Degassing of reduced carbon from planetary basalts.

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

Volatile content of lunar volcanic glasses and the presence of water in the Moon's interior.

The Moon is generally thought to have formed and evolved through a single or a series of catastrophic heating events, during which most of the highly volatile elements were lost. Hydrogen, being the lightest element, is believed to have been completely lost during this period. Here we make use of considerable advances in secondary ion mass spectrometry to obtain improved limits on the indigenous volatile (CO(2), H(2)O, F, S and Cl) contents of the most primitive basalts in the Moon-the lunar volcanic glasses. Although the pre-eruptive water content of the lunar volcanic glasses cannot be precisely constrained, numerical modelling of diffusive degassing of the very-low-Ti glasses provides a best estimate of 745 p.p.m. water, with a minimum of 260 p.p.m. at the 95 per cent confidence level. Our results indicate that, contrary to prevailing ideas, the bulk Moon might not be entirely depleted in highly volatile elements, including water. Thus, the presence of water must be considered in models constraining the Moon's formation and its thermal and chemical evolution.

Insights into the dynamics of mantle plumes from uranium-series geochemistry.

The long-standing paradigm that hotspot volcanoes such as Hawaii or Iceland represent the surface expression of mantle plumes--hot, buoyant upwelling regions beneath the Earth's lithosphere--has recently been the focus of controversy. Whether mantle plumes exist or not is pivotal for our understanding of the thermal, dynamic and compositional evolution of the Earth's mantle. Here we show that uranium-series disequilibria measured in hotspot lavas indicate that hotspots are indeed associated with hot and buoyant upwellings and that weaker (low buoyancy flux) hotspots such as Iceland and the Azores are characterized by lower excess temperatures than stronger hotspots such as Hawaii. This direct link between buoyancy flux and mantle temperature is evidence for the existence of mantle plumes.

Large sulfur isotope fractionation in lunar volcanic glasses reveals the magmatic differentiation and degassing of the Moon.

Sulfur isotope variations in mantle-derived lavas provide important constraints on the evolution of planetary bodies. Here, we report the first in situ measurements of sulfur isotope ratios dissolved in primitive volcanic glasses and olivine-hosted melt inclusions recovered from the Moon by the Apollo 15 and 17 missions. The new data reveal large variations in 34S/32S ratios, which positively correlates with sulfur and titanium contents within and between the distinct compositional groups of volcanic glasses analyzed. Our results uncover several magmatic events that fractionated the primordial sulfur isotope composition of the Moon: the segregation of the lunar core and the crystallization of the lunar magma ocean, which led to the formation of the heterogeneous sources of the lunar magmatism, followed by magma degassing during generation, transport, and eruption of the lunar lavas. Whether the Earth's and Moon's interiors share a common 34S/32S ratio remains a matter of debate.

Hydrogen isotopes in lunar volcanic glasses and melt inclusions reveal a carbonaceous chondrite heritage.

Water is perhaps the most important molecule in the solar system, and determining its origin and distribution in planetary interiors has important implications for understanding the evolution of planetary bodies. Here we report in situ measurements of the isotopic composition of hydrogen dissolved in primitive volcanic glass and olivine-hosted melt inclusions recovered from the Moon by the Apollo 15 and 17 missions. After consideration of cosmic-ray spallation and degassing processes, our results demonstrate that lunar magmatic water has an isotopic composition that is indistinguishable from that of the bulk water in carbonaceous chondrites and similar to that of terrestrial water, implying a common origin for the water contained in the interiors of Earth and the Moon.

High pre-eruptive water contents preserved in lunar melt inclusions.

The Moon has long been thought to be highly depleted in volatiles such as water, and indeed published direct measurements of water in lunar volcanic glasses have never exceeded 50 parts per million (ppm). Here, we report in situ measurements of water in lunar melt inclusions; these samples of primitive lunar magma, by virtue of being trapped within olivine crystals before volcanic eruption, did not experience posteruptive degassing. The lunar melt inclusions contain 615 to 1410 ppm water and high correlated amounts of fluorine (50 to 78 ppm), sulfur (612 to 877 ppm), and chlorine (1.5 to 3.0 ppm). These volatile contents are very similar to primitive terrestrial mid-ocean ridge basalts and indicate that some parts of the lunar interior contain as much water as Earth's upper mantle.

Vapour undersaturation in primitive mid-ocean-ridge basalt and the volatile content of Earth's upper mantle.

The analysis of volatiles in magmatic systems can be used to constrain the volatile content of the Earth's mantle and the influence that magmatic degassing has on the chemistry of the oceans and the atmosphere. But most volatile elements have very low solubilities in magmas at atmospheric pressure, and therefore virtually all erupted lavas are degassed and do not retain their primary volatile signatures. Here we report the undersaturated pre-eruptive volatile content for a suite of mid-ocean-ridge basalts from the Siqueiros intra-transform spreading centre. The undersaturation leads to correlations between volatiles and refractory trace elements that provide new constraints on volatile abundances and their behaviour in the upper mantle. Our data generate improved limits on the abundances of carbon dioxide, water, fluorine, sulphur and chlorine in the source of normal mid-ocean-ridge basalt. The incompatible behaviour of carbon dioxide, together with the CO(2)/Nb and CO(2)/Cl ratios, permit estimates of primitive carbon dioxide and chlorine to be made for degassed and chlorine-contaminated mid-ocean-ridge basalt magmas, and hence constrain degassing and contamination histories of mid-ocean ridges.