Anomalous sulphur isotopes in plume lavas reveal deep mantle storage of Archaean crust.

Basaltic lavas erupted at some oceanic intraplate hotspot volcanoes are thought to sample ancient subducted crustal materials. However, the residence time of these subducted materials in the mantle is uncertain and model-dependent, and compelling evidence for their return to the surface in regions of mantle upwelling beneath hotspots is lacking. Here we report anomalous sulphur isotope signatures indicating mass-independent fractionation (MIF) in olivine-hosted sulphides from 20-million-year-old ocean island basalts from Mangaia, Cook Islands (Polynesia), which have been suggested to sample recycled oceanic crust. Terrestrial MIF sulphur isotope signatures (in which the amount of fractionation does not scale in proportion with the difference in the masses of the isotopes) were generated exclusively through atmospheric photochemical reactions until about 2.45 billion years ago. Therefore, the discovery of MIF sulphur in these young plume lavas suggests that sulphur--probably derived from hydrothermally altered oceanic crust--was subducted into the mantle before 2.45 billion years ago and recycled into the mantle source of Mangaia lavas. These new data provide evidence for ancient materials, with negative Δ(33)S values, in the mantle source for Mangaia lavas. Our data also complement evidence for recycling of the sulphur content of ancient sedimentary materials to the subcontinental lithospheric mantle that has been identified in diamond-hosted sulphide inclusions. This Archaean age for recycled oceanic crust also provides key constraints on the length of time that subducted crustal material can survive in the mantle, and on the timescales of mantle convection from subduction to upwelling beneath hotspots.

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.

Nominally hydrous magmatism on the Moon.

For the past 40 years, the Moon has been described as nearly devoid of indigenous water; however, evidence for water both on the lunar surface and within the lunar interior have recently emerged, calling into question this long-standing lunar dogma. In the present study, hydroxyl (as well as fluoride and chloride) was analyzed by secondary ion mass spectrometry in apatite [Ca(5)(PO(4))(3)(F,Cl,OH)] from three different lunar samples in order to obtain quantitative constraints on the abundance of water in the lunar interior. This work confirms that hundreds to thousands of ppm water (of the structural form hydroxyl) is present in apatite from the Moon. Moreover, two of the studied samples likely had water preserved from magmatic processes, which would qualify the water as being indigenous to the Moon. The presence of hydroxyl in apatite from a number of different types of lunar rocks indicates that water may be ubiquitous within the lunar interior, potentially as early as the time of lunar formation. The water contents analyzed for the lunar apatite indicate minimum water contents of their lunar source region to range from 64 ppb to 5 ppm H(2)O. This lower limit range of water contents is at least two orders of magnitude greater than the previously reported value for the bulk Moon, and the actual source region water contents could be significantly higher.

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.

Sulfur isotopes in diamonds reveal differences in continent construction.

Neoproterozoic West African diamonds contain sulfide inclusions with mass-independently fractionated (MIF) sulfur isotopes that trace Archean surficial signatures into the mantle. Two episodes of subduction are recorded in these West African sulfide inclusions: thickening of the continental lithosphere through horizontal processes around 3 billion years ago and reworking and diamond growth around 650 million years ago. We find that the sulfur isotope record in worldwide diamond inclusions is consistent with changes in tectonic processes that formed the continental lithosphere in the Archean. Slave craton diamonds that formed 3.5 billion years ago do not contain any MIF sulfur. Younger diamonds from the Kaapvaal, Zimbabwe, and West African cratons do contain MIF sulfur, which suggests craton construction by advective thickening of mantle lithosphere through conventional subduction-style horizontal tectonics.

Experimental constraints on the damp peridotite solidus and oceanic mantle potential temperature.

Decompression of hot mantle rock upwelling beneath oceanic spreading centers causes it to exceed the melting point (solidus), producing magmas that ascend to form basaltic crust ~6 to 7 kilometers thick. The oceanic upper mantle contains ~50 to 200 micrograms per gram of water (H2O) dissolved in nominally anhydrous minerals, which-relative to its low concentration-has a disproportionate effect on the solidus that has not been quantified experimentally. Here, we present results from an experimental determination of the peridotite solidus containing known amounts of dissolved hydrogen. Our data reveal that the H2O-undersaturated peridotite solidus is hotter than previously thought. Reconciling geophysical observations of the melting regime beneath the East Pacific Rise with our experimental results requires that existing estimates for the oceanic upper mantle potential temperature be adjusted upward by about 60°C.

Early accretion of water and volatile elements to the inner Solar System: evidence from angrites.

Inner Solar System bodies are depleted in volatile elements relative to chondrite meteorites, yet the source(s) and mechanism(s) of volatile-element depletion and/or enrichment are poorly constrained. The timing, mechanisms and quantities of volatile elements present in the early inner Solar System have vast implications for diverse processes, from planetary differentiation to the emergence of life. We report major, trace and volatile-element contents of a glass bead derived from the D'Orbigny angrite, the hydrogen isotopic composition of this glass bead and that of coexisting olivine and silicophosphates, and the 207Pb-206Pb age of the silicophosphates, 4568 ± 20 Ma. We use volatile saturation models to demonstrate that the angrite parent body must have been a major body in the early inner Solar System. We further show via mixing calculations that all inner Solar System bodies accreted volatile elements with carbonaceous chondrite H and N isotope signatures extremely early in Solar System history. Only a small portion (if any) of comets and gaseous nebular H species contributed to the volatile content of the inner Solar System bodies.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

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.

