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Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

Contributions to Mineralogy and Petrology volume 172, Article number: 51 (2017) Cite this article

Abstract

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.

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References

  • Bénard A, Koga KT, Shimizu N et al (2017) Chlorine and fluorine partition coefficients and abundances in sub-arc mantle xenoliths (Kamchatka, Russia): implications for melt generation and volatile recycling processes in subduction zones. Geochim Cosmochim Acta 199:324–350. doi:10.1016/j.gca.2016.10.035

    Article  Google Scholar 

  • Bernini D, Wiedenbeck M, Dolejš D, Keppler H (2013) Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones. Contrib Mineral Petrol 165:117–128. doi:10.1007/s00410-012-0799-4

    Article  Google Scholar 

  • Beyer C, Klemme S, Wiedenbeck M et al (2012) Fluorine in nominally fluorine-free mantle minerals: experimental partitioning of F between olivine, orthopyroxene and silicate melts with implications for magmatic processes. Earth Planet Sci Lett 337–338:1–9. doi:10.1016/j.epsl.2012.05.003

    Article  Google Scholar 

  • Beyer C, Klemme S, Grützner T et al (2016) Fluorine partitioning between eclogitic garnet, clinopyroxene, and melt at upper mantle conditions. Chem Geol 437:88–97. doi:10.1016/j.chemgeo.2016.05.032

    Article  Google Scholar 

  • Bonifacie M, Busigny V, Mével C et al (2008) Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes. Geochim Cosmochim Acta 72:126–139. doi:10.1016/j.gca.2007.10.010

    Article  Google Scholar 

  • Bouvier AS, Métrich N, Deloule E (2008) Slab-derived fluids in the magma sources of St. Vincent (Lesser Antilles Arc): volatile and light element imprints. J Petrol 49:1427–1448

    Article  Google Scholar 

  • Bouvier AS, Deloule E, Métrich N (2010) Fluid inputs to magma sources of St. Vincent and Grenada (Lesser Antilles): new insights from trace elements in olivine-hosted melt inclusions. J Petrol 51:1597–1615

    Article  Google Scholar 

  • Brenan J (1994) Role of aqueous fluids in slab to mantle transfer of B, Be, Li during subduction. Chem Geol 110:195–210

    Article  Google Scholar 

  • Bromiley DW, Kohn SC (2007) Comparisons between fluoride and hydroxide incorporation in nominally anhydrous and fluorine-free mantle minerals. Geochim Cosmochim Acta 71:3570–3580

    Article  Google Scholar 

  • Cabral RA, Jackson MG, Koga KT et al (2014) Volatile cycling of H 2O, CO2, F, and Cl in the HIMU mantle: a new window provided by melt inclusions from oceanic hot spot lavas at Mangaia, Cook Islands. Geochem Geophys Geosyst 15:4445–4467. doi:10.1002/2014GC005473

    Article  Google Scholar 

  • Dalou C, Mysen BO (2015) The effect of H2O on F and Cl solubility and solution mechanisms of in aluminosilicate melts at high pressure and high temperature. Am Miner 100:633–643. doi:10.2138/am-2015-4814

    Article  Google Scholar 

  • Dalou C, Koga KT, Shimizu N et al (2012) Experimental determination of F and Cl partitioning between lherzolite and basaltic melt. Contrib Mineral Petrol 163:591–609. doi:10.1007/s00410-011-0688-2

    Article  Google Scholar 

  • Dalou C, Koga KT, Le-Voyer M, Shimizu N (2014) Contrasting partition behavior of F and Cl during hydrous mantle melting: implications for Cl/F signature in arc magmas. Prog Earth Planet Sci. doi:10.1186/s40645-014-0026-1

    Google Scholar 

  • Debret B, Koga KT, Nicollet C et al (2013) F, Cl and S input via serpentinite in subduction zones: implications for the nature of the fluid released at depth. Terra Nova 26:96–101. doi:10.1111/ter.12074

    Article  Google Scholar 

  • Dingwell DB (1989) Effect of fluorine on the viscosity of diopside liquid. Am Mineral 3–4:333–338

