represented by the?Kea-mid8? array defined by the majority (>75%)of the younger HSDP2 samples [Eisele et al.,2003]. The second array is constituted by samplesR6-2.15-3.0 and R184-1.15-2.1 (two low SiO2 andlow Zr/Nb intrusive units at 3098.2 and 3400.9 mbsl,respectively) that plot together with the low SiO2basalts recovered higher in the core stratigraphythat define the ?Kea-hi8? array [Eisele et al., 2003].Samples R210-3.3-3.95 and R219-5.55-6.2; 7.25-7.7,at the bottom of the core, extend the Pb isotopiccompositions of Mauna Kea to significantly less ra-diogenic values, plotting in between the ?Kea-mid8?and ?-lo8? Pb arrays. Although these samples have el-emental compositions and 208Pb/204Pb that are withinthe range of values for Mauna Loa, their 206Pb/204Pband 207Pb/204Pb (not shown) are higher, comparableto those of lavas from Kohala, Kilauea, and post-shield stage of Mauna Kea (Figure 6).5. Discussion5.1. HSDP2: A Record of the Evolution of aSingle Volcano or the Output of DifferentVolcanoes?[18] Hawaiian volcanoes evolve through severalgrowth stages that are marked by changes in compo-sition and eruption rates as they are carried by the Pa-cific plate across the magma-production region of theHawaiian mantle plume [e.g., Chen and Frey, 1983;Clague and Dalrymple, 1987; Moore and Clague,1992]. Oceanic lithosphere does not significantly influ-ence the isotopic compositions of Hawaiian lavas [e.g.,Lassiter et al., 1996; Blichert-Toft et al., 2003;Fekiacova et al., 2007; Marske et al., 2007; Hananoet al., 2010]. The geochemical variations within thestratigraphic sequence of lavas derived from a singlevolcano therefore reflect the temporal variationswithin its magma source [e.g., Kurz and Kammer,1991; Rhodes and Hart, 1995; Lassiter et al., 1996;Rhodes, 1996; Pietruszka and Garcia, 1999;DePaolo et al., 2001; Bryce et al., 2005; Abouchamiet al., 2005; Marske et al., 2007, 2008]. As differentvolcanoes grow to form the Hawaiian Islands, theirlavas overlap and interlay, with older volcanoes be-coming partially covered by lavas from younger vol-canoes [e.g.,Moore and Clague, 1992; DePaolo andStolper, 1996]. Mauna Kea is built on top of ~6 kmthick Cretaceous oceanic crust plus pelagic and clas-tic sediments and, on the flank of the adjacent, olderKohala volcano [e.g., Moore and Clague, 1992;DePaolo and Stolper, 1996].[19] It has been suggested that the low SiO2-high208Pb*/206Pb* lavas encountered in the deeper sec-tion of the HSDP2 core may not represent the vari-able output of Mauna Kea but instead that of Kohala[Holcomb et al., 2000] or of another unknown vol-cano [e.g., Stolper et al., 2004; Blichert-Toft andAlbar?de, 2009]. The isotopic similarities betweenbasalts dredged along the Hilo Ridge below ~1100mbsl and sub-aerial lavas from Kohala volcano(Pololu and Hawi volcanic rocks), plus the older agesof the deeper section of the Hilo Ridge, suggest that itmay be part of Kohala?s southeast rift zone ratherthan belonging to Mauna Kea [Holcomb et al.,2000; Lipman and Calvert, 2011]. Based on the ele-mental and isotopic distinction between HSDP2lavas shallower than 3098 mbsl and known Kohalasamples, Rhodes and Vollinger [2004] and Stolperet al. [2004] argued against the presence of Kohalalavas within this section of the HSDP2 core, althoughthey did not dismiss the possibility of encounteringlavas from this volcano at deeper levels.