Mantle shear-wave velocity structure beneath the Hawaiian hot spot.

Defining the mantle structure that lies beneath hot spots is important for revealing their depth of origin. Three-dimensional images of shear-wave velocity beneath the Hawaiian Islands, obtained from a network of sea-floor and land seismometers, show an upper-mantle low-velocity anomaly that is elongated in the direction of the island chain and surrounded by a parabola-shaped high-velocity anomaly. Low velocities continue downward to the mantle transition zone between 410 and 660 kilometers depth, a result that is in agreement with prior observations of transition-zone thinning. The inclusion of SKS observations extends the resolution downward to a depth of 1500 kilometers and reveals a several-hundred-kilometer-wide region of low velocities beneath and southeast of Hawaii. These images suggest that the Hawaiian hot spot is the result of an upwelling high-temperature plume from the lower mantle.

Osmium isotopes and mantle convection.

The decay of (187)Re to (187)Os (with a half-life of 42 billion years) provides a unique isotopic fingerprint for tracing the evolution of crustal materials and mantle residues in the convecting mantle. Ancient subcontinental mantle lithosphere has uniquely low Re/Os and (187)Os/(188)Os ratios due to large-degree melt extraction, recording ancient melt-depletion events as old as 3.2 billion years. Partial melts have Re/Os ratios that are orders of magnitude higher than their sources, and the subduction of oceanic or continental crust introduces into the mantle materials that rapidly accumulate radiogenic (187)Os. Eclogites from the subcontinental lithosphere have extremely high (187)Os/(188)Os ratios, and record ages as old as the oldest peridotites. The data show a near-perfect partitioning of Re/Os and (187)Os/(188)Os ratios between peridotites (low) and eclogites (high). The convecting mantle retains a degree of Os-isotopic heterogeneity similar to the lithospheric mantle, although its amplitude is modulated by convective mixing. Abyssal peridotites from the ocean ridges have low Os isotope ratios, indicating that the upper mantle had undergone episodes of melt depletion prior to the most recent melting events to produce mid-ocean-ridge basalt. The amount of rhenium estimated to be depleted from the upper mantle is 10 times greater than the rhenium budget of the continental crust, requiring a separate reservoir to close the mass balance. A reservoir consisting of 5-10% of the mantle with a rhenium concentration similar to mid-ocean-ridge basalt would balance the rhenium depletion of the upper mantle. This reservoir most likely consists of mafic oceanic crust recycled into the mantle over Earth's history and provides the material that melts at oceanic hotspots to produce ocean-island basalts (OIBs). The ubiquity of high Os isotope ratios in OIB, coupled with other geochemical tracers, indicates that the mantle sources of hotspots contain significant quantities (greater than 10%) of lithologically distinct mafic material which represents ancient oceanic lithosphere cycled through the convecting mantle on a time-scale of 800 million years or more.

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.

Numerical models, geochemistry and the zero-paradox noble-gas mantle.

Numerical models of whole-mantle convection demonstrate that degassing of the mantle is an inefficient process, resulting in ca. 50% of the (40)Ar being degassed from the mantle system. In this sense the numerical simulations are consistent with the (40)Ar mass balance between the atmosphere and mantle reservoir. These models, however, are unable to preserve the large-scale heterogeneity predicted by models invoking geochemical layering of the mantle system. We show that the three most important noble-gas constraints on the geochemically layered mantle are entirely dependent on the (3)He concentration of the convecting mantle derived from the (3)He flux into the oceans and the average ocean-crust generation rate. A factor of 3.5 increase in the convecting-mantle noble-gas concentration removes all requirements for: a (3)He flux into the upper mantle from a deeper high (3)He source; a boundary in the mantle capable of separating heat from helium; and a substantial deep-mantle reservoir to contain a hidden (40)Ar rich reservoir. We call this model concentration for the convecting mantle the 'zero-paradox' concentration. The time-integrated flux of (3)He into the oceans is a robust observation, but only representative of the ocean-floor activity over the last 1000 years. In contrast, ocean-floor generation occurs over tens of millions of years. We argue that combining these two observations to obtain the (3)He concentration of the mantle beneath mid-ocean ridges is unsound. Other indicators of mantle (3)He concentration suggest that the real value may be at least a factor of two higher. As the zero-paradox concentration is approached, the noble-gas requirement for mantle layering is removed. We further consider the role that recycled material plays in ocean-island-basalt generation and show that a source with high (3)He and (3)He/(4)He must exist within the mantle. Nevertheless, only a small amount of this material is required to generate both the observed ocean-island (3)He/(4)He ratios and the concentrations inferred from basalt samples for this mantle source.