Phosphorus and aluminum zoning in olivine: contrasting behavior of two nominally incompatible trace elements

  • Thomas SheaEmail author
  • Julia E. Hammer
  • Eric Hellebrand
  • Adrien J. Mourey
  • Fidel Costa
  • Emily C. First
  • Kendra J. Lynn
  • Oleg Melnik
Original Paper


Phosphorus zoning in olivine is receiving considerable attention for its capacity to preserve key information about rates and mechanisms of crystal growth. Its concentration can vary significantly over sub-micron spatial scales and form intricate, snowflake-like patterns that are generally attributed to fast crystal growth. Ostensibly similar aluminum enrichment patterns have also been observed, suggesting comparable incorporation and partitioning behavior for both elements. We perform 1-atm crystallization experiments on a primitive Kīlauea basalt to examine the formation of P and Al zoning as a function of undercooling − ΔT (− ΔT = Tliquidus − Tcrystallization) during olivine growth. After 24 h spent at Tinitial = 1290 °C (10 °C above olivine stability), charges are rapidly cooled to final temperatures Tfinal = 1220–1270 °C, corresponding to undercoolings − ΔT  = 10–60 °C (with Tliquidus = 1280 °C). Compositional X-ray maps of experimental olivine reveal that only a small undercooling (≤ 25 °C) is required to produce the fine-scale enrichments in P and Al associated with skeletal growth. Concentration profiles indicate that despite qualitatively similar enrichment patterns in olivine, P and Al have contrasting apparent crystal/melt mass distribution coefficients of \(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) = 0.01‒1 and \(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) = 0.002‒0.006. Phosphorus can be enriched by a factor > 40-fold in the same crystal, whereas Al enrichment never exceed factors of 2. Glass in the vicinity of synthetic and natural olivine is usually enriched in Al, but, within analytical uncertainty, not in P. Thus, we find no direct evidence for a compositional boundary layer enriched in P that would suffice to produce P enrichments in natural and synthetic olivine. Numerical models combining growth and diffusion resolve the conditions at which Al-rich boundary layers produce the observed enrichment patterns in olivine. In contrast, the same models fail to reproduce the observed P enrichments, consistent with our observation that P-rich boundary layers are insignificant. If instead, P olivine/melt partitioning is made to depend on growth rate, models adequately reproduce our observations of 40-fold enrichment without boundary layer formation. We surmise that near-partitionless behavior (\(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) close to 1) of P is related to the olivine lattice being perhaps less stiff in accommodating P during rapid crystallization, and/or to enhanced formation of vacancy defects during fast growth. Our results confirm that P is a robust marker of initial rapid growth, but reveal that the undercooling necessary to induce these enrichments is not particularly large. The near-ubiquitous process of magma mixing under volcanoes, for instance, is likely sufficient to induce low-to-moderate degrees of undercooling required for skeletal growth.


Olivine Phosphorus Aluminum Growth kinetics Trace-element partitioning 



This work was funded by National Science Foundation Grant EAR-17225321 to TS and by a National Research Foundation Investigatorship Award (Grant number NRF-NRFI2017-06) to FC. The authors acknowledge Benoît Welsch, Francois Faure, Caroline Bouvet-de-Maisonneuve, and Mike Garcia, for the conversations that stimulated some of the ideas presented in this work. Reviews by Bruce Watson and Youxue Zhang helped improve the clarity of the manuscript. We also thank the editor Gordon Moore for his timely handling of the manuscript. This is SOEST contribution 10796.