    Google Scholar 

  • Dixon JE, Dixon TH, Bell DR, Malservisi R (2004) Lateral variation in upper mantle viscosity: role of water. Earth Planet Sci Lett 222:451–467. doi:10.1016/j.epsl.2004.03.022

    Article  Google Scholar 

  • Fabbrizio A, Stalder R, Hametner K et al (2013) Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300°C. Contrib Mineral Petrol 166:639–653. doi:10.1007/s00410-013-0902-5

    Article  Google Scholar 

  • Gaetani GA (2004) The influence of melt structure on trace element partitioning near the peridotite solidus. Contrib Mineral Petrol 147:511–527. doi:10.1007/s00410-004-0575-1

    Article  Google Scholar 

  • Gale A, Dalton CA, Langmuir CH et al (2013) The mean composition of ocean ridge basalts. Geochem Geophys Geosyst 14:489–518. doi:10.1029/2012GC004334

    Article  Google Scholar 

  • Giovanardi T, Morishita T, Zanetti A et al (2013) Igneous sapphirine as a product of melt-peridotite interactions in the Finero Phlogopite-Peridotite Massif, Western Italian Alps. Eur J Mineral 25:17–31. doi:10.1127/0935-1221/2013/0025-2251

    Article  Google Scholar 

  • Guggino SN (2012) Fluorine partitioning between nominally anhydrous minerals (olivine, clinopyroxene, and plagioclase) and silicate melt using secondary ion mass spectrometry and newly synthesized basaltic fluorine microanalytical glass standards. Arizona State University, Tempe

    Google Scholar 

  • Guggino SN, Hervig RL (2012) Fluorine partitioning between nominally anhydrous minerals (cpx, ol, plag) and silicate melt. In: AGU fall meeting abstracts

  • Hauri E, Wang J, Dixon JE et al (2002) SIMS analysis of volatiles in silicate glasses. Chem Geol 183:99–114. doi:10.1016/S0009-2541(01)00375-8

    Article  Google Scholar 

  • Hauri E, Gaetani G, Green T (2006) Partitioning of water during melting of the Earth’s upper mantle at H2O-undersaturated conditions. Earth Planet Sci Lett 248:715–734. doi:10.1016/j.epsl.2006.06.014

    Article  Google Scholar 

  • Humphreys ER, Niu Y (2009) On the composition of ocean island basalts (OIB): the effects of lithospheric thickness variation and mantle metasomatism. Lithos 112:118–136. doi:10.1016/j.lithos.2009.04.038

    Article  Google Scholar 

  • Jenner FE, O’Neill HSC (2012) Analysis of 60 elements in 616 ocean floor basaltic glasses. Geochem Geophys Geosyst. doi:10.1029/2011GC004009

    Google Scholar 

  • John T, Scambelluri M, Frische M et al (2011) Dehydration of subducting serpentinite: implications for halogen mobility in subduction zones and the deep halogen cycle. Earth Planet Sci Lett 308:65–76. doi:10.1016/j.epsl.2011.05.038

    Article  Google Scholar 

  • Kendrick MA, Jackson MG, Kent AJR et al (2014) Contrasting behaviours of CO2, S, H2O and halogens (F, Cl, Br, and I) in enriched-mantle melts from Pitcairn and Society seamounts. Chem Geol 370:69–81. doi:10.1016/j.chemgeo.2014.01.019

    Article  Google Scholar 

  • Konzett J, Frost DJ (2009) The high P-T stability of hydroxyl-apatite in natural and simplified MORB—an experimental study to 15 GPa with Implications for transport and storage of phosphorus and halogens in subduction zones. J Petrol 50:2043–2062. doi:10.1093/petrology/egp068

    Article  Google Scholar 

  • Le Roux P, Shirey S, Hauri E et al (2006) The effects of variable sources, processes and contaminants on the composition of northern EPR MORB (8–10°N and 12–14°N): evidence from volatiles (H2O, CO2, S) and halogens (F, Cl). Earth Planet Sci Lett 251:209–231. doi:10.1016/j.epsl.2006.09.012

    Article  Google Scholar 

  • Le Roux V, Dick HJB, Shimizu N (2014) Tracking flux melting and melt percolation in supra-subduction peridotites (Josephine ophiolite, USA). Contrib Mineral Petrol 168:1064. doi:10.1007/s00410-014-1064-9