[20] The last phase of drilling of the HSDP2 ex-tended the core to ~3500 mbsl. Within the deepest408 m of the core, high SiO2 lavas of variable Zr/Nbare the most abundant [Rhodes et al., 2012]. The twolow-SiO2 intrusive units found in this section have iso-topic compositions that are indistinguishable fromother Mauna Kea samples, except for their higher208Pb/204Pb and 208Pb*/206Pb* values, that are Loihi-like (Figures 2?6). These two units may be feederdikes for the other low SiO2-high208Pb*/206Pb*lavas encountered higher in the core stratigraphy[Rhodes et al., 2012]. Some of the basalts at thebottom of the drill core do show isotopic similaritiesto late-shield (Pololu) and post-shield (Hawi) lavasfrom Kohala, as suggested by Holcomb et al. [2000],but also to post-shield lavas from Mauna Kea [e.g.,Eisele et al., 2003; Bryce et al., 2005; Hananoet al., 2010] (Figures 3?6). To assume that thesesamples in question are derived from Kohala impliesthat ~680 kyr ago, this volcano was reaching the endof its evolution. This is not supported by growthmodels for Kohala, which at this time should havebeen in its vigorous tholeiitic shield-building stage[Moore and Clague, 1992; Lipman and Calvert,2011], nor it is supported by the ages of sub-aeriallyexposed Kohala post-shield lavas (~175?450 ka)[Clague and Dalrymple, 1987; Aciego et al.,2010]. Although little is known about the historyand interactions between Hawaiian volcanoesGeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047669[Stolper et al., 2004], it is difficult to geometricallyreconcile the existence of an unknown volcano olderthan Mauna Kea [e.g., Baker et al., 2003]. The over-all isotopic consistency of the basalts deeper in theHSDP2 core stratigraphy with those from the overly-ing youngerMaunaKea lavas (Figures 3?6) attests tothe continuity of the Mauna Kea section and to therelative homogeneity of the Mauna Kea sourcethroughout its evolution.[21] The ~3263.7 m long Mauna Kea section of theHSDP2 core represents the continuous record of thelast ~680 kyr of volcanic activity of the Mauna Keavolcano as it crossed ~60?80 km over the melting re-gion of the Hawaiian mantle plume [e.g., Stolperet al., 2009]. Assuming a model ~1.5 Ma lifetimefor typical Hawaiian volcanoes [e.g., Garcia et al.,2006], it is unlikely that the early growth history(pre-shield stage) of Mauna Kea was sampled by thedeep HSDP2 core. This is supported by the fact thatthe deeper section of the core is constituted solely oftholeiitic basalts. Nevertheless, the duration of indi-vidual volcanoes is likely to vary depending on theproximity of the volcano track to the center of the hot-spot?s melting region, which influences the amount ofmagma supplied to each volcano [e.g., DePaolo andStolper, 1996; DePaolo et al., 2001; Baker et al.,2003]. According to the model of DePaolo andStolper [1996], Mauna Kea likely started to grow at~1.050 Ma. This would place the bottom of theHSDP2 core (>680 kyr) close to the transitionbetween the pre-shield and shield growth stages.[22] The older basalts recovered from deeper in theHSDP2 core stratigraphy show greater isotopic vari-ability compared to the overlying younger tholeiiticbasalts and are isotopically similar, especially in206Pb/204Pb, 87Sr/86Sr, and 143Nd/144Nd, to MaunaKea post-shield lavas (Figures 2?6). Together withthe overall lower Zr/Nb of these basalts, characteristicof Kilauea and Loihi [Rhodes and Vollinger, 2004,Rhodes et al., 2012], this suggests that the deeperbasalts of the HSDP2 core may represent the veryearly shield stage of Mauna Kea?s growth. At thistime, the degrees of melting would have increasedenough to produce tholeiitic compositions; however,the volcano?s capture zone must have still been closeenough to the edge of the plume?s melting region tosample a similar compositional domain to that sam-pled later during the post-shield phase.5.2. HSDP2 Isotope Variability and theHawaiian Source Components[23] The isotopic heterogeneity amongst Hawaiianshield basalts is explained by mixing of at leastthree isotopically distinct source components [e.g.,Staudigel et al., 1984; Stille et al., 1986; Eiler et al.,1996; Hauri et al., 1996]. These include: a relatively?depleted? component (with low 87Sr/86Sr, 3He/4He,207Pb/204Pb, and d18O, and high 206Pb/204Pb,208Pb/204Pb, 143Nd/144Nd, and 176Hf/177Hf), best ob-served in basalts from Kilauea (especially