Supplementary material

410_2019_1618_MOESM1_ESM.docx (2.4 mb)
Supplementary material 1 (DOCX 2474 kb)
410_2019_1618_MOESM2_ESM.xlsx (31.5 mb)
Supplementary material 2 (XLSX 32276 kb)


  1. Agrell SO, Charnley NR, Chinner GA (1998) Phosphoran olivine from Pine Canyon, Piute Co, Utah. Miner Mag 62:265–269Google Scholar
  2. Albarède F, Bottinga Y (1972) Kinetic disequilibrium in trace-element partitioning between phenocrysts and host lava. Geochim Cosmochim Acta 36:141–156Google Scholar
  3. Armstrong JT (1988) Quantitative analysis of silicate and oxide materials: comparison of Monte Carlo, ZAF, and ϕ(ρz) procedures. In: DE Newbury (ed) Microbeam analysis 1988: proceedings of the 23rd annual conference of the microbeam analysis society, Milwaukee, Wisconsin, 8–12 August 1988. San Francisco Press, San Francisco, p 527Google Scholar
  4. Bacon CR (1989) Crystallization of accessory phases in magmas by local saturation adjacent to phenocrysts. Geochim Cosmochim Acta 53:1055–1066Google Scholar
  5. Batanova VG, Sobolev AV, Kuzmin DV (2015) Trace element analysis of olivine: high precision analytical method for JEOL JXA-8230 electron probe microanalyser. Chem Geol 419:149–157Google Scholar
  6. Baziotis I, Asimow PD, Ntaflos T, Boyce JW, McCubbin FM, Koroneos A, Berndt J (2017) Phosphorus zoning as a recorder of crystal growth kinetics: application to second-generation olivine in mantle xenoliths from the Cima Volcanic Field. Contrib Miner Petrol 172:58. CrossRefGoogle Scholar
  7. 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 117:57–71Google Scholar
  8. Blundy JD, Wood BJ (1994) Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372:452–454Google Scholar
  9. Boesenberg JS, Hewins RH (2010) An experimental investigation into the metastable formation of phosphoran olivine and pyroxene. Geochim Cosmochim Acta 74:1923–1941Google Scholar
  10. Boesenberg JS, Ebel DS, Hewins RH (2004) An experimental study of phosphoran olivine and its significance in main group pallasites. In: 35th Lunar and Planetary Science Conference, March 15–19, 2004, League City, Texas, abstract no.1366Google Scholar
  11. Bussweiler Y, Brey GP, Pearson DG, Stachel T, Stern RA, Hardman MF, Kjarsgaard BA, Jackson SE (2017) The aluminum-in-olivine thermometer for mantle peridotites—experimental versus empirical calibration and potential applications. Lithos 272:301–314Google Scholar
  12. Cherniak DJ (2010) REE diffusion in olivine. Am Mineral 95:362–368Google Scholar
  13. Colman A, Sinton JM, Rubin KH (2016) Magmatic processes at variable magma supply along the Galápagos spreading center: constraints from single eruptive units. J Petrol 57:981–1018Google Scholar
  14. Conte AM, Perinelli C, Trigila R (2006) Cooling kinetics experiments on different Stromboli lavas: effects on crystal morphologies and phases compositions. J Volcanol Geotherm Res 155:179–200Google Scholar
  15. Coogan LA, Saunders AD, Wilson RN (2014) Aluminum-in-olivine thermometry of primitive basalts: evidence of an anomalously hot mantle source for large igneous provinces. Chem Geol 368:1–10Google Scholar
  16. Costa F, Dungan M (2005) Short time scales of magmatic assimilation from diffusion modelling of multiple elements in olivine. Geology 33:837–840Google Scholar
  17. de Maisonneuve CB, Costa F, Huber C, Vonlanthen P, Bachmann O, Dungan MA (2016) How do olivines record magmatic events? Insights from major and trace element zoning. Contrib Miner Petrol 171:56. CrossRefGoogle Scholar
  18. Dohmen R, Chakraborty S (2007) Fe–Mg diffusion in olivine II: point defect chemistry, change of diffusion mechanisms and a model for calculation of diffusion coefficients in natural olivine. Phys Chem Miner 34:409. CrossRefGoogle Scholar
  19. Donaldson CH (1976) An experimental investigation of olivine morphology. Contrib Mineral Petrol 57:187–213. CrossRefGoogle Scholar
  20. Donovan JJ, Tingle TN (1996) An improved mean atomic number background correction for quantitative microanalysis. Microsc Microanal 2:1–7Google Scholar
