Deep hydrous mantle reservoir provides evidence for crustal recycling before 3.3 billion years ago.

Water strongly influences the physical properties of the mantle and enhances its ability to melt or convect. Its presence can also be used to trace recycling of surface reservoirs down to the deep mantle1, which makes knowledge of the water content in the Earth's interior and its evolution crucial for understanding global geodynamics. Komatiites (MgO-rich ultramafic magmas) result from a high degree of mantle melting at high pressures2 and thus are excellent probes of the chemical composition and water contents of the deep mantle. An excess of water over elements that show similar geochemical behaviour during mantle melting (for example, cerium) was recently found in melt inclusions in the most magnesium-rich olivine in 2.7-billion-year-old komatiites from Canada3 and Zimbabwe4. These data were taken as evidence for a deep hydrated mantle reservoir, probably the transition zone, in the Neoarchaean era (2.8 to 2.5 billion years ago). Here we confirm the mantle source of this water by measuring deuterium-to-hydrogen ratios in these melt inclusions and present similar data for 3.3-billion-year-old komatiites from the Barberton greenstone belt. From the hydrogen isotope ratios, we show that the mantle sources of these melts contained excess water, which implies that a deep hydrous mantle reservoir has been present in the Earth's interior since at least the Palaeoarchaean era (3.6 to 3.2 billion years ago). The reconstructed initial hydrogen isotope composition of komatiites is more depleted in deuterium than surface reservoirs or typical mantle but resembles that of oceanic crust that was initially altered by seawater and then dehydrated during subduction. Together with an excess of chlorine and depletion of lead in the mantle sources of komatiites, these results indicate that seawater-altered lithosphere recycling into the deep mantle, arguably by subduction, started before 3.3 billion years ago.

Komatiites reveal a hydrous Archaean deep-mantle reservoir.

Archaean komatiites (ultramafic lavas) result from melting under extreme conditions of the Earth's mantle. Their chemical compositions evoke very high eruption temperatures, up to 1,600 degrees Celsius, which suggests even higher temperatures in their mantle source. This message is clouded, however, by uncertainty about the water content in komatiite magmas. One school of thought holds that komatiites were essentially dry and originated in mantle plumes while another argues that these magmas contained several per cent water, which drastically reduced their eruption temperature and links them to subduction processes. Here we report measurements of the content of water and other volatile components, and of major and trace elements in melt inclusions in exceptionally magnesian olivine (up to 94.5 mole per cent forsterite). This information provides direct estimates of the composition and crystallization temperature of the parental melts of Archaean komatiites. We show that the parental melt for 2.7-billion-year-old komatiites from the Abitibi greenstone belt in Canada contained 30 per cent magnesium oxide and 0.6 per cent water by weight, and was depleted in highly incompatible elements. This melt began to crystallize at around 1,530 degrees Celsius at shallow depth and under reducing conditions, and it evolved via fractional crystallization of olivine, accompanied by minor crustal assimilation. As its major- and trace-element composition and low oxygen fugacities are inconsistent with a subduction setting, we propose that its high H2O/Ce ratio (over 6,000) resulted from entrainment into the komatiite source of hydrous material from the mantle transition zone. These results confirm a plume origin for komatiites and high Archaean mantle temperatures, and evoke a hydrous reservoir in the deep mantle early in Earth's history.

Isotopic evidence for continental ice sheet in mid-latitude region in the supergreenhouse Early Cretaceous.

Cretaceous represents one of the hottest greenhouse periods in the Earth's history, but some recent studies suggest that small ice caps might be present in non-polar regions during certain periods in the Early Cretaceous. Here we report extremely negative δ(18)O values of -18.12‰ to -13.19‰ for early Aptian hydrothermal zircon from an A-type granite at Baerzhe in northeastern China. Given that A-type granite is anhydrous and that magmatic zircon of the Baerzhe granite has δ(18)O value close to mantle values, the extremely negative δ(18)O values for hydrothermal zircon are attributed to addition of meteoric water with extremely low δ(18)O, mostly likely transported by glaciers. Considering the paleoaltitude of the region, continental glaciation is suggested to occur in the early Aptian, indicating much larger temperature fluctuations than previously thought during the supergreenhouse Cretaceous. This may have impact on the evolution of major organism in the Jehol Group during this period.