from theHilina bench) [e.g., Chen et al., 1996; Abouchamiet al., 2005; Kimura et al., 2006] and Mauna Kea, re-ferred to as the ?Kea? component; (2) a ?modestly de-pleted? component (with low 87Sr/86Sr; high 3He/4He,143Nd/144Nd, and 176Hf/177Hf; and higher 208Pb/204Pb),best expressed in basalts from Loihi, referred to as the?Loihi? component; and (3) an ?enriched?component(with high 87Sr/86Sr, 207Pb/204Pb, and d18O, and low206Pb/204Pb, 208Pb/204Pb, 143Nd/144Nd, and176Hf/177Hf), best recognized in basalts from Koolauand Lanai, referred to as the ?Koolau? component[e.g., Eiler et al., 1996]. Two end-member composi-tions have been proposed to contribute to the Koolaucomponent [e.g., Tanaka et al., 2002; 2008; Fekiacovaet al., 2007]. The enriched Koolau end-member,observed in the Makapuu stage lavas, is widelyreferred to as the ?enriched Makapuu component?(EMK). However, two different isotopic compositionshave been attributed to the depleted Koolau end-member. Fekiacova et al. [2007] considered that theKahili stage lavas represent best the depleted Koolauend-member and referred to it as the ?Kahili? compo-nent, whereas Tanaka et al. [2008] considered thedepleted Koolau end-member to also include rejuve-nated-stage lavas and termed it the ?depletedMakapuucomponent? (DMK).[24] The isotopic variability of a single Hawaiianvolcano can similarly be explained by mixing differentproportions of these components. Koolau (or enrichedMakapuu) and Loihi components are extreme compo-sitions of the Loa trend volcano variability, and Kea isthe major component in Kea trend volcanoes [e.g.,Eiler et al., 1996; Kimura et al., 2006; Tanaka et al.,2008; Weis et al., 2011]. Based on the Pb isotopevariations within the first 3100 m of the HSDP2 core,Eisele et al. [2003] recognized the need of fourdistinct components in the Mauna Kea source to ex-plain the geometry of the three ?Kea? Pb arrays. ThePb isotope variability of the basalts recovered in thedeeper 408 m of the HSDP2 core is consistentwith this isotopic end-member scenario, involving aradiogenic Pb end-member, most similar to the Keacomponent, and three other distinct end-members ofunradiogenic Pb isotopic compositions with distinct208Pb/204Pb, most similar to ?Loihi,? EMK, andDMK components (Figure 6). Whereas Kea is acommon component throughout the long-termGeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047670evolution of Mauna Kea [Tanaka et al., 2008],?Loihi-,? EMK-, and DMK-like components were in-volved at different stages of the volcano?s eruptivehistory and each contributed to the short-term isotopicvariability of Mauna Kea as represented by the differ-ent ?Kea-hi8,? ?-mid8,? and ?-lo8? arrays of Eiseleet al. [2003], respectively (Figure 6). The two low-SiO2 intrusive units within the deeper stratigraphicsection of the core plot along the ?Kea-hi8? array ofEisele et al. [2003], together with the other lowSiO2-high208Pb*/206Pb* lavas higher in the strati-graphic section of Mauna Kea. This restricted groupof basalts of Loihi-like characteristics may reflect thepresence of a local small-scale ?Loa? heterogeneitywithin the melting regime of Mauna Kea [Abouchamiet al., 2005; Rhodes et al., 2012]. It may also indicatethat the component responsible for producing lowSiO2-high208Pb*/206Pb* lavas was sampled early inMauna Kea?s history and not only for a short time pe-riod (~45 kyr, corresponding to a depth interval of~900 m) of its evolution. Basalts at depths of 3098.2to 3308.2 mbsl form the longest interval (~10 kyr)of limited compositional variation within the sampledoutput record of Mauna Kea and likely reflect thesampling of a more homogeneous domain within themagma source region of Mauna Kea.5.3. Chemical Structure of the HawaiianPlume During the Growth of Mauna Kea[25] The geochemical differences observed betweenvolcanoes younger than 5 Ma along the two sub-parallel Kea