Contributions to Mineralogy and Petrology

, Volume 160, Issue 2, pp 279–295 | Cite as

Redistribution of HFSE elements during rutile replacement by titanite

  • Friedrich LucassenEmail author
  • Peter Dulski
  • Rainer Abart
  • Gerhard Franz
  • Dieter Rhede
  • Rolf L. Romer
Original Paper


Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.


Rutile Titanite Metamorphic reaction HFSE distribution Nb, Zr diffusion in rutile 



We are grateful to Dr. Ulrike Troitzsch for providing the sample, who in turn thanks Prof. Erling Krogh Ravna and the Geology Department of the University of Tromsø for logistical support during the field work. Constructive and exhaustive reviews by Frank Spear, Thomas Zack, and Armin Zeh improved the manuscript and are grateful acknowledged. The study was supported by DFG grant DR 744/3-1 in the framework of the research group FOR 741 ‘Nanoscale processes and geomaterials properties’. We thank our colleagues of FOR 741 for stimulating discussions.

Supplementary material

410_2009_477_MOESM1_ESM.tif (29.6 mb)
AFigure 1 a, b, c Positions of the EMP profile lines and LA profile lines and LA individual spots probing the trace element composition of titanite in relation to the variable crystal chemistry. EMP profiles (the green lines) of UT1 and UT2 are labelled using numbers in accordance with Figure 4 c and d. LA-spots not labelled were used for testing and tuning the machine. AFigure a UT1; LA–spots are colour-coded and labelled according to ATable 2; line 4 is not shown in its whole extent and continues into the large single crystal titanite
410_2009_477_MOESM2_ESM.tif (29.4 mb)
AFigure 1 b UT2; laser spots at are colour-coded and labelled according to ATable 2
410_2009_477_MOESM3_ESM.tif (28.1 mb)
AFigure 1 c UT2; laser spots in rutile and titanite along the interface of both; data in ATable 2
410_2009_477_MOESM4_ESM.eps (1.1 mb)
AFigure 2 a-h Distribution of Nb, Zr, Ta, Hf, W, Nb/Ta, Zr/Hf, and Zr/Nb along profile lines through titanite overgrowth and rutile (a, b, c, d) UT1 and (e, f, g, h) UT2; (e) Nb in titanite and rutile and Zr in rutile at a high spatial resolution by EMP; inclusions with high Nb contents in the titanite overgrowth are rutile. The scatter in the W distribution is large in UT1 and UT2, but it follows the pattern of the other elements in UT1. In UT2 the W contents is high and extremely enriched at the contact with line 1; the left and the right y-axes in (d, g, h) have different scales
410_2009_477_MOESM5_ESM.eps (429 kb)
AFigure 2 i-n LA - sample points along the interface rutile-titanite UT1 (line 5 in Fig. 1c) and UT2 (line 4 in Fig.1d); (i, j, k) UT1 Nb, Ta, Zr, Hf, W concentrations (i) in rutile (j) in titanite; (k) Nb/Ta, Zr/Hf, and Nb/Zr in rutile and titanite; (l, m, n) for UT2
410_2009_477_MOESM6_ESM.xls (76 kb)
ATable 1 EMP analyses of the minerals in UT (except titanite)
410_2009_477_MOESM7_ESM.xls (359 kb)
ATable 2 EMP and LA analyses from profiles and compositional zoning in titanite according to Fig. 1 and AFigure 1. Trace element analyses (EMP) of small rutile inclusions and surrounding titanite


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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Friedrich Lucassen
    • 1
    • 2
    Email author
  • Peter Dulski
    • 2
  • Rainer Abart
    • 3
  • Gerhard Franz
    • 1
  • Dieter Rhede
    • 2
  • Rolf L. Romer
    • 2
  1. 1.Technische Universität BerlinBerlinGermany
  2. 2.Deutsches GeoForschungsZentrumPotsdamGermany
  3. 3.Freie Universität Berlin, FB GeowissenschaftenBerlinGermany

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