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Compositional effects on the solubility of minor and trace elements in oxide spinel minerals: insights from crystal-crystal partition coefficients in chromite exsolution

  • Vanessa Colás EMAIL logo , José Alberto Padrón-Navarta , José María González-Jiménez , William L. Griffin , Isabel Fanlo , Suzanne Y. O’Reilly , Fernando Gervilla , Joaquín A. Proenza , Norman J. Pearson and Monica P. Escayola
Published/Copyright: June 3, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 6

Abstract

Chromite from Los Congos and Los Guanacos in the Eastern Pampean Ranges of Córdoba (Argentinian Central Andes) shows homogenous and exsolution textures. The composition of the exsolved phases in chromite approaches the end-members of spinel (MgAl2O4; Spl) and magnetite (Fe2+Fe23+O4; Mag) that define the corners of the spinel prism at relatively constant Cr3+/R3+ ratio (where R3+ is Cr+Al+Fe3+). The exsolution of these phases from the original chromite is estimated to have accounted at ≥600 °C on the basis of the major element compositions of chromite with homogenous and exsolution textures that are in equilibrium with forsterite-rich olivine (Fo95). The relatively large size of the exsolved phases in chromite (up to ca. 200 μm) provided, for the first time, the ability to conduct in situ analysis with laser ablation-inductively coupled plasma-mass spectrometry for a suite of minor and trace elements to constrain their crystal-crystal partition coefficient between the spinel-rich and magnetite-rich phases (DiSpl/Mag). Minor and trace elements listed in increasing order of compatibility with the spinel-rich phase are Ti, Sc, Ni, V, Ge, Mn, Cu, Sn, Co, Ga, and Zn. DiSpl/Mag values span more than an order of magnitude, from DTiSpl/Mag = 0.30 ± 0.06 to DZnSpl/Mag= 5.48 ± 0.63. Our results are in remarkable agreement with data available for exsolutions of spinel-rich and magnetite-rich phases in other chromite from nature, despite their different Cr3+/R3+ ratio. The estimated crystal-crystal partitioning coefficients reflect the effect that crystal-chemistry of the exsolved phases from chromite imposes on all investigated elements, excepting Cu and Sc (and only slightly for Mn). The observed preferential partitioning of Ti and Sc into the magnetite-rich phase is consistent with high-temperature chromite/melt experiments and suggests a significant dependence on Fe3+ substitution in the spinel structure. A compositional effect of major elements on Ga, Co, and Zn is observed in the exsolved phases from chromite but not in the experiments; this might be due to crystal-chemistry differences along the MgFe–1-Al2Fe−23+ exchange vector, which is poorly covered experimentally. This inference is supported by the strong covariance of Ga, Co, and Zn observed only in chromite from layered intrusions where this exchange vector is important. A systematic increase of Zn and Co coupled with a net decrease in Ga during hydrous metamorphism of chromitite bodies cannot be explained exclusively by compositional changes of major elements in the chromite (which are enriched in the magnetite component). The most likely explanation is that the contents of minor and trace elements in chromite from metamorphosed chromitites are controlled by interactions with metamorphic fluids involved in the formation of chlorite.

Key words: Chromite exsolution; spinel-magnetite; partition coefficient; minor and trace elements; hydrous metamorphism

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments

This research was supported by the project CGL2010-15171 and F.P.I. grant BES-2011-045423 of the Ministerio de Econonía y Competitividad (Spain). Support for this study has also been provided by the FONDECYT #11140005 and “Millenium Nucleus for Metal Tracing Along Subduction NC130065” to José María González-Jiménez. We thank Steve Barnes and an anonymous reviewer for their careful and constructive comments and Ferdinando Bosi for his proficient editorial handling of this manuscript. The analytical data were obtained using instrumentation funded by DEST Systemic Infrastructure Grants, ARC LIEF, NCRIS, industry partners and Macquarie University. This is a contribution 701 from the ARC Centre of Excellence for Core to Crust Fluid Systems (www.ccfs.mq.edu.au) and 1055 in the GEMOC Key Centre (www.gemoc.mq.edu.au).

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Appendix

Data sources for calculated crystal-crystal partition coefficients

The crystal-crystal partition coefficients of exsolved phases in chromite from previously published data sets were calculated using reported EMPA data for minor elements. Chromite with exsolution textures come from the layered complexes of Carr Boyd Rocks Complex (Western Australia, Purvis et al. 1972), Giant Nickel Mine (British Columbia, Muir and Naldrett 1973), Red Lodge district (Montana, U.S.A., Loferski and Lipin 1983), Kuså (Sweden, Zakrzewski 1989), Chilas (Pakistan, Jan et al. 1992), Isua Greenstone Belt (Greenland, Appel et al. 2002) and the Eastern Desert (Egypt, Ahmed et al. 2008); from the Uralian-Alaskan-type complexes of Staré Ransko (Czech Republic, van der Veen and Maaskant 1995), Uktus (Russia, Garuti et al. 2003) and the Central Ural Mountains (Krause et al. 2007); and from the peridotite complex of Iwanai-dake (Japan, Tamura and Arai 2005).

