Abstract
To understand partitioning of hydrogen between hydrous basaltic and andesitic liquids and coexisting clinopyroxene and garnet, experiments using a mid-ocean ridge basalt (MORB) + 6 wt.% H2O were conducted at 3 GPa and 1,150–1,325°C. These included both isothermal and controlled cooling rate crystallization experiments, as crystals from the former were too small for ion microprobe (SIMS) analyses. Three runs at lower bulk water content are also reported. H2O was measured in minerals by SIMS and in glasses by SIMS, Fourier Transform infrared spectroscopy (FTIR), and from oxide totals of electron microprobe (EMP) analyses. At 3 GPa, the liquidus for MORB with 6 wt.% H2O is between 1,300 and 1,325°C. In the temperature interval investigated, the melt proportion varies from 100 to 45% and the modes of garnet and clinopyroxene are nearly equal. Liquid composition varies from basaltic to andesitic. The crystallization experiments starting from above the liquidus failed to nucleate garnets, but those starting from below the liquidus crystallized both garnet and clinopyroxene. SIMS analyses of glasses with >7 wt.% H2O yield spuriously low concentrations, perhaps owing to hydrogen degassing in the ultra-high vacuum of the ion microprobe sample chamber. FTIR and EMP analyses show that the glasses have 3.4 to 11.9 wt.% water, whilst SIMS analyses indicate that clinopyroxenes have 1,340–2,330 ppm and garnets have 98–209 ppm H2O. D H cpx−gt is 11 ± 3, D cpx−melt H is 0.023 ± 0.005 and D gt−melt H is 0.0018 ± 0.0006. Most garnet/melt pairs have low values of D gt−melt H , but D gt−melt H increases with TiO2 in the garnet. As also found by previous studies, values of D H cpx−melt increase with Al2O3 of the crystal. For garnet pyroxenite, estimated values of D H pyroxenite−melt decrease from 0.015 at 2.5 GPa to 0.0089 at 5 GPa. Hydration will increase the depth interval between pyroxenite and peridotite solidi for mantle upwelling beneath ridges or oceanic islands. This is partly because the greater pyroxene/olivine ratio in pyroxenite will tend to enhance the H2O concentration of pyroxenite, assuming that neighboring pyroxenite and peridotite bodies have similar H2O in their pyroxenes.
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References
Adam J, Green T (2003) The influence of pressure, mineral composition and water on trace element partitioning between clinopyroxene, amphibole and basanitic melts. Eur J Mineral 15:831–841
Adam J, Green TH (1994) The effects of pressure and temperature on the partitioning of Ti, Sr and REE between amphibole, clinopyroxene and basanitic melts. Chem Geol 117:219–233
Asimow PD, Dixon JE, Langmuir CH (2004) A hydrous melting and fractionation model for mid-ocean ridge basalts: application to the Mid-Atlantic Ridge near the Azores. Geochem Geophys Geosyst 5(1):Q01E16. doi:10.1029/2003GC000568
Asimow PD, Langmuir CH (2003) The importance of water to ocean ridge melting regimes. Nature 421:815–820
Aubaud C, Hauri EH, Hirschmann MM (2004) Hydrogen partition coefficients between nominally anhydrous minerals and basaltic melts. Geophys Res Lett 31:L20611. doi:20610.21029/22004GL021341
Aubaud C, Withers AC, Hirschmann MM, Guan Y, Leshin LA, Mackwell SJ, Bell DR (2007) Intercalibration of FTIR and SIMS for hydrogen measurements in glasses and nominally anhydrous minerals. Am Mineral 92:811–828
Bartholomew RF, Butler BL, Hoover HL, Wu CK (1980) Infrared spectra of a water-containing glass. J Am Ceram Soc 63:481–485
Bell DR, Rossman GR (1992a) The distribution of hydroxyl in garnets from the subcontinental mantle of southern Africa. Contrib Mineral Petrol 111:161–178
