Abstract
Clinopyroxene–melt trace element partitioning experiments were carried out in the system Na2O–CaO–MgO–Al2O3–SiO2 at pressures of 1, 2.3 and 3 GPa and temperatures of 1508 to 1811 K, to investigate the effects of temperature (T), pressure (P) and composition (X) on partition coefficients. Of particular interest were elements entering the octahedral M1-site. Ion probe analyses of run products produced crystal–melt partition coefficients (D) for 16 elements (Na, Ca, Al, Cl, Sc, Ti, Fe, Zr, In, La, Ce, Nd, Sm, Ho, Yb and Hf). With the exception of D Na, partition coefficients for all elements studied decrease with increased P and T, despite the concomitant increase in the Al content of the T-site. Fitting partition coefficients for isovalent series of cations to the elastic strain model of Blundy and Wood (1994) produced values for the site radius (r 0), effective elastic modulus (E) and strain-free partition coefficient (D 0). At each pressure, E values for the M1 and M2-sites increase with increasing Al concentration in the T-site \( \left( {X_{\text{Al}}^{T} } \right) \). For a given bulk composition, E values decrease with increased T. The decrease in E with increasing T accounts for the remarkable constancy of the degree of fractionation between chemically similar elements, e.g. \( D\left( {{\frac{\text{Zr}}{\text{Hf}}}} \right) \), over the range of pressures studied here. \( E_{{{\text{M}}1}}^{4 + } \) for our experiments is found to be higher than predicted by the Hazen and Finger (1979) relationship between elastic moduli and interatomic distance. This is explained by deformation of the M1-site polyhedron leading to relative displacement and kinking of the clinopyroxene T-site chains. We developed expressions for \( E_{{{\text{M}}1}}^{4 + } \), \( r_{{0,{\text{M}}1}}^{4 + } \), D Sc and D Ti as functions of P, T and composition. We show the feasibility of using calculated D Ti values in the prediction of D Zr and D Hf. Scandium and Ti partition coefficients were modelled based on the thermodynamic description for the crystal–melt exchange reaction and in terms of the energetics of the different charge-imbalanced configurations produced by insertion of a heterovalent trace cation. The resulting equations produce values of D Sc and D Ti that are within a factor of 2 of other experimentally determined values. Fits of the equations along the lherzolite solidus show that D Sc remains compatible in clinopyroxene at high pressure and that ratios of Zr/Hf and Ti/Eu should vary subtly with the pressure at which melting occurred.
Similar content being viewed by others
References
Bartels KS, Kinzler RJ, Grove TL (1991) High pressure phase relations of primitive high-alumina basalts from Medicine Lake volcano, northern California. Contrib Mineral Petrol 108(3):253–270. doi:10.1007/BF00285935
Beattie P (1994) Systematics and energetics of trace element partitioning between olivine and silicate melts: implications for the nature of mineral/melt partitioning. Chem Geol 117:57–71
Blundy JD (1997) Experimental study of a Kiglapait marginal rock and implications for trace element partitioning in layered intrusions. Chem Geol 141:73–92. ISSN: 0009-2541
Blundy J, Dalton J (2000) Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism. Contrib Mineral Petrol 139:356–371
Blundy JD, Wood BJ (1991) Crystal-chemical controls on the partitioning of Sr and Ba between plagioclase feldspar, silicate melts and hydrothermal solutions. Geochim Cosmochim Acta 55:193–209
Blundy JD, Wood BJ (1994) Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372:452–454
Blundy J, Wood B (2003a) Mineral-melt partitioning of uranium, thorium and their daughters. In: Bourdon B et al (ed) Uranium-series geochemistry. Rev Mineral 52:39–123
Blundy J, Wood B (2003b) Partitioning of trace elements between crystals and melts. Earth Planet Sci Lett (Frontiers) 210:387–397
Blundy JD, Falloon TJ, Dalton JA (1995) Sodium partitioning between clinopyroxene and silicate melts. J Geophys Res 100:15501–15516
Blundy JD, Wood BJ, Davies A (1996) Thermodynamics of rare earth element partitioning between clinopyroxe and in the system CaO–MgO–Al2O3–SiO2. Geochim Cosmochim Acta 60(2):359–364
Blundy JD, Robinson JAC, Wood BJ (1998) Heavy REE compatible in clinopyroxene on thespinel lherzolite solidus. Earth Planet Sci Lett 160(3–4):493–504
Boisen MB Jr, Gibbs GV (1993) A modelling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite. Phys Chem Minerals 20:123–135
Born M (1920) Volumen und Hydrationswärme der Ionen. Z Phys 1:45–48