and Loa volcanic chains likely resultfrom sampling different components within differ-ent domains of the Hawaiian mantle plume [e.g.,Tatsumoto, 1978; Frey and Rhodes, 1993; Hauriet al., 1996; Blichert-Toft et al., 2003; Abouchamiet al., 2005; Weis et al., 2011]. The similarity ofthe Sr and Nd isotopic compositions of basalts fromthe deeper section of the HSDP2 core to those oflavas erupted during the post-shield stage indicatesthat during both the early and late stages of MaunaKea?s growth, the volcano sampled a composition-ally similar domain within the plume?s meltingregion. This would be consistent with a concentri-cally zoned chemical structure of the Hawaiian plume[e.g., Hauri et al., 1994, 1996; Lassiter et al., 1996;DePaolo et al., 2001; Bryce et al., 2005]. However,the Pb isotopic compositions of the deeper basaltsof Mauna Kea?s HSDP2 core differ from the respec-tive post-shield lavas, having higher 208Pb/206Pb(Figure 6). This indicates that early shield stage lavassampled a domain of the plume characterized byhigher Th/U than the post-shield stage lavas. In acomparative study of the geochemistry of post-shield and shield lavas from consecutive Kea andLoa volcano pairs, Hanano et al. [2010] concludedthat the post-shield lavas on the Big Island retain theirKea- and Loa-like Pb isotope signatures, which doesnot support a concentrically zoned plume structure.[26] The isotopic similarity of the older Mauna KeaHSDP2 basalts to pre-historic and young Kilaueabasalts [Kimura et al., 2006; Marske et al., 2007,2008; Blichert-Toft and Albar?de, 2009] supportsthe proposals that heterogeneities within the Hawai-ian plume are sampled by the melting regions ofconsecutive Kea volcanoes [Abouchami et al.,2005; Farnetani and Hofmann, 2010]. Verticalheterogeneity appears to be an intrinsic feature of theHawaiian plume that is superimposed on radialheterogeneity derived from the thermal structure ofthe plume [e.g., Hauri et al., 1994, 1996]. The Srand Nd isotopic compositions of Hawaiian basalts fol-low the concentric thermal structure of the Hawaiianplume, increasing and decreasing, respectively, duringthe lifetime of Hawaiian volcanoes as the potentialtemperature of the plume varies from the periphery tothe core [e.g., DePaolo et al., 2001; Bryce et al.,2005]. In contrast, the Pb isotopic compositions sam-pled during the lifetime of Hawaiian volcanoes supportan aspect of bilateral asymmetry in the distribution ofcompositional heterogeneities in the Hawaiian plume.These heterogeneities may be restricted to the ?corezone? of the plume [Bryce et al., 2005] or distributedthrough the entire plume radius [e.g., Abouchamiet al., 2005; Farnetani and Hofmann, 2010].5.4. The Nature of the Hawaiian KeaComponent and the Deep Pacific Mantle[27] The enriched nature of the Koolau component isconsistent with incorporation of ancient subductedoceanic crust and sediments into the source of theHawaiian plume [e.g., Lassiter and Hauri, 1998;Blichert-Toft et al., 1999; Tanaka et al., 2008],whereas the depleted nature of the Kea componentcontinues to be a matter of debate. On the basis ofSr and Nd isotopic compositions, Kea was firstinterpreted to result from entrainment of depleted as-thenospheric mantle [Lassiter et al., 1996], butO, Os, and Pb isotopic studies precluded this hypoth-esis and instead support assimilation of Pacific litho-sphere [Eiler et al., 1996], or the presence of recycledoceanic lithosphere [Lassiter and Hauri, 1998] or?young HIMU? material (recycled oceanic crustyounger than 1.5 Ga) in the Hawaiian plume source[Thirlwall, 1997; Eisele et al., 2003]. Some of thebasalts recovered in the bottom 408 m of the HSDP2GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047671core, together with the pre-historical Kilauea basaltsfrom the Hilina bench [Kimura et al., 2006], havethe most ?depleted? Sr, Nd, and Hf isotopic character-istics and the most radiogenic Pb compositions of allHawaiian shield basalts. This suggests that duringthe early shield-building phase of a Kea trend volcano,the Kea component is sampled in higher proportionscompared to later periods of volcano growth. Thecompositions of these basalts erupted early in thegrowth history of a Kea trend volcano thus provide in-sight into the nature of the Hawaiian Kea component.