Data source for minor and trace elements in chromite

The data sources for minor and trace elements in chromite used in this study consist of previously published and new data sets. Chromite samples are classified based on magmatic setting (ophiolitic peridotites, lavas, and layered intrusions) and by metamorphic assemblage (chromite and Fe3+-rich chromite in equilibrium with chlorite).

Reported minor and trace element compositions of chromite in ophiolitic peridotites come from the Thetford Mine Ophiolite (Canada, Pagé and Barnes 2009), Ouen Island and Dyne (New Caledonia, González-Jiménez et al. 2011; Colás et al. 2014), Mercedita, Tres Amigos and Rupertina (Cuba, Colás et al. 2014; González-Jiménez et al. 2015), and Luobusa (Tibet, Zhou et al. 2014). Chromite samples of lavas are taken from the East Pacific Rise, Bonin Island (Japan), Thetford Mine Ophiolite (Canada) (Pagé and Barnes 2009), and Solomon Island (Yao 1999); and those of layered intrusions from the Bushveld Complex (South Africa) and the Great Dike (Zimbabwe) (Yao 1999). Data for the metamorphosed chromite come from ophiolitic chromitites of Los Congos and Los Guanacos (Argentina), Central and Eastern Rhodope (Bulgaria, González-Jiménez et al. 2015; Colás et al. 2014), Ouen Island (New Caledonia, González-Jiménez et al. 2011) and Southeastern Turkey (Akmaz et al. 2014); and those from the greenstone belt of Nuggihalli (India, Mukherjee et al. 2015).

Matlab script to plot spinel prism in 3D

The following is a simple Matlab script to plot the spinel prism that reads an input csv file consisting in four columns (without headers) as follow Cr/R3+, Al/R3+, Cr/R3+, and XMg in mole proportions.

clear all

data = importdata(’CongosExs.csv’);

λ = data(:,1:3);

points_x = transpose(1-data(:,4));

% Cartesian components of the triangle vertices r1, r2, r3;

% ri = (yi, zi), i = 1:3

% r1 r2 r3

vertex = [0 1 0.5; % y

0 0 1]; % z

% transformation to cartesian coordinates

points_y = zeros(1,length(λ));

points_z = zeros(1,length(λ));

for i = 1:length(λ)

points_y(i) = λ(i,1)*vertex(1,1)...

+λ(i,2)*vertex(1,2)...

+λ(i,3)*vertex(1,3);

points_z(i) = λ(i,1)*vertex(2,1)...

+λ(i,2)*vertex(2,2)...

+λ(i,3)*vertex(2,3);

end

scatter3(points_x,points_y,points_z)

xlabel(‘x’), ylabel(‘y’), zlabel(‘z’),

xlim([0 1]), zlim([0 1])

text(-0.05,-0.15,0,[‘Pc’],‘FontSize’,14)

text(-0.05,1.15,-0.1,[‘Sp’],‘FontSize’,14)

text(1,-0.15,0,[‘Chr’],‘FontSize’,14)

text(0,0.5,1.1,[‘Mf’],‘FontSize’,14)

text(1,0.5,1.1,[‘Mt’],‘FontSize’,14)

text(1.15,1.25,-0.1,[‘Her’],‘FontSize’,14)

hold on

daspect([1.7 1 1.1753])

% Prism

plot3([0 0 0 0 1 1 1 1 1 0 0 1],...

[0 1 0.5 0 0 1 0.5 0 0.5 0.5 1 1],...

[0 0 1 0 0 0 1 0 1 1 0 0])

Received: 2015-10-26
Accepted: 2016-2-5
Published Online: 2016-6-3
Published in Print: 2016-6-1