    Article  Google Scholar 

  • Le Voyer M, Rose-Koga EF, Shimizu N et al (2010) Two contrasting H2O-rich components in primary melt inclusions from Mount Shasta. J Petrol 51:1571–1595. doi:10.1093/petrology/egq030

    Article  Google Scholar 

  • Le Voyer M, Cottrell E, Kelley KA et al (2015) The effect of primary versus secondary processes on the volatile content of MORB glasses: an example from the equatorial Mid-Atlantic Ridge (5°N-3°S). Journal of Geophysical Research: Solid Earth 120:125–144. doi:10.1002/2014JB011160

    Google Scholar 

  • Lee CTA (2005) Trace element evidence for hydrous metasomatism at the base of the North American lithosphere and possible association with Laramide low-angle subduction. J Geol 113:673–685. doi:10.1086/449327

    Article  Google Scholar 

  • Li Z-XA, Lee C-TA, Peslier AH et al (2008) Water contents in mantle xenoliths from the Colorado Plateau and vicinity: implications for the mantle rheology and hydration-induced thinning of continental lithosphere. J Geophys Res 113:B09210–B09222. doi:10.1029/2007JB005540

    Article  Google Scholar 

  • Luffi P, Saleeby JB, Lee C-TA, Ducea MN (2009) Lithospheric mantle duplex beneath the central Mojave Desert revealed by xenoliths from Dish Hill, California. J Geophys Res Solid Earth 114:B03202. doi:10.1029/2008JB005906

    Article  Google Scholar 

  • Marschall HR, Altherr R, Gméling K, Kasztovszky Z (2009) Lithium, boron and chlorine as tracers for metasomatism in high-pressure metamorphic rocks: a case study from Syros (Greece). Miner Petrol 95:291–302. doi:10.1007/s00710-008-0032-3

    Article  Google Scholar 

  • Michael PJ, Schilling JG (1989) Chlorine in mid-ocean ridge magmas: evidence for assimilation of seawater-influenced components. Geochim Cosmochim Acta 53:3131–3143. doi:10.1016/0016-7037(89)90094-X

    Article  Google Scholar 

  • Mosenfelder JL, Rossman GR (2013a) Analysis of hydrogen and fluorine in pyroxenes: I. Orthopyroxene. Am Mineral 98:1026–1041. doi:10.2138/am.2013.4291

    Article  Google Scholar 

  • Mosenfelder JL, Rossman GR (2013b) Analysis of hydrogen and fluorine in pyroxenes: II. Clinopyroxene. Am Mineral 98:1042–1054. doi:10.2138/am.2013.4413

    Article  Google Scholar 

  • Mysen B (2007a) Partitioning of calcium, magnesium, and transition metals between olivine and melt governed by the structure of the silicate melt at ambient pressure. Am Mineral 92:844–862. doi:10.2138/am.2007.2260

    Article  Google Scholar 

  • Mysen BO (2007b) The solution behavior of H2O in peralkaline aluminosilicate melts at high pressure with implications for properties of hydrous melts. Geochim Cosmochim Acta 71:1820–1834. doi:10.1016/j.gca.2007.01.007

    Article  Google Scholar 

  • Mysen BO, Cody GD (2004) Solubility and solution mechanism of H2O in alkali silicate melts and glasses at high pressure and temperature. Geochim Cosmochim Acta 68:5113–5126. doi:10.1016/j.gca.2004.07.021

    Article  Google Scholar 

  • O’Leary JA, Gaetani GA, Hauri EH (2010) The effect of tetrahedral Al3+ on the partitioning of water between clinopyroxene and silicate melt. Earth Planet Sci Lett 297:111–120. doi:10.1016/j.epsl.2010.06.011

    Article  Google Scholar 

  • Peslier A, Luhr J (2006) Hydrogen loss from olivines in mantle xenoliths from Simcoe (USA) and Mexico: mafic alkalic magma ascent rates and water budget of the sub-continental lithosphere. Earth Planet Sci Lett 242:302–319. doi:10.1016/j.epsl.2005.12.019

    Article  Google Scholar 

  • Philippot P, Agrinier P, Scambelluri M (1998) Chlorine cycling during subduction of altered oceanic crust. Earth Planet Sci Lett 161:33–44. doi:10.1016/S0012-821X(98)00134-4