  21. Dunn T (1987) Partitioning of Hf, Lu, Ti, and Mn between olivine, clinopyroxene and basaltic liquid. Contrib Miner Petrol 96:476–484Google Scholar
  22. Ersoy O, Nikogosian IK, van Bergen MJ, Mason PRD (2019) Phosphorous incorporation in olivine crystallized from potassium-rich magmas. Geochim Cosmochim Acta 5:454. (in press) CrossRefGoogle Scholar
  23. Evans TM, O’Neill HSTC, Tuff J (2008) The influence of melt composition on the partitioning of REEs, Y, Sc, Zr and Al between forsterite and melt in the system CMAS. Geochim Cosmochim Acta 72:5708–5721Google Scholar
  24. Faure F, Schiano P (2005) Experimental investigation of equilibration conditions during forsterite growth and melt inclusion formation. Earth Planet Sci Lett 236:882–898Google Scholar
  25. Faure F, Trolliard G, Nicollet C, Montel J-M (2003) A developmental model of olivine morphology as a function of the cooling rate and the degree of undercooling. Contrib Mineral Petrol 145:251. CrossRefGoogle Scholar
  26. Faure F, Arndt N, Libourel G (2006) Formation of spinifex texture in komatiites: an experimental study. J Petrol 47:1591–1610. CrossRefGoogle Scholar
  27. Faure F, Schiano P, Trolliard G, Nicollet C, Soulestin B (2007) Textural evolution of polyhedral olivine experiencing rapid cooling rates. Contrib Miner Petrol 153:405. CrossRefGoogle Scholar
  28. First E, Hammer JE (2016) Igneous cooling history of olivine-phyric shergottite Yamato 980459 constrained by dynamic crystallization experiments. Meteorit Planet Sci 51:1233–1255Google Scholar
  29. Fonseca RO, Mallmann G, Sprung P, Sommer JE, Heuser A, Speelmanns IM, Blanchard H (2014) Redox controls on tungsten and uranium crystal/silicate melt partitioning and implications for the U/W and Th/W ratio of the lunar mantle. Earth Planet Sci Lett 404:1–13Google Scholar
  30. Garcia MO, Pietruszka AJ, Rhodes JM (2003) A petrologic perspective of Kilauea Volcano’s Summit Magma reservoir. J Petrol 44:2313–2339. CrossRefGoogle Scholar
  31. Gordeychik B, Churikova T, Kronz A, Sundermeyer C, Simakin A, Wörner G (2018) Growth of, and diffusion in, olivine in ultra-fast ascending basalt magmas from Shiveluch volcano. Sci Rep 8:11775Google Scholar
  32. Grant TB, Kohn SC (2013) Phosphorus partitioning between olivine and melt: an experimental study in the system Mg2SiO4–Ca2Al2Si2O9–NaAlSi3O8–Mg3(PO4)2. Am Miner 98:1860–1869Google Scholar
  33. Grugel RN (1993) Secondary and tertiary dendrite arm spacing relationships in directionally solidified Al–Si alloys. J Mater Sci 28:677–683Google Scholar
  34. Gualda GAR, Ghiorso MS, Lemons RV, Carley TL (2012) Rhyolite-MELTS: a modified calibration of MELTS optimized for silica-rich, fluid-bearing magmatic systems. J Petrol 53:875–890Google Scholar
  35. Hammer JE (2008) Experimental studies of the kinetics and energetics of magma crystallization. Rev Min 69:9–59Google Scholar
  36. Hammer JE, Ishii HA, Bradley JP, Shea T, Welsch B, Hellebrand E (2017) Advanced materials characterization of P-rich and P-poor regions within single crystal olivine. Lunar Planet Sci 48:2375Google Scholar
  37. Helz RT, Cottrell E, Brounce MN, Kelley KA (2017) Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES. J Volcanol Geotherm Res 333–334:1–14. CrossRefGoogle Scholar
  38. Huang R, Audetat A (2012) The titanium-in-quartz (TitaniQ) thermobarometer: a critical examination and re-calibration. Geochim Cosmochim Acta 84:75–89Google Scholar
  39. Jambon A, Lussiez P, Clocchiatti R, Weisz J, Hernandez J (1992) Olivine growth rates in a tholeiitic basalt; an experimental study of melt inclusions in plagioclase. Chem Geol 96:277–287. CrossRefGoogle Scholar
  40. Jarosewich E, Nelen JA, Norberg JA (1980) Reference samples for electron microprobe analysis. Geostand Newsl 4:43–47Google Scholar
  41. Jollands MC, O’Neill HSC, Hermann J (2014) The importance of defining chemical potentials, substitution mechanisms and solubility in trace element diffusion studies: the case of Zr and Hf in olivine. Contrib Miner Petrol 168:1–19Google Scholar