Brennan JM, Shaw HF, Ryerson FJ, Phinney DL (1995) Experimental determination of trace element partitioning between pargasite and a synthetic hydrous andesitic melt. Earth Planet Sci Lett 135:1–11
Brice JC (1975) Some thermodynamic aspects of the growth of strained crystals. J Crystal Growth 28:249–253
Cameron M, Papike JJ (1981) Structural and chemical variations in pyroxenes. Am Mineral 66:1–50
Draper DS, Johnston AD (1992) Anhydrous PT phase relations of an Aleutian high-MgO basalt: an investigation of the role of olivine-liquid reaction in the generation of arc high-alumina basalts. Contrib Mineral Petrol 112(4):501–519
Falloon TJ, Green DH (1987) Anhydrous partial melting of MORB pyrolite and other peridotite compositions at 10 kbar: Implications for the origin of primitive MORB glasses. Mineral Petrol 37(3–4):181–219. doi:10.1007/BF01161817
Falloon TJ, Green DH, Hatton CJ, Harris KL (1988) Anhydrous partial melting of a fertile and depleted peridotite from 2 to 30kbars and application to basalt petrogenesis. J Petrol 29:1257–1282
Forsythe LM, Nielsen RL, Fisk MR (1994) High-field-strength element partitioning between pyroxene and basaltic to dacitic magmas. Chem Geol 117:107–125
Frei D, Liebscher A, Franz G, Wunder B, Klemme S, Blundy J (2009) Trace element partitioning between orthopyroxene and anhydrous silicate melt on the lherzolite solidus from 1.1 to 3.2 GPa and 1230 to 1535°C in the model Na2O–CaO–MgO–Al2O3–SiO2. Contrib Mineral Petrol 157:473–490. doi:10.1007/s00410-008-0346-5
Gaetani GA (2004) The influence of melt structure on trace element partitioning near the peridotite solidus. Contrib Mineral Petrol 147(5):511–527. doi:10.1007/s00410-004-0575-1
Gaetani GA, Grove TL (1995) Partitioning of rare earth elements between clinopyroxene and silicate melt: crystal-chemical controls. Geochim Cosmochim Acta 59(10):1951–1962
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 1080-1200°C. Lithos 53:165–187
Grove TL, Bryan WB (1992) Fractionation of mid-ocean ridge basalt (MORB). Mantle flow and melt generation at Mid-Ocean Ridges. In: Morgan JP, Blackman DK, Sinton JM (ed) AGU Geophys Monogr 71:361
Hazen RM, Finger LW (1979) Bulk Modulus-volume relationship for cation-anion polyhedra. J Geophys Res 84(10):6723–6728
Hill E (2001) Trace element partitioning between the M1 site of clinopyroxene and anhydrous silicate melt. Thesis. Bristol University
Hill E, Wood BJ, Blundy JD (2000) The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt. Lithos 53:203–215
Irving AJ, Frey FA (1978) The distribution of trace elements between garnet megacrysts and volcanic liquids of kimbelitic to rhyolitic composition. Geochim Cosmochim Acta 42:771–787
Jensen BB (1973) Patterns of trace element partitioning. Geochim Cosmochim Acta 37:2227–2242
Jonston AD (1986) Anhydrous P-T phase-relations of near-primary high-Alumina basalt from South Sandwhich islands—implications for the origin of island arcs and tonalite-trondhjemite series rocks. Contrib Mineral Petrol 92(3):368–382
Kinzler RJ, Grove TL (1992) Primary magmas of mid-ocean ridge basalts, 1, experiments and methods. J Geophys Res 97:6885–6906. doi:10.1029/91JB02840
Klein M, Stosch HG, Seck A, Shimizu N (2000) Experimental partitioning of high field strength and rare earth elements between clinopyroxene and garnet in andesitic to tonalitic systems. Geochim Cosmochim Acta 64:99–115
Klemme S, Blundy JD, Wood BJ (2002) Partial melting of eclogite: some comments on trace element transfer during melting of subducted oceanic lithosphere. Geochim Cosmochim Acta 66:3109–3123
Landwehr D, Blundy J, Chamorro-Perez EM, Hill E, Wood B (2001) U-series disequilibria generated by partial melting of spinel lherzolite. EPSL 188:329–348
Langmuir CH, Klein EM, Plank T (1992) Petrological systematics of mid-ocean ridge basalts: constraints on melt generation beneath ocean ridges. Mantle Flow and Melt Generation at Mid-Ocean Ridges. In: Morgan JP, Blackman DK, Sinton JM (ed) Geophys Monogr AGU 71:361
LaTourrette T, Hervig RL, Holloway JR (1995) Trace element partitioning between amphibole, phlogopite and basanite melt. Earth Planet Sci Lett 135:13–30
Law KM, Blundy JD, Wood BJ, Ragnarsdottir KV (1999) An investigation of the crystal chemical controls on trace element partitioning between carbonated melts and wollastonite, Witherite and Calcite. EOS Trans Am Geophys Union 80(S357)
Law KM, Blundy JD, Wood BJ, Ragnarsdottir KV (2000) Trace element partitioning between wollastonite and carbonate-silicate melt. Mineral Mag 64(4):651–661. ISSN: 0026-461X
Levien L, Prewitt CT (1981) High-pressure structural study of diopside. Am Mineral 66:315–323
