Zn/Fe systematics in mafic and ultramafic systems: Implications for detecting major element heterogeneities in the Earth’s mantle

Oceanic basalts, such as mid-ocean ridge basalts (MORB) and ocean island basalts (OIB), are characterized by large isotopic and trace element variability that is hard to reconcile with partial melting of a peridotitic mantle alone. Their variability has been attributed to the presence of heterogeneities within the mantle, such as recycled crust, metasomatized material or outer core contribution. There have been few attempts to constrain the major element composition of those heterogeneities, most studies focusing on incompatible trace elements and radiogenic isotopes. Here, we report Zn, Mn and Fe systematics in mafic and ultramafic systems (whole-rocks and minerals) and we explore their use for detecting lithological heterogeneities that deviate from peridotitic mantle dominated by olivine and orthopyroxene. We suggest that Zn/Fe ratio is a particularly promising proxy. Zn/Fe fractionates equally between olivine, orthopyroxene and melt (e.g. the inter-mineral exchange coefficients  ∼  is ∼0.9-1), and the distribution of Zn/Fe between minerals appears to be temperature-independent within error. In contrast, clinopyroxene and garnet are characterized by low Zn/Fe ratios compared to co-existing melt, olivine and orthopyroxene, that is, and are both <<1. These partitioning behaviors imply that Zn/Fe ratios are minimally fractionated during partial melting of peridotite and differentiation of primitive basalts, if differentiation is dominated by olivine control. Thus, the Zn/Fe ratios of primitive basalts preserve the Zn/Fe ratio of the primary parental magma, providing insight into the signature of the mantle source region. We also infer that Zn/Fe ratios in melts are unlikely to be fractionated by modal variations in peridotitic material but are highly fractionated if garnet and/or clinopyroxene are the main phases in the source during melting. Similar Zn/Fe ratios between MORB and average upper mantle confirm the lack of fractionation during peridotite melting. However, high Zn/Fe ratios of some OIB cannot be explained by peridotite melting alone, but instead require the presence of high Zn/Fe lithologies or lithologies that have bulk exchange coefficients  < 1. All garnet-bearing or clinopyroxene-bearing lithologies, such as eclogites and garnet pyroxenites, fit the latter requirement.