Comet water in lunar rocks

Halebopp031197
Comet Hale-Bopp.Image via Wikipedia

There are two main hypotheses about the origin of Earth’s oceans: that they are filled with water that was locked in the meteoritic matter that initially accreted to form the Earth, or ocean water was delivered by massive comet bombardment in the first half billion years of the Earth’s history. It hasn’t yet been possible to decide whether one of these, or both were  involved, but the Moon might give a clue, even though until very recently it was regarded as being bone dry (see Moon rocks turn out to be wetter and stranger in May 2010 issue of EPN). The ratio between deuterium and hydrogen (D/H) gives a clue to the origin of water, in which both hydrogen isotopes occur (Greenwood, J.P. et al. 2011. Hydrogen isotope ratios in lunar rocks indicate delivery of cometary water to the Moon. Nature Geoscience, v. 4, p. 79-82). Using an ion microprobe to analyse the water in apatite, its dominant host in lunar rock samples, the authors were able to report two things. First, there is water in magmatic rocks of all ages found on the Moon: the earliest anorthosites of the lunar highlands and the younger basalts that fill the dark maria. Secondly, the water has D/H ratios significantly outside the terrestrial range. In detail, apatites with the greatest enrichment of deuterium relative to hydrogen are found in the maria basalts which fill enormous basins thought to have formed around 4 Ga ago as a result of cometary impacts. The D/H ratios are lower in apatites from the lunar highland anorthosites, which probably formed through flotation of low density calcium-rich feldspar as the Moon’s initially molten mantle crystallized not long after its formation through the impact of a small planet with the Earth. The highland D/H values are not wildly dissimilar from those found on Earth, yet those found in the mare basalts match the admittedly less well-constrained levels determined from comets hale-Bopp, Hyakutake and Halley. Because the Earth’s mass would ensure that it would corral 15 times more incoming extraterrestrial matter than would the Moon, the argument goes that if the Moon captured cometary water then Earth did so in trumps. The difference is that the Earths greater gravitational pull and thick atmosphere allowed