Atmospheric oxygenation caused by a change in volcanic degassing pressure.

The Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria and to changes in the compositions of volcanic gases, but not to the composition of erupting lavas--geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO(2)/H(2)S < 1 and low sulphur content. Emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late Archaean then led to widespread subaerial volcanism, which in turn yielded gases much richer in sulphur and dominated by SO(2). Dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere.

Linking mantle plumes, large igneous provinces and environmental catastrophes.

Large igneous provinces (LIPs) are known for their rapid production of enormous volumes of magma (up to several million cubic kilometres in less than a million years), for marked thinning of the lithosphere, often ending with a continental break-up, and for their links to global environmental catastrophes. Despite the importance of LIPs, controversy surrounds even the basic idea that they form through melting in the heads of thermal mantle plumes. The Permo-Triassic Siberian Traps--the type example and the largest continental LIP--is located on thick cratonic lithosphere and was synchronous with the largest known mass-extinction event. However, there is no evidence of pre-magmatic uplift or of a large lithospheric stretching, as predicted above a plume head. Moreover, estimates of magmatic CO(2) degassing from the Siberian Traps are considered insufficient to trigger climatic crises, leading to the hypothesis that the release of thermogenic gases from the sediment pile caused the mass extinction. Here we present petrological evidence for a large amount (15 wt%) of dense recycled oceanic crust in the head of the plume and develop a thermomechanical model that predicts no pre-magmatic uplift and requires no lithospheric extension. The model implies extensive plume melting and heterogeneous erosion of the thick cratonic lithosphere over the course of a few hundred thousand years. The model suggests that massive degassing of CO(2) and HCl, mostly from the recycled crust in the plume head, could alone trigger a mass extinction and predicts it happening before the main volcanic phase, in agreement with stratigraphic and geochronological data for the Siberian Traps and other LIPs.

Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event.

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse, but this explanation is difficult to reconcile with the rock record. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached approximately 400 nM throughout much of the Archaean eon, but dropped below approximately 200 nM by 2.5 Gyr ago and to modern day values ( approximately 9 nM) by approximately 550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.

The amount of recycled crust in sources of mantle-derived melts.

Plate tectonic processes introduce basaltic crust (as eclogite) into the peridotitic mantle. The proportions of these two sources in mantle melts are poorly understood. Silica-rich melts formed from eclogite react with peridotite, converting it to olivine-free pyroxenite. Partial melts of this hybrid pyroxenite are higher in nickel and silicon but poorer in manganese, calcium, and magnesium than melts of peridotite. Olivine phenocrysts' compositions record these differences and were used to quantify the contributions of pyroxenite-derived melts in mid-ocean ridge basalts (10 to 30%), ocean island and continental basalts (many >60%), and komatiites (20 to 30%). These results imply involvement of 2 to 20% (up to 28%) of recycled crust in mantle melting.

Evidence from meimechites and other low-degree mantle melts for redox controls on mantle-crust fractionation of platinum-group elements.

Understanding of the geochemistry of the chalcophile elements [i.e., Os, Ir, Ru, Pt, Pd (platinum-group elements), and Au, Cu, Ni] has been informed for at least 20 years by the common assumption that when crust-forming partial melts are extracted from the upper mantle, sulfide liquid in the restite sequesters chalcophile elements until the extent of partial melting exceeds approximately 25% and all of the sulfide has been dissolved in silicate melt [Hamlyn, P. R. & Keays, R. R. (1985) Geochim. Cosmochim. Acta 49, 1797-1811]. Here we document very high, unfractionated, chalcophile element concentrations in small-degree partial melts from the mantle that cannot be reconciled with the canonical residual sulfide assumption. We show that the observed high, unfractionated platinum-group element concentrations in small-degree partial melts can be attained if the melting takes place at moderately high oxygen fugacity, which will reduce the amount of sulfide due to the formation of sulfate and will also destabilize residual monosulfide solid solution by driving sulfide melts into the spinel-liquid divariant field. Magmas formed at high oxygen fugacity by small degrees of mantle melting can be important agents for the transfer of chalcophile elements from the upper mantle to the crust and may be progenitors of significant ore deposits of Pt, Pd, and Au.