Bell DR, Rossman GR (1992b) Water in Earth’s mantle: the role of nominally anhydrous minerals. Science 255:1391–1397
Bell DR, Rossman GR, Moore RO (2004) Abundance and partitioning of OH in a high-pressure magmatic system: megacrysts from the Monastery kimberlite, South Africa. J Petrol 45(8):1539–1564
Bercovici D, Karato S-I (2003) Whole-mantle convection and the transition-zone water filter. Nature 425:39–44
Berry AJ, Hermann J, O’Neill HSC, Foran GJ (2005) Fingerprinting the water site in mantle olivine. Geology 33(11):869–872
Bromiley GD, Keppler H (2004) An experimental investigation of hydroxyl solubility in jadeite and Na-rich clinopyroxenes. Contrib Mineral Petrol 147:189–200
Bromiley GD, Keppler H, McCammon C, Bromiley FA, Jacobsen SD (2004) Hydrogen solubility and speciation in natural, gem quality chromian diopside. Am Mineral 89:941–949
Dasgupta R, Hirschmann MM, Withers AC (2004) Deep global cycling of carbon constrained by the solidus of anydrous, carbonated eclogite under upper mantle conditions. Earth Planet Sci Lett 227:73–85
Dixon JE, Clague DA, Wallace P, Poreda R (1997) Volatiles in alkalic basalts from the North Arch Volcanic Field, Hawaii: extensive degassing of deep submarine-erupted alkalic series lavas. J Petrol 38:911–939
Dobson PF, Skogby H, Rossman GR (1995) Water in boninite glass and coexisting orthopyroxene: concentration and partitioning. Contrib Mineral Petrol 118:414–419
Gaetani GA, Grove TL (1998) The influence of water on melting of mantle peridotite. Contrib Mineral Petrol 131:323–346
Grant KJ, Kohn SC, Brooker RA (2006) Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O ± Al2O3. Contrib Mineral Petrol 151:651–664
Grant KJ, Kohn SC, Brooker RA (2007) The partitioning of water between olivine, orthopyroxene and melt synthesised in the system Albite–Forsterite–H2O. Earth Planet Sci Lett 26:227–241
Green TH, Blundy JD, Adam J, Yaxley GM (2000) SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1,080–1,200°C. Lithos 53:165–187
Hauri EH, Gaetani GA, Green TH (2006) Partitioning of water during melting of the Earth’s upper mantle at H2O-undersaturated conditions. Earth Planet Sci Lett 248:715–734
Hirschmann MM (2000) Mantle solidus: experimental constraints and the effects of peridotite composition. Geochem. Geophys. Geosyst. 1(10), doi:10.1029/2000GC000070
Hirschmann MM, Aubaud C, Withers AC (2005) Storage capacity of H2O in nominally anhydrous minerals in the upper mantle. Earth Planet Sci Lett 236:167–181
Hirschmann MM, Kogiso T, Baker MB, Stolper EM (2003) Alkalic magmas generated by partial melting of garnet pyroxenite. Geology 31:481–484
Hirschmann MM, Stolper EM (1996) A possible role for garnet pyroxenite in the origin of the “garnet signature” in MORB. Contrib Mineral Petrol 124:185–208
Hirth G, Kohlstedt D (2003) Rheology of the upper mantle and the mantle wedge: a view from the experimentalists. In: Eiler J (ed) Inside the Subduction Factory. American Geophysical Union, Washington D. C. Geophysical Monograph 138:83–105
Hirth G, Kohlstedt DL (1996) Water in the oceanic upper mantle: implications for rheology, melt extraction and the evolution of the lithosphere. Earth Planet Sci Lett 144:93–108
Ito G, Hirth YSG, Wolfe CJ (1999) Mantle flow, and dehydration of the Iceland mantle plume. Earth Planet Sci Lett 165:81–96
Karato S-I, Jung H (1998) Water, partial melting and the origin of the seismic low velocity and high attenuation zone in the upper mantle. Earth Planet Sci Lett 157:193–207
Katayama I, Nakashima S (2003) Hydroxyl in clinopyroxene from the deep subducted crust: evidence for H2O transport into the mantle. Am Mineral 88:229–234