  42. Kahl M, Chakraborty S, Pompilio M, Costa F (2015) Constraints on the nature and evolution of the magma plumbing system of Mt. Etna Volcano (1991–2008) from a combined thermodynamic and kinetic modelling of the compositional record of minerals. J Petrol 56:2025–2068Google Scholar
  43. Lanzillo NA, Watson EB, Thomas JB, Nayak SK, Curioni A (2014) Near-surface controls on the composition of growing crystals: car-Parrinello molecular dynamics (CPMD) simulations of Ti energetics and diffusion in alpha quartz. Geochim Cosmochim Acta 131:33–46. CrossRefGoogle Scholar
  44. Lasaga AC (1982) Toward a master equation in crystal growth. Am J Sci 282:1264–1288. CrossRefGoogle Scholar
  45. Libourel G, Portail M (2018) Chondrules as direct thermochemical sensors of solar protoplanetary disk gas. Sci Adv 4:eaar3321Google Scholar
  46. Lofgren GE, Huss GR, Wasserburg GJ (2006) An experimental study of traceelement partitioning between Ti-Al-clinopyroxene and melt: equilibrium and kinetic effects including sector zoning. Am Miner 91:1596–1606Google Scholar
  47. Lynn KJ, Garcia MO, Shea T, Costa F, Swanson DA (2017) Timescales of mixing and storage for Keanakako’i Tephra magmas (1500–1820 CE), Kilauea Volcano, Hawai’i. Contrib Miner Petrol 172:76Google Scholar
  48. Lynn KJ, Shea T, Garcia MO, Costa F, Norman MD (2018) Lithium diffusion in olivine records priming of explosive basaltic eruptions. Earth Planet Sci Lett 500:127–135Google Scholar
  49. Manzini M, Bouvier A-S, Baumgartner L, Muntener O, Rose-Koga E, Schiano P, Escrig S, Meiborn A, Shimizu N (2017) Weekly to monthly time scale of melt inclusion entrapment prior to eruption recorded by phosphorus distribution in olivine from mid-ocean ridges. Geology 45:1059–1062Google Scholar
  50. Matzen AK, Baker MB, Beckett JR, Stolper EM (2011) Fe-Mg partitioning between olivine and high-magnesian melts and the nature of Hawaiian parental liquids. J Petrol 52:1243–1263Google Scholar
  51. McCanta MC, Beckett JR, Stolper EM (2016) Correlations and zoning patterns of phosphorus and chromium in olivine from H chondrites and the LL chondrite Semarkona. Meteorit Planet Sci 51:520–546Google Scholar
  52. Milman-Barris MS, Beckett JR, Baker MB, Hofmann AE, Morgan Z, Crowley MR, Vielzeuf D, Stolper E (2008) Zoning of phosphorus in igneous olivine. Contrib Miner Petrol 155:739. CrossRefGoogle Scholar
  53. Mollo S, Putirka K, Iezzi G, Del Gaudio P, Scarlato P (2011) Plagioclase-melt (dis)equilibrium due to cooling dynamics: implications for thermometry, barometry and hygrometry. Lithos 125:221–235Google Scholar
  54. Mollo S, Blundy J, Scarlato P, Iezzi G, Langone A (2013) The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth. Contrib Miner Petrol 166:1633–1654Google Scholar
  55. Mourey A, Shea T (2018) 3D quantification of olivine growth rates. Goldschmidt Abstracts 2018:1822Google Scholar
  56. Pack A, Palme H (2003) Partitioning of Ca and Al between forsterite and silicate melt in dynamic systems with implications for the origin of Ca, Al-rich forsterites in primitive meteorites. Meteorit Planet Sci 38:1263–1281Google Scholar
  57. Rhodes JM, Vollinger MJ (2005) Ferric/ferrous ratios in 1984 Mauna Loa lavas: a contribution to understanding the oxidation state of Hawaiian magmas. Contrib Miner Petrol 149:666. CrossRefGoogle Scholar
  58. Rubin AE, Cooper KM, Till CB, Kent AJ, Costa F, Bose M, Gravley D, Deering C, Cole J (2017) Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals. Science 356:1154–1156Google Scholar
  59. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst A32:751–767Google Scholar
  60. Shea T, Lynn KJ, Garcia MO (2015) Cracking the olivine zoning code: distinguishing between crystal growth and diffusion. Geology 43:935–938. CrossRefGoogle Scholar
  61. Sliwinski JT, Kueter N, Marxer F, Ulmer P, Guillong M, Bachmann O (2018) Controls on lithium concentration and diffusion in zircon. Chem Geol 501:1–11Google Scholar
  62. Smith VG, Tiller WA, Rutter JW (1955) A mathematical analysis of solute redistribution during solidification. Can J Phys 33:723–745Google Scholar