[28] The correlation between high 143Nd/144Nd,208-7-6Pb/204Pb, and low 87Sr/86Sr of Kea composi-tions reflects derivation from a source that developedhigh Sm/Nd and (U,Th)/Pb with lower Th/U and Rb/Sr over time. Such geochemical characteristics arenormally attributed to a HIMU-like source, generatedby recycling of ancient subduction-modified oceaniclithosphere [e.g., Hofmann and White, 1982; Zindlerand Hart, 1986; Chauvel et al., 1992; Stracke et al.,2005; Willbold and Stracke, 2006]. Compared toKea, HIMU-like compositions have much moreradiogenic Pb isotopic signatures, which indicatesthat the Kea component must be derived from asource with significantly lower m (238U/204Pb) valuesto produce 206Pb/204Pb ratios below 19.[29] The Hawaiian plume is one of the most pro-ductive mantle plumes on Earth, having erupted~7 106 km3 of volcanic material over the forma-tion of the Hawaiian-Emperor chain [Vidal andBonneville, 2004], and Kea-like compositions havebeen erupted since the mid-Cretaceous [e.g., Regelouset al., 2003;Abouchami et al., 2005;Portnyagin et al.,2008; Tanaka et al., 2008]. When comparingradiogenic (Pb, Sr, Nd, Hf) isotopic compositions ofHawaiian basalts to other Pacific Ocean island groups,the Kea component occupies an intermediate positionin binary diagrams, toward which the general trendsformed by other OIB (from EM-I, EM-II, and HIMU)converge (Figures 7 and 8). Basalts from the greatOntong Java plateau [Tejada et al., 2004] and fromthe Wrangellia oceanic plateau [Greene et al., 2008]also trend toward Kea-like compositions. The isotopiccharacteristics of Kea are not very different from thoseof the common mantle component ?C? [Hanan andGraham, 1996] or ?PREMA? [Zindler and Hart,1986]. This is in agreement with the proposition ofWeis et al. [2011] that Kea trend volcanoes, comparedto Loa trend volcanoes, sample ?average? Pacificmantle compositions. In the super-chondritic Earthmodel reference frame [e.g., Boyet and Carlson,2005, 2006; Caro et al., 2008; Caro and Bourdon,2010; Jackson et al., 2010], the isotopic compositions0.7020.7030.7040.7050.7060.7070.7080.7090.710206Pb/204Pb87Sr/86SrHIMUEM IIEM IKeaMORBHawaiiGalapagosSamoaSociety Is.Austral-CookMarquesasPitcairn-GambierEasterJuan Fernandez?Kea? end-memberOntong Java initOntong Java measWrangelliaC05010015020025017.5 18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.517.6 18.0 18.4 18.8 19.2 19.6 20.0 20.4 20.8 21.2 21.6 22.0206Pb/204PbFrequencyAustralSocietySamoaMarquesasPitcairn-GambierJuan FernadezCocosEasterHawaiiGalapagosKoolauKeaMLMKaFigure 7. 87Sr/86Sr versus 206Pb/204Pb diagram comparing the isotopic compositions of Hawaiian basalts and theHawaiian Kea component to those of other groups of Pacific ocean island basalts. Data compiled from the GEOROC(http://www.georoc.mpch-mainz.gwdg.de) and PetDB (http://www.petdb.org) databases. End-member compositionsare from Zindler and Hart [1986]. Inset shows a frequency histogram of several Pacific Ocean island groups206Pb/204Pb isotopic compositions. Arrows indicate the location/significance of the Kea and Koolau components.