Trace element partitioning into sulfide: How lithophile elements become chalcophile and vice versa.

Sulfides, although modally of low abundance in most igneous rocks, have strong influences on the geochemical behavior of many elements including Pb, Cu, Ni, and the PGEs. In a recent paper, we demonstrated a simple relationship between the sulfide-silicate partition coefficients D_M^sulf/sil of such elements and the FeO content of the coexisting silicate melt (Kiseeva and Wood 2013). logD_M^sulf/sil A-n/2 log [FeO] where n is the valency of element M, [FeO] is the concentration of FeO in the silicate in wt%, and A is a constant that depends on temperature and pressure. Elements that closely obey the simple model are Pb, In, Sb, Cd, Co, Zn, and Cr. We show here, however, that the fitted slope n depends not only on the valency of element M, but also on how M interacts with oxygen, the dissolution of which as FeO in the sulfide increases as the FeO content of the silicate melt increases. To take account of interactions of trace element M with FeO dissolved in the sulfide we introduce an additional parameter ... (Wagner 1962), which represents the difference between the lithophile and chalcophile properties of M and those of Fe. If ... is positive, then element M is more chalcophile than Fe and if negative more lithophile. We performed experiments to investigate partitioning of lithophile Nb, Ta, Ce, and Ti between sulfide and simplified basaltic melt and find that they all exhibit, as expected, concave upward behavior on a plot of logD vs. log[FeO]. New experiments on Cu at low FeO contents confirm that it is more chalcophile than Fe, yielding a concave-downward curve of logD vs. log[FeO]. The combined results mean that nominally lithophile elements may partition more strongly into sulfide than nominally chalcophile elements at either very low or very high FeO contents of the silicate melt. For example, as the FeO content of the silicate melt declines below about 1 wt%, the partition coefficient of Cu, D_Cu^sulf/sil declines to an unusually low value (D_Cu^sulf/sil ~80), whereas those for Nb (D_Nb^sulf/sil ~600), and rare earths (REE's) increase strongly. Under these conditions, Nb is, therefore, substantially more "chalcophile" than Cu in that it partitions much more strongly into sulfide. The implications of these observations for the Earth are that under a wide range of conditions one would expect significant partitioning of REE, Nb, Ta, Ti, and other lithophile elements into sulfides. Wohlers and Wood (2015) have, for example, shown that the partitioning of U and the REE into sulfides at low FeO content of the silicate is sufficiently pronounced that addition of a reduced sulfur-rich body to the accreting Earth could generate observable fractionation of Nd from Sm and, together with S, transfer sufficient U to the core to provide a significant energy source for the geodynamo. [ABSTRACT FROM AUTHOR]