© 2016 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Invited Centennial Article
  2. On the nature and significance of rarity in mineralogy
  3. Special collection: mechanisms, rates, and timescales of geochemical transport processes in the crust and mantle
  4. Zircon saturation and Zr diffusion in rhyolitic melts, and zircon growth geospeedometer
  5. Review
  6. On silica-rich granitoids and their eruptive equivalents
  7. Special collection: advances in ultrahigh-pressure metamorphism
  8. Discovery of in situ super-reducing, ultrahigh-pressure phases in the Luobusa ophiolitic chromitites, Tibet: new insights into the deep upper mantle and mantle transition zone
  9. Special collection: from magmas to ore deposits
  10. Uraninite from the Olympic Dam IOCG-U-Ag deposit: linking textural and compositional variation to temporal evolution
  11. Special collection: from magmas to ore deposits
  12. A story of olivine from the McIvor Hill complex (Tasmania, Australia): Clues to the origin of the Avebury metasomatic Ni sulfide deposit
  13. Special collection: perspectives on origins and evolution of crustal magmas
  14. The origin of extensive Neoarchean high-silica batholiths and the nature of intrusive complements to silicic ignimbrites: Insights from the Wyoming batholith, U.S.A.
  15. Special collection: perspectives on origins and evolution of crustal magmas
  16. From the Hadean to the Himalaya: 4.4 Ga of felsic terrestrial magmatism
  17. Spinels renaissance: the past, present, and future of those ubiquitous minerals and materials
  18. Compositional effects on the solubility of minor and trace elements in oxide spinel minerals: insights from crystal-crystal partition coefficients in chromite exsolution
  19. Spinels renaissance: the past, present, and future of those ubiquitous minerals and materials
  20. An X-ray magnetic circular dichroism (XMCD) study of Fe ordering in a synthetic MgAl2O4-Fe3O4 (spinel-magnetite) solid-solution series: Implications for magnetic properties and cation site ordering
  21. Research Article
  22. High concentrations of manganese and sulfur in deposits on Murray Ridge, Endeavour Crater, Mars
  23. Research Article
  24. A Cr3+ luminescence study of spodumene at high pressures: effects of site geometry, a phase transition, and a level-crossing
  25. Research Article
  26. Phase transitions between high- and low-temperature orthopyroxene in the Mg2Si2O6-Fe2Si2O6 system
  27. Research Article
  28. High-temperature and high-pressure behavior of carbonates in the ternary diagram CaCO3-MgCO3-FeCO3
  29. Research Article
  30. Natural Mg-Fe clinochlores: enthalpies of formation and dehydroxylation derived from calorimetric study
  31. Research Article
  32. Trace element thermometry of garnet-clinopyroxene pairs
  33. Research Article
  34. Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite
  35. Research Article
  36. Ni-phyllosilicates (garnierites) from the Falcondo Ni-laterite deposit (Dominican Republic): mineralogy, nanotextures, and formation mechanisms by HRTEM and AEM
  37. Research Article
  38. Cu diffusion in a basaltic melt
  39. Research Article
  40. High-pressure behavior of the polymorphs of FeOOH
  41. New Mineral Names
  42. New Mineral Names
https://doi.org/10.2138/am-2016-5611
Keywords for this article
Chromite exsolution; spinel-magnetite; partition coefficient; minor and trace elements; hydrous metamorphism

Articles in the same Issue

  1. Invited Centennial Article
  2. On the nature and significance of rarity in mineralogy
  3. Special collection: mechanisms, rates, and timescales of geochemical transport processes in the crust and mantle
  4. Zircon saturation and Zr diffusion in rhyolitic melts, and zircon growth geospeedometer
  5. Review
  6. On silica-rich granitoids and their eruptive equivalents
  7. Special collection: advances in ultrahigh-pressure metamorphism
  8. Discovery of in situ super-reducing, ultrahigh-pressure phases in the Luobusa ophiolitic chromitites, Tibet: new insights into the deep upper mantle and mantle transition zone
  9. Special collection: from magmas to ore deposits
  10. Uraninite from the Olympic Dam IOCG-U-Ag deposit: linking textural and compositional variation to temporal evolution
  11. Special collection: from magmas to ore deposits
  12. A story of olivine from the McIvor Hill complex (Tasmania, Australia): Clues to the origin of the Avebury metasomatic Ni sulfide deposit
  13. Special collection: perspectives on origins and evolution of crustal magmas
  14. The origin of extensive Neoarchean high-silica batholiths and the nature of intrusive complements to silicic ignimbrites: Insights from the Wyoming batholith, U.S.A.
  15. Special collection: perspectives on origins and evolution of crustal magmas
  16. From the Hadean to the Himalaya: 4.4 Ga of felsic terrestrial magmatism
  17. Spinels renaissance: the past, present, and future of those ubiquitous minerals and materials
  18. Compositional effects on the solubility of minor and trace elements in oxide spinel minerals: insights from crystal-crystal partition coefficients in chromite exsolution
  19. Spinels renaissance: the past, present, and future of those ubiquitous minerals and materials
  20. An X-ray magnetic circular dichroism (XMCD) study of Fe ordering in a synthetic MgAl2O4-Fe3O4 (spinel-magnetite) solid-solution series: Implications for magnetic properties and cation site ordering
  21. Research Article
  22. High concentrations of manganese and sulfur in deposits on Murray Ridge, Endeavour Crater, Mars
  23. Research Article
  24. A Cr3+ luminescence study of spodumene at high pressures: effects of site geometry, a phase transition, and a level-crossing
  25. Research Article
  26. Phase transitions between high- and low-temperature orthopyroxene in the Mg2Si2O6-Fe2Si2O6 system
  27. Research Article
  28. High-temperature and high-pressure behavior of carbonates in the ternary diagram CaCO3-MgCO3-FeCO3
  29. Research Article
  30. Natural Mg-Fe clinochlores: enthalpies of formation and dehydroxylation derived from calorimetric study
  31. Research Article
  32. Trace element thermometry of garnet-clinopyroxene pairs
  33. Research Article
  34. Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite
  35. Research Article
  36. Ni-phyllosilicates (garnierites) from the Falcondo Ni-laterite deposit (Dominican Republic): mineralogy, nanotextures, and formation mechanisms by HRTEM and AEM
  37. Research Article
  38. Cu diffusion in a basaltic melt
  39. Research Article
  40. High-pressure behavior of the polymorphs of FeOOH
  41. New Mineral Names
  42. New Mineral Names
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