Vanadium in peridotites as a proxy for paleo-fO2 during partial melting : prospects, limitations, and implications

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO₂): at high fO₂’s, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO₂ at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO₂. V-MgO and V-Al₂O₃ systematics were found to be sensitive to fO₂ variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO₂ differences greater than ∼2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al₂O₃ systematics that can be modeled by 1.5 GPa melting between FMQ − 3 and FMQ − 1. This is consistent with fO₂’s of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe³⁺ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO₂’s as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO₂’s in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO₂ during partial melting, whereas the activity of Fe³⁺ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively.Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ∼FMQ − 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO₂’s. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO₂ content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO₂’s significantly greater than that of modern oceanic mantle. Instead, the fO₂’s inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.