University of Oulu

Park, J., Kamenetsky, V., Campbell, I., Park, G., Hanski, E., Pushkarev, E. (2017) Empirical constraints on partitioning of platinum group elements between Cr-spinel and primitive terrestrial magmas. Geochimica et Cosmochimica Acta, 216 (), 393-416. doi:10.1016/j.gca.2017.05.039

Empirical constraints on partitioning of platinum group elements between Cr-spinel and primitive terrestrial magmas

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Author: Park, Jung-Woo1; Kamenetsky, Vadim2,3; Campbell, Ian4;
Organizations: 1School of Earth and Environmental Sciences & Research Institute of Oceanography, Seoul National University
2School of Physical Sciences, University of Tasmania
3Institute of Experimental Mineralogy RAS
4Research School of Earth Sciences, Australian National University
5Oulu Mining School, University of Oulu
6Institute of Geology and Geochemistry, Ural Branch of the Russian Academy of Science
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 4 MB)
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Language: English
Published: Elsevier, 2017
Publish Date: 2018-01-02


Recent experimental studies and in situ LA-ICP-MS analysis on natural Cr-spinel have shown that Rh and IPGEs (Ir-group platinum group elements: Ru, Ir, Os) are enriched in the lattice of Cr-spinel. However, the factors controlling the partitioning behaviour of these elements are not well constrained. In this study, we report the Rh, IPGE, and trace element contents in primitive Cr-spinel, measured by LA-ICP-MS, from nine volcanic suites covering various tectonic settings including island arc picrites, boninites, large igneous province picrites and mid-ocean ridge basalts. The aim is to understand the factors controlling the enrichment of Rh and IPGEs in Cr-spinels, to estimate empirical partition coefficients between Cr-spinel and silicate melts, and to investigate the role of Cr-spinel fractional crystallization on the PGE geochemistry of primitive magmas during the early stages of fractional crystallization.

There are systematic differences in trace elements, Rh and IPGEs in Cr-spinels from arc-related magmas (Arc Group Cr-spinel), intraplate magmas (Intraplate Group Cr-spinel), and mid-ocean ridge magmas (MORB Group Cr-spinel). Arc Group Cr-spinels are systematically enriched in Sc, Co and Mn and depleted in Ni compared to the MORB Group Cr-spinels. Intraplate Group Cr-spinels are distinguished from the Arc Group Cr-spinels by their high Ni contents. Both the Arc and Intraplate Group Cr-spinels have total Rh and IPGE contents of 22–689 ppb whereas the MORB Group Cr-spinels are depleted in Rh and IPGE (total < 20 ppb). Palladium and Pt contents are below detection limit for all of the studied Cr-spinels (<1–5 ppb). The time-resolved spectra of LA-ICP-MS data for Cr-spinels mostly show constant count rates for trace element and Rh and IPGEs, suggesting homogeneous distribution of these elements in Cr-spinels. The PGE spikes observed in several Cr-spinels were interpreted to be PGE-bearing mineral inclusions and excluded from calculating the PGE contents of the Cr-spinels.

On primitive mantle normalized diagrams the Arc Group Cr-spinels are characterized by a fractionated pattern with high Rh and low Os. The Intraplate Group Cr-spinels show flat patterns with positive Ru anomalies. Our results, together with the experimental and empirical data from previous studies, show that PGE patterns of Cr-spinel largely mimic that of the rock in which they are found, and that Rh, Ir and Os contents increase with increasing Fe3+ contents (i.e. magnetite component) in Cr-spinel, although Ru does not. These observations suggest that the enrichment of Rh and IPGEs in Cr-spinel is controlled by a combination of the Rh and IPGE contents in parental melts and the magnetite component of the spinel. Empirical partition coefficients (D) for Rh and IPGEs between Cr-spinels and silicate melts were calculated using the Rh and IPGE contents of the Cr-spinel and their host volcanic rocks after subtracting the accumulation effect of Cr-spinel. The D values for the Intraplate and MORB Group Cr-spinels increase with increasing magnetite component in Cr-spinel and range from 6 to 512, which is consistent with previously reported experimental and empirical values. In contrast, the Arc Group Cr-spinels have significantly higher D values (e.g. up to ∼3700 for Ru) than those of the Intraplate and MORB Group at the same magnetite concentration in the Cr-spinel, suggesting Rh and IPGEs dissolved in silicate melt have stronger affinity for Cr spinel under arc magma conditions than in intraplate magmas. This may be partly attributed to the low temperature of arc magmas relative to intraplate magmas, which leads to the Arc Group Cr-spinels having more octahedral sites at the same magnetite components than the Intraplate Group Cr-spinels. Because of significantly higher D values for the Arc Group Cr-spinels, compared with the Intraplate Group and MORB Group spinels, fractional crystallization of Cr-spinel will more efficiently fractionate Rh and IPGE from Pd and Pt in arc systems than in intraplate and MORB systems, which accounts for the highly fractionated PGE patterns in arc basalts.

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Series: Geochimica et cosmochimica acta
ISSN: 0016-7037
ISSN-E: 1872-9533
ISSN-L: 0016-7037
Volume: 216
Pages: 393 - 416
DOI: 10.1016/j.gca.2017.05.039
Type of Publication: A1 Journal article – refereed
Field of Science: 1171 Geosciences
Funding: This study was funded by the Korea government Ministry of Science, ICT and Future Planning (NRF-2015R1C1A1A01054101) to J.-W. Park. The Russian Science Foundation (Grant #16-17-10145) provided funding to V. Kamenetsky. E. Hanski acknowledges support from Academy of Finland Grant #281859. The mineralogy and geochemistry of the Urals ankaramite was supported by RFBR Grant N 16-05-00508 to E. Pushkarev.
Academy of Finland Grant Number: 281859
Detailed Information: 281859 (Academy of Finland Funding decision)
Copyright information: © 2017 The Authors. This is an open access article under the CC BY-NC-ND license (