Katayama I, Nakashima S, Yurimoto H (2006) Water content in natural eclogite and implication for water transport into the deep upper mantle. Lithos 86:245–259
Kawamoto T, Hirose K (1994) Au–Pd sample containers for melting experiments on iron and water bearing systems. Eur J Mineral 6:381–385
Keshav S, Gudfinnsson GH, Sen G, Fei Y (2004) High-pressure melting experiments on garnet clinopyroxenite and the alkalic to tholeiitic transition in ocean-island basalts. Earth Planet Sci Lett 223:365–379
Koga K, Hauri E, Hirschmann MM, Bell D (2003) Hydrogen concentration analyses using SIMS and FTIR: comparison and calibration for nominally anhydrous minerals. Geochem Geophys Geosyst 4(2):1019. doi:1010.1029/2002GC000378
Kogiso T, Hirschmann MM (2006) Partial melting experiments of bimineralic eclogite and the role of recycled mafic oceanic crust in the genesis of ocean island basalts. Earth Planet Sci Lett 249:188–199
Kogiso T, Hirschmann MM, Frost DJ (2003) High-pressure partial melting of garnet pyroxenite: possible mafic lithologies in the source of ocean island basalts. Earth Planet Sci Lett 216:603–617
Kogiso T, Hirschmann MM, Pertermann M (2004a) High pressure partial melting of mafic lithologies in the mantle. J Petrol 45:2407–2422
Kogiso T, Hirschmann MM, Reiners PW (2004b) Length scales of mantle heterogeneities and their relationship to ocean island basalt geochemistry. Geochim Cosmochim Acta 68(2):345–360
Kohn SC (1996) Solubility of H2O in nominally anhydrous mantle minerals using 1H MAS NMR. Am Mineral 81:1523–1526
Kohn SC, Grant KJ (2006) The partitioning of water between nominally anhydrous minerals and silicate melts. Rev Mineral Geochem 62:231–241
Kohn SC, Roome BM, Smith ME, Howes AP (2005) Testing a potential mantle geohygrometer; the effect of dissolved water on the intracrystalline partitioning of Al in orthopyroxene. Earth Planet Sci Lett 238:342–350
Lesher CE, Walker D (1988) Cumulate maturation and melt migration in a temperature gradient. J Geophys Res 93(B9):10295–10311
Lu R, Keppler H (1997) Water solubility in pyrope to 100 kbar. Contrib Mineral Petrol 129:35–42
Mackwell SJ, Kohlstedt DL (1990) Diffusion of hydrogen in olivine: implications for water in the mantle. J Geophys Res 95(B4):5079–5088
Michael PJ (1988) The concentration, behavior and storage of H2O in the suboceanic upper mantle: implications for mantle metasomatism. Geochim Cosmochim Acta 52:555–566
Michael PJ (1995) Regionally distinctive sources of depleted MORB: evidence from trace elements and H2O. Earth Planet Sci Lett 131:301–320
Mierdel K, Keppler H, Smyth JR, Langenhorst F (2007) Water solubility in aluminous orthopyroxene and the origin of Earth’s asthenosphere. Science 315:364–368
Miyashiro A, Shido F, Ewing M (1969) Diversity and origin of abyssal tholeiite from the mid-Atlantic ridge near 24° and 30° North latitude. Contrib Mineral Petrol 23:38–52
Ohlhorst S, Behrens H, Holtz F (2001) Compositional dependence of molar absorptivities of near-infrared OH- and H2O bands in rhyolitic to basaltic glasses. Chem Geol 174:5–20
Pertermann M, Hirschmann MM (2002) Trace-element partitioning between vacancy-rich eclogitic clinopyroxene and silicate melt. Am Mineral 87:1365–1376
Pertermann M, Hirschmann MM (2003a) Anhydrous partial melting experiments on MORB-like eclogite: phase relations, phase compositions and mineral-melt partitioning of major elements at 2–3 GPa. J Petrol 44(12):2173–2201
Pertermann M, Hirschmann MM (2003b) Partial melting experiments on a MORB-like pyroxenite between 2 and 3 GPa: constraints on the presence of pyroxenite in basalt source regions from solidus location and melting rate. J Geophys Res 108(B2):2125. doi:2110.1020/2000JB000118
