Olivine water contents in the continental lithosphere and the longevity of cratons.

Cratons, the ancient cores of continents, contain the oldest crust and mantle on the Earth (>2 Gyr old). They extend laterally for hundreds of kilometres, and are underlain to depths of 180-250 km by mantle roots that are chemically and physically distinct from the surrounding mantle. Forming the thickest lithosphere on our planet, they act as rigid keels isolated from the flowing asthenosphere; however, it has remained an open question how these large portions of the mantle can stay isolated for so long from mantle convection. Key physical properties thought to contribute to this longevity include chemical buoyancy due to high degrees of melt-depletion and the stiffness imparted by the low temperatures of a conductive thermal gradient. Geodynamic calculations, however, suggest that these characteristics are not sufficient to prevent the lithospheric mantle from being entrained during mantle convection over billions of years. Differences in water content are a potential source of additional viscosity contrast between cratonic roots and ambient mantle owing to the well-established hydrolytic weakening effect in olivine, the most abundant mineral of the upper mantle. However, the water contents of cratonic mantle roots have to date been poorly constrained. Here we show that olivine in peridotite xenoliths from the lithosphere-asthenosphere boundary region of the Kaapvaal craton mantle root are water-poor and provide sufficient viscosity contrast with underlying asthenosphere to satisfy the stability criteria required by geodynamic calculations. Our results provide a solution to a puzzling mystery of plate tectonics, namely why the oldest continents, in contrast to short-lived oceanic plates, have resisted recycling into the interior of our tectonically dynamic planet.

Oxidation state and metasomatism of the lithospheric mantle beneath the Rae Craton, Canada: strong gradients reflect craton formation and evolution.

We present the first oxidation state measurements for the subcontinental lithospheric mantle (SCLM) beneath the Rae craton, northern Canada, one of the largest components of the Canadian shield. In combination with major and trace element compositions for garnet and clinopyroxene, we assess the relationship between oxidation state and metasomatic overprinting. The sample suite comprises peridotite xenoliths from the central part (Pelly Bay) and the craton margin (Somerset Island) providing insights into lateral and vertical variations in lithospheric character. Our suite contains spinel, garnet-spinel and garnet peridotites, with most samples originating from 100 to 140 km depth. Within this narrow depth range we observe strong chemical gradients, including variations in oxygen fugacity (ƒO2) of over 4 log units. Both Pelly Bay and Somerset Island peridotites reveal a change in metasomatic type with depth. Observed geochemical systematics and textural evidence support the notion that Rae SCLM developed through amalgamation of different local domains, establishing chemical gradients from the start. These gradients were subsequently modified by migrating melts that drove further development of different types of metasomatic overprinting and variable oxidation at a range of length scales. This oxidation already apparent at ~ 100 km depth could have locally destabilised any pre-existing diamond or graphite.

Reduced methane-bearing fluids as a source for diamond.

Diamond formation in the Earth has been extensively discussed in recent years on the basis of geochemical analysis of natural materials, high-pressure experimental studies, or theoretical aspects. Here, we demonstrate experimentally for the first time, the spontaneous crystallization of diamond from CH4-rich fluids at pressure, temperature and redox conditions approximating those of the deeper parts of the cratonic lithospheric mantle (5-7 GPa) without using diamond seed crystals or carbides. In these experiments the fluid phase is nearly pure methane, even though the oxygen fugacity was significantly above metal saturation. We propose several previously unidentified mechanisms that may promote diamond formation under such conditions and which may also have implications for the origin of sublithospheric diamonds. These include the hydroxylation of silicate minerals like olivine and pyroxene, H2 incorporation into these phases and the "etching" of graphite by H2 and CH4 and reprecipitation as diamond. This study also serves as a demonstration of our new high-pressure experimental technique for obtaining reduced fluids, which is not only relevant for diamond synthesis, but also for investigating the metasomatic origins of diamond in the upper mantle, which has further implications for the deep carbon cycle.

Evidence for a dominantly reducing Archaean ambient mantle from two redox proxies, and low oxygen fugacity of deeply subducted oceanic crust.

Oxygen fugacity (ƒO2) is an intensive variable implicated in a range of processes that have shaped the Earth system, but there is controversy on the timing and rate of oxidation of the uppermost convecting mantle to its present ƒO2 around the fayalite-magnetite-quartz oxygen buffer. Here, we report Fe3+/ΣFe and ƒO2 for ancient eclogite xenoliths with oceanic crustal protoliths that sampled the coeval ambient convecting mantle. Using new and published data, we demonstrate that in these eclogites, two redox proxies, V/Sc and Fe3+/ΣFe, behave sympathetically, despite different responses of their protoliths to differentiation and post-formation degassing, seawater alteration, devolatilisation and partial melting, testifying to an unexpected robustness of Fe3+/ΣFe. Therefore, these processes, while causing significant scatter, did not completely obliterate the underlying convecting mantle signal. Considering only unmetasomatised samples with non-cumulate and little-differentiated protoliths, V/Sc and Fe3+/ΣFe in two Archaean eclogite suites are significantly lower than those of modern mid-ocean ridge basalts (MORB), while a third suite has ratios similar to modern MORB, indicating redox heterogeneity. Another major finding is the predominantly low though variable estimated ƒO2 of eclogite at mantle depths, which does not permit stabilisation of CO2-dominated fluids or pure carbonatite melts. Conversely, low-ƒO2 eclogite may have caused efficient reduction of CO2 in fluids and melts generated in other portions of ancient subducting slabs, consistent with eclogitic diamond formation ages, the disproportionate frequency of eclogitic diamonds relative to the subordinate abundance of eclogite in the mantle lithosphere and the general absence of carbonate in mantle eclogite. This indicates carbon recycling at least to depths of diamond stability and may have represented a significant pathway for carbon ingassing through time.

Oxidising agents in sub-arc mantle melts link slab devolatilisation and arc magmas.

Subduction zone magmas are more oxidised on eruption than those at mid-ocean ridges. This is attributed either to oxidising components, derived from subducted lithosphere (slab) and added to the mantle wedge, or to oxidation processes occurring during magma ascent via differentiation. Here we provide direct evidence for contributions of oxidising slab agents to melts trapped in the sub-arc mantle. Measurements of sulfur (S) valence state in sub-arc mantle peridotites identify sulfate, both as crystalline anhydrite (CaSO4) and dissolved SO42- in spinel-hosted glass (formerly melt) inclusions. Copper-rich sulfide precipitates in the inclusions and increased Fe3+/∑Fe in spinel record a S6+-Fe2+ redox coupling during melt percolation through the sub-arc mantle. Sulfate-rich glass inclusions exhibit high U/Th, Pb/Ce, Sr/Nd and δ34S (+ 7 to + 11‰), indicating the involvement of dehydration products of serpentinised slab rocks in their parental melt sources. These observations provide a link between liberated slab components and oxidised arc magmas.