Cora Wohlgemuth-Ueberwasser

The Earth’s missing lead may not be in the core

Relative to the CI chondrite class of meteorites (widely thought to be the ‘building blocks’ of the terrestrial planets), the Earth is depleted in volatile elements. For most elements this depletion is thought to be a solar nebular signature, as chondrites show depletions qualitatively similar to that of the Earth. On the other hand, as lead is a volatile element, some Pb may also have been lost after accretion. The unique 206Pb/204Pb and 207Pb/204Pb ratios of the Earth’s mantle suggest that some lead was lost about 50 to 130 Myr after Solar System formation. This has commonly been explained by lead lost via the segregation of a sulphide melt to the Earth’s core, which assumes that lead has an affinity towards sulphide. Some models, however, have reconciled the Earth’s lead deficit with volatilization. Whichever model is preferred, the broad coincidence of U–Pb model ages with the age of the Moon suggests that lead loss may be related to the Moon-forming impact. Here we report partitioning experiments in metal–sulphide–silicate systems. We show that lead is neither siderophile nor chalcophile enough to explain the high U/Pb ratio of the Earth’s mantle as being a result of lead pumping to the core. The Earth may have accreted from initially volatile-depleted material, some lead may have been lost to degassing following the Moon-forming giant impact, or a hidden reservoir exists in the deep mantle with lead isotope compositions complementary to upper-mantle values; it is unlikely though that the missing lead resides in the core.

Sulfide oxidation as a process for the formation of copper rich magmatic sulfides

Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic–ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.