Prouteau G, Scaillet B, Pichavant M, Maury R (2001) Evidence for mantle metasomatism by hydrous silicic melts derived from subducted oceanic crust. Nature 410:197–200
Ratajeski K, Sisson TW (1999) Loss of iron to gold capsules in rock-melting experiments. Am Mineral 84:1521–1527
Rauch M, Keppler H (2002) Water solubility in orthopyroxene. Contrib Mineral Petrol 143:525–536
Scholze H (1960) Zur frage der unterscheidung zwischen H2O-moleceln und OH-gruppen in gläsern and mineralen. Naturwiss 47:226–227
Skogby H, Bell DR, Rossman GR (1990) Hydroxide in pyroxene: variations in the natural environment. Am Mineral 75:764–774
Smyth JR, Bell DR, Rossman GR (1991) Incorporation of hydroxyl in upper mantle clinopyroxenes. Nature 351:732–735
Spandler C, Yaxley G, Green DH, Rosenthal A (2007) Phase relations and melting of anhydrous K-bearing eclogite from 1,200 to 1,600°C and 3–5 GPa. J Petrol 49(4):717–740
Stalder R (2004) Influence of Fe, Cr and Al on hydrogen incorporation in orthopyroxene. Eur J Mineral 16(5):703–711
Stalder R, Skogby H (2002) Hydrogen incorporation in enstatite. Eur J Mineral 14:1139–1144
Stolper EM (1982) The speciation of water in silicate melts. Geochim Cosmochim Acta 46:2609–2620
Tuff J, Takahashi E, Gibson SA (2005) Experimental constraints on the role of garnet pyroxenite in the genesis of high-Fe mantle plume derived melts. J Petrol 46:2023–2058
Withers AC, Behrens H (1999) Temperature-induced changes in the NIR spectra of hydrous albitic and rhyolitic glasses between 300 and 100 K. Phys Chem Minerals 27:119–132
Withers AC, Wood BJ, Carroll MR (1998) The OH content of pyrope at high pressure. Chem Geol 147:161–171
Workman RK, Hauri E, Hart SR, Wang J, Blusztajn J (2006) Volatile and trace elements in basaltic glasses from Samoa: implications for water distribution in the mantle. Earth Planet Sci Lett 241:932–951
Xirouchakis D, Hirschmann MM, Simpson JA (2001) The effect of titanium on the silica content and on mineral-liquid partitioning of mantle-equilibrated melts. Geochim Cosmochim Acta 65:2201–2217
Yasuda A, Fujii T, Kurita K (1994) Melting phase relations of an anhydrous mid-ocean ridge basalt from 3 to 20 GPa: implications for the behavior of subducted oceanic crust in the mantle. J Geophys Res 99(B5):9401–9414
Yaxley GM, Green DH (1998) Reactions between eclogite and peridotite: mantle refertilisation by subduction of oceanic crust. Schweiz Mineral Petrogr Mitt 78:243–255
Zhao Y-H, Ginsberg SB, Kohlstedt DL (2004) Solubility of hydrogen in olivine: dependence on temperature and iron content. Contrib Mineral Petrol 147:155–161
Acknowledgments
We thank David Kohlstedt and Mark Zimmermann for providing starting materials and Dan Ruscitto for the HF dissolution of the iron pretreated capsules. We are grateful to Ellery Frahm for help with electron microprobe analyses, to Yunbin Guan for his help during the early developments of the SIMS analysis at ASU, and to Simon Kohn and an anonymous reviewer for helpful and detailed reviews. Parts of this work were carried out in the Minnesota Characterization Facility, which receives partial support from NSF through the NNIN program. This work was supported by NSF EAR-0456405 and OCE-0623550.
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Communicated by T.L. Grove.
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Aubaud, C., Hirschmann, M.M., Withers, A.C. et al. Hydrogen partitioning between melt, clinopyroxene, and garnet at 3 GPa in a hydrous MORB with 6 wt.% H2O. Contrib Mineral Petrol 156, 607–625 (2008). https://doi.org/10.1007/s00410-008-0304-2
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DOI: https://doi.org/10.1007/s00410-008-0304-2