    Article  Google Scholar 

  • Portnyagin M, Hoernle K, Plechov P et al (2007) Constraints on mantle melting and composition and nature of slab components in volcanic arcs from volatiles (H2O, S, Cl, F) and trace elements in melt inclusions from the Kamchatka Arc. Earth Planet Sci Lett 255:53–69. doi:10.1016/j.epsl.2006.12.005

    Article  Google Scholar 

  • Roden MF (1981) Origin of coexisting minette and ultramafic breccia, Navajo volcanic field. Contrib Mineral Petrol 77:195–206. doi:10.1007/BF00636523

    Article  Google Scholar 

  • Rose-Koga EF, Shimizu N, Devidal J, et al (2008) Investigation of F, S, and Cl standards by ion probe and electron microprobe. In: AGU fall meeting abstracts

  • Rose-Koga EF, Koga KT, Schiano P et al (2012) Mantle source heterogeneity for South Tyrrhenian magmas revealed by Pb isotopes and halogen contents of olivine-hosted melt inclusions. Chem Geol 334:266–279

    Article  Google Scholar 

  • Rose-Koga EF, Koga KT, Hamada M et al (2014) Volatile (F and Cl) concentrations in Iwate olivine-hosted melt inclusions indicating low-temperature subduction. Earth Planets Space 66:1–12. doi:10.1186/1880-5981-66-81

    Article  Google Scholar 

  • Rose-Koga EF, Koga KT, Moreira M et al (2017) Geochemical systematics of Pb isotopes, fluorine, and sulfur in melt inclusions from São Miguel, Azores. Chem Geol 239:138–155

    Google Scholar 

  • Saal AE, Hauri EH, Langmuir CH, Perfit MR (2002) Vapour undersaturation in primitive mid-ocean-ridge basalt and the volatile content of Earth’s upper mantle. Nature 419:451–455. doi:10.1038/nature01073

    Article  Google Scholar 

  • Sadofsky SJ, Portnyagin M, Hoernle K, van den Bogaard P (2008) Subduction cycling of volatiles and trace elements through the Central American volcanic arc: evidence from melt inclusions. Contrib Mineral Petrol 155:433–456. doi:10.1007/s00410-007-0251-3

    Article  Google Scholar 

  • Salters VJM, Stracke A (2004) Composition of the depleted mantle. Geochem Geophys Geosyst. doi:10.1029/2003GC000597

    Google Scholar 

  • Scambelluri M, Müntener O, Ottolini L et al (2004) The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids. Earth Planet Sci Lett 222:217–234. doi:10.1016/j.epsl.2004.02.012

    Article  Google Scholar 

  • Selverstone J, Sharp ZD (2011) Chlorine isotope evidence for multicomponent mantle metasomatism in the Ivrea Zone. Earth Planet Sci Lett 310:429–440. doi:10.1016/j.epsl.2011.08.034

    Article  Google Scholar 

  • Shaw AM, Behn MD, Humphris SE et al (2010) Deep pooling of low degree melts and volatile fluxes at the 85°E segment of the Gakkel Ridge: evidence from olivine-hosted melt inclusions and glasses. Earth Planet Sci Lett 289:311–322. doi:10.1016/j.epsl.2009.11.018

    Article  Google Scholar 

  • Shimizu K, Saal AE, Myers CE et al (2016) Two-component mantle melting-mixing model for the generation of mid-ocean ridge basalts: implications for the volatile content of the Pacific upper mantle. Geochim Cosmochim Acta 176:44–80. doi:10.1016/j.gca.2015.10.033

    Article  Google Scholar 

  • Silantyev SA, Bortnikov NS, Shatagin KN et al (2016) Petrogenetic conditions at 18°–20°N MAR: interaction between hydrothermal and magmatic systems. Petrology 24:336–366. doi:10.1134/S0869591116040044

    Article  Google Scholar 

  • Smith DK, Schouten H, Dick HJB et al (2014) Development and evolution of detachment faulting along 50 km of the Mid-Atlantic Ridge near 16.5°N. Geochem Geophys Geosyst 15:4692–4711. doi:10.1002/2014GC005563