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047672of Kea are very close to those of bulk-silicate Earth.The resemblance of the Hawaiian Kea componentto non-chondritic primitive mantle compositions[Jackson et al., 2010; Jackson and Carlson, 2011]suggests that Kea is itself part of the primitive mantleof a non-chondritic Earth. Moreover, the presence ofKea-like compositions amongst other Pacific oceanisland basalts suggests that this non-chondriticmantlecomposition is a common and widespread composi-tion within the Pacific deep mantle.6. Conclusions[30] High-precision Sr, Nd, and Pb isotopic composi-tions of basalts from the bottom 408 m of the ~3500m deep HSDP2 drill core on Mauna Kea reveal com-positional continuity with the overlying basalts andthe presence of two distinct sample groups. Basaltsfrom the top 210 m form the longest interval(~10 kyr) of limited variation within the sampledoutput record of Mauna Kea and correspond to thesampling of a more homogeneous domain withinthe magma source region of Mauna Kea. Basaltsfrom the bottom 192 m show the largest range of var-iation in their Pb isotopic compositions, extendingthe isotopic compositions of Mauna Kea to signifi-cantly more radiogenic values, similar to those of?ancestral? Kilauea lavas, and also to significantlyless radiogenic values, similar to those of late-shieldand post-shield lavas (<400 kyr) from Mauna Keaand Kohala. Based on their ages (>680 kyr) andcompositional characteristics, these basalts likelyerupted in the very early shield phase of MaunaKea, rather than representing part of the output ofKohala or another unknown volcano. The isotopiccompositions of the HSDP2 basalts are consistentwith the presence of four source components duringthe growth of Mauna Kea and include the ?Kea,??Loihi,? EMK, and DMK components. Kea is theprevailing component throughout the evolution ofMauna Kea, whereas the remaining three compo-nents are involved in different stages of the volcanodevelopment and contribute to the short-term isotopicvariability ofMauna Kea basalts. In Pb-Sr-Nd isotopebinary diagrams, Kea occupies an intermediateposition toward which the general trends formed byother Pacific Ocean island groups (from EM-I, EM-II, and HIMU) converge. The Kea component is notonly the common composition within the Hawaiianmantle plume but also a common composition withinthe deep Pacific mantle.-8-6-4-20246810121417.5 18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.5206Pb/204PbNdHIMUEM IIEM IKea MORBHawaiiGalapagosSamoaSociety Is.Austral-CookMarquesasPitcairn-GambierEasterJuan Fernandez?Kea? end-memberOntong Java initOntong Java measWrangelliaC0501001502002503003504004505000.512370.512470.512570.512670.512770.512870.512970.513070.51317143Nd/144NdFrequencyAustralSocietySamoaMarquesasPitcairn-GambierJuan FernadezCocosEasterHawaiiGalapagosaKoolauKeaFigure 8. 143Nd/144Nd versus 206Pb/204Pb diagram comparing the isotopic compositions of Hawaiian basalts and of theHawaiian Kea component to those of other groups of Pacific Ocean island basalts. Data compiled from the GEOROC(http://www.georoc.mpch-mainz.gwdg.de) and PetDB (http://www.petdb.org) databases. End-member compositionsare from Zindler and Hart [1986]. Inset shows a frequency histogram of the 143Nd/144Nd isotopic compositions of PacificOcean island groups.GeochemistryGeophysicsGeosystems G3 NOBRE SILVA ET AL.: EARLY SHIELD PHASE OF MAUNA KEA 10.1002/ggge.20047673Acknowledgments[31] We thank Bruno Kieffer and Claude Maerschalk for help inthe clean lab and with TIMS analyses, and Jane Barling for assis-tance in operating the MC-ICP-MS. We are grateful to DonaldDePaolo for providing the samples and to Michael Garcia,Albrecht Hofmann, and Elspeth Barnes for scientific discussions.We thank reviewers William White and J. Michael Rhodes, andEditor Joel Baker for their insightful comments. I. Nobre Silvawas supported by the POCTI program of the Funda??o para aCi?ncia e Tecnologia (Portugal). This research was funded byNSERCDiscovery Grants (Canada) to D.Weis and J. S. Scoates.ReferencesAbouchami,W., S. J. G. Galer, andA.W.Hofmann (2000), Highprecision lead isotope systematics of lavas from the HawaiianScientific Drilling Project, Chem. 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