Lindstrom DJ (1976) Experimental study of the partitioning of the transition metals between clinopyroxene and coexisting silicate liquids. PhD Thesis, University of Oregon, OR, USA
Liu CQ, Masuda A, Shimizu H, Takahashi K, Xie GH (1992) Evidence for pressure dependence in the peak position in the REE mineral/melt partition patterns of clinopyroxene. Geochim Cosmochim Acta 56:1523–1530
Lundstrom CC, Shaw HF, Ryerson FJ, Phinney DL, Gill JB, Williams Q (1994) Compositional controls on the partitioning of U, Th, Ba, Pb, Sr and Zr between clinopyroxene and haplobasaltic melts: implications for uranium series disequilibria in basalts. Earth Planet Sci Lett (128):407–423
Lundstrom CC, Shaw HF, Ryerson FJ, Williams Q, Gill J (1998) Crystal chemical control of clinopyroxene-melt partitioning in the Di-Ab-An system: Implications for elemental fractionations in the depleted mantle. Geochim Cosmochim Acta 62(16):2849–2862
McDade P, Wood BJ, van Westrenen W, Brooker R, Gudmundson G, Soulard H, Najorka J, Blundy J (2002) Pressure corrections for a selection of piston cylinder cell assemblies. Mineral Mag 66(6):1021–1028. doi:10.1180/0026461026660074
Mott NF, Littletton MJ (1938) Conduction in polar crystals. 1. Electrolytic conduction in solid salts. Tran Faraday Soc 34:485–499. doi:10.1039/TF9383400485
Mysen BO, Virgo D, Seifert FA (1982) The structure of silicate melts: implications for chemical and physical properties of natural magma. Rev Geophys Space Phys 20:353–383
Onuma N, Higuchi H, Wakita H, Nagasawa H (1968) Trace element partitioning between two pyroxenes and the host lava. Earth Planet Sci Lett 5:47–51
Pertemann M, Hirschmann MM (2002) Trace-element partitioning between vacancy-rich eclogitic clinopyroxene and silicate melt. Am Mineral 87:1365–1376
Putirka K, Jonhson M, Kinzler R, Longhi J, Walker D (1996) Thermobarometry of mafic igneous rocks based on clinopyroxene-liquid equilibria, 0–30 kbar. Contrib Mineral Petrol 123(1):92–108
Ray GL, Shimizu N, Hart SR (1983) An ion microprobe study of the partitioning of trace elements between clinopyroxene and liquid in the system diopside–albite–anorthite. Geochim Cosmochim Acta 47:2131–2140
Salters VJM, Longhi J (1999) Trace element partitioning during the initial stages of melting beneath mid-ocean ridges. Earth Planet Sci Lett 166:15–30
Salters VJM, Longhi JE, Bizimis M (2002) Near mantle solidus trace element partitioning at pressures up to 3.4 GPa. Geochem Geophys Geosyst 3(7):1038. doi:10.1029/2001GC000148
Schosnig M, Hoffer E (1998) Compositional dependence of REE partitioning between diopside and melt at 1 atmosphere. Contrib Mineral Petrol 113(3):205–216. doi:10.1007/s004100050448
Shannon RD (1976) Revised effetive ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A32:751–767
Smyth JR, Bish DL (1988) Crystal structures and cation sites of the rock-forming minerals. Allen & Unwin, Boston, 332 pp
Van Westrenen W, Blundy JD, Wood BJ (1999) Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am Mineral 84:838–847
Walter MJ, Presnall DC (1994) Melting behaviour of simplified lherzolite in the system CaO–MgO–Al2O3–SiO2–Na2O from 7 to 35 kbar. J Petrol 35(2):329–359
Wood BJ, Blundy JD (1997) A predictive model for rare earth element partitioning between clinopyroxene and anhydrous silicate melt. Contrib Mineral Petrol 129:166–181
Wood BJ, Blundy JD (2001) The effect of cation charge on crystal-melt partitioning of trace elements. Earth Planet Sci Lett 188:59–71
Wood BJ, Blundy JD, Robinson AC (1999) The role of clinopyroxene in generating U-series disequilibrium during mantle melting. Geochim Cosmochim Acta 63(10):1613–1620
Yang HJ, Kinzler RJ, Grove TL (1996) Experiments and models of anhydrous, basaltic olivine-plagioclase-augite saturated melts from 0.001 to 10 kbar. Contrib Mineral Petrol 124(1):1–18
Acknowledgments
Thanks are extended to D. Draper and an anonimous reviewer for comments on the manuscript. The authors acknowledge the assistance provided by the following grants: NERC - NE/B502936/2 (BJW); GR3/12643, NER/A/S/2000/01165, NER/B/S/2003/00188 (JDB).
Author information
Authors and Affiliations
Corresponding author
Additional information
Communicated by G. Moore.
An erratum to this article can be found at http://dx.doi.org/10.1007/s00410-011-0716-2
Rights and permissions
About this article
Cite this article
Hill, E., Blundy, J.D. & Wood, B.J. Clinopyroxene–melt trace element partitioning and the development of a predictive model for HFSE and Sc. Contrib Mineral Petrol 161, 423–438 (2011). https://doi.org/10.1007/s00410-010-0540-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00410-010-0540-0