  63. Spandler C, O’Neill HSC (2010) Diffusion and partition coefficients of minor and trace elements in San Carlos olivine at 1300 C with some geochemical implications. Contrib Miner Petrol 159(6):791–818Google Scholar
  64. Sun C, Liang Y (2017) A REE-in-plagioclase–clinopyroxene thermometer for crustal rocks. Contrib Mineral Petrol 172:24Google Scholar
  65. Tang M, Rudnick RL, McDonough WF, Bose M, Goreva Y (2017) Multi-mode Li diffusion in natural zircons: evidence for diffusion in the presence of step-function concentration boundaries. Earth Planet Sci Lett 474:110–119Google Scholar
  66. Taura H, Yurimoto H, Kurita K, Sueno S (1998) Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts. Phys Chem Miner 25(7):469–484Google Scholar
  67. Tiller WA, Jackson KA, Rutter JW, Chalmers B (1953) The redistribution of solute atoms during solidification of metals. Acta Metall 1:428–437Google Scholar
  68. Tollan PME, O’Neill HSC, Hermann J (2018) The role of trace elements in controlling H incorporation in San Carlos olivine. Contrib Miner Petrol 173:89Google Scholar
  69. Trail D, Cherniak DJ, Watson EB, Harrison TM, Weiss BP, Szumila I (2016) Li zoning in zircon as a potential geospeedometer and peak temperature indicator. Contrib Miner Petrol 171:25Google Scholar
  70. Ubide T, McKenna CA, Chew DM, Kamber BS (2015) High-resolution LA-ICP-MS trace element mapping of igneous minerals: in search of magma histories. Chem Geol 409:157–159Google Scholar
  71. Watkins J, DePaolo D, Watson EB (2017) Kinetic fractionation of non-traditional stable isotopes by diffusion and crystal growth reactions. Rev Miner Geochem 82:85–125Google Scholar
  72. Watson EB (2004) A conceptual model for near-surface kinetic controls on the trace-element and stable-isotope composition of abiogenic calcite. Geochim Cosmochim Acta 68:1473–1488Google Scholar
  73. Watson EB, Liang Y (1995) A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am Miner 80(11–12):1179–1187Google Scholar
  74. Watson EB, Müller T (2009) Non-equilibrium isotopic and elemental fractionation during diffusion-controlled crystal growth under static and dynamic conditions. Chem Geol 267:111–124. CrossRefGoogle Scholar
  75. Watson EB, Cherniak DJ, Holycross ME (2015) Diffusion of phosphorus in olivine and molten basalt. Am Miner 100:2053–2065. CrossRefGoogle Scholar
  76. Welsch B, Faure F, Famin V, Baronnet A, Bachelery P (2013) Dendritic crystallization: a single process for all the textures of olivine in basalts? J Petrol 54:539–574. CrossRefGoogle Scholar
  77. Welsch B, Hammer J, Hellebrand E (2014) Phosphorus zoning reveals dendritic architecture of olivine. Geology 42:867–870. CrossRefGoogle Scholar
  78. Wilson CJ, Morgan DJ, Charlier BL, Barker SJ (2017) Comment on “Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals”. Science 358(6370)Google Scholar
  79. Xing C-M, Wang CY, Tan W (2017) Disequilibrium growth of olivine in mafic magmas revealed by phosphorus zoning patterns of olivine from mafic-ultramafic intrusions. Earth Planet Sci Lett 479:108–119Google Scholar
  80. Yurimoto H, Sueno S (1984) Anion and cation partitioning between olivine, plagioclase phenocrysts and the host magma: a new application of ion microprobe study. Geochem J 18:85–94Google Scholar
  81. Zhang Y (2008) Geochemical kinetics. Princeton University Press, Princeton, p 664Google Scholar
  82. Zhang Y, Ni H, Chen Y (2010) Diffusion data in silicate melts. Rev Miner Geochem 72:311–408Google Scholar
  83. Zhukova I, O’Neill H, Campbell IH (2017) A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions. Contrib Miner Petrol 172:53Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Earth Sciences, SOESTUniversity of Hawaii at MānoaHonoluluUSA
  2. 2.Department of Earth SciencesUtrecht UniversityUtrechtThe Netherlands
  3. 3.Earth Observatory of Singapore, Nanyang Technological UniversitySingaporeSingapore
  4. 4.Brown University, DEEPSProvidenceUSA
  5. 5.Department of Geological SciencesUniversity of DelawareNewarkUSA
  6. 6.Institute of MechanicsMoscow State UniversityMoscowRussia

Personalised recommendations