    Article  Google Scholar 

  • Spilliaert N, Métrich N, Allard P (2006) S-Cl–F degassing pattern of water-rich alkali basalt: modelling and relationship with eruption styles on Mount Etna volcano. Earth Planet Sci Lett 248:772–786. doi:10.1016/j.epsl.2006.06.031

    Article  Google Scholar 

  • Straub SM, Layne GD (2003) The systematics of chlorine, fluorine, and water in Izu arc front volcanic rocks: implications for volatile recycling in subduction zones. Geochim Cosmochim Acta 67:4179–4203. doi:10.1016/S0016-7037(03)00307-7

    Article  Google Scholar 

  • Van den Bleeken G, Koga KT (2015) Experimentally determined distribution of fluorine and chlorine upon hydrous slab melting, and implications for F-Cl cycling through subduction zones. Geochim Cosmochim Acta 171:353–373. doi:10.1016/j.gca.2015.09.030

    Article  Google Scholar 

  • Wanless VD, Shaw AM (2012) Lower crustal crystallization and melt evolution at mid-ocean ridges. Nat Geosci 5:651–655. doi:10.1038/ngeo1552

    Article  Google Scholar 

  • Wanless VD, Behn MD, Shaw AM, Plank T (2014) Variations in melting dynamics and mantle compositions along the Eastern Volcanic Zone of the Gakkel Ridge: insights from olivine-hosted melt inclusions. Contrib Mineral Petrol 167:1005. doi:10.1007/s00410-014-1005-7

    Article  Google Scholar 

  • Wanless VD, Shaw AM, Behn MD et al (2015) Magmatic plumbing at Lucky Strike volcano based on olivine-hosted melt inclusion compositions. Geochem Geophys Geosyst 16:126–147. doi:10.1002/2014GC005517

    Article  Google Scholar 

  • Warren JM, Hauri EH (2014) Pyroxenes as tracers of mantle water variations. J Geophys Res Solid Earth 119:1851–1881. doi:10.1002/2013JB010328

    Article  Google Scholar 

  • Workman RK, Hart SR (2005) Major and trace element composition of the depleted MORB mantle (DMM). Earth Planet Sci Lett 231:53–72. doi:10.1016/j.epsl.2004.12.005

    Article  Google Scholar 

  • Wu J, Koga KT (2013) Fluorine partitioning between hydrous minerals and aqueous fluid at 1GPa and 770–947°C: a new constraint on slab flux. Geochim Cosmochim Acta 119:77–92. doi:10.1016/j.gca.2013.05.025

    Article  Google Scholar 

  • Zanetti A, Mazzucchelli M, Rivalenti G, Vannucci R (1999) The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism. Contrib Mineral Petrol 134:107–122. doi:10.1007/s004100050472

    Article  Google Scholar 

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Acknowledgements

This research was supported by Grant NSF EAR-P&G 1524311 and DOEI Award 18563 to VLR. We thank two anonymous reviewers for their insights, which improved the manuscript. We also thank Erik Hauri for providing the Herasil glasses, Henry Dick for providing the MAR sample, and Nobumichi Shimizu for providing the Synthetic Forsterite grains. Urann was supported by the Stanley W. Watson Student Fellowship Fund based at WHOI.

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  1. Woods Hole Oceanographic Institution, 266 Woods Hole Road, Woods Hole, MA, 02543, USA

    B. M. Urann, V. Le Roux, K. Hammond, H. R. Marschall & B. D. Monteleone

  2. Goethe Universität Frankfurt, Institut für Geowissenschaften, Altenhöferallee 1, 60438, Frankfurt am Main, Germany

    H. R. Marschall

  3. Department of Earth Science, Rice University, MS-126, 6100 Main St., Houston, TX, 77005, USA

    C.-T. A. Lee

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  1. B. M. Urann
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Communicated by Timothy L. Grove.

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Urann, B.M., Le Roux, V., Hammond, K. et al. Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle. Contrib Mineral Petrol 172, 51 (2017). https://doi.org/10.1007/s00410-017-1368-7

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Keywords

  • Fluorine and chlorine content of mantle minerals
  • Halogen partitioning
  • Halogen budget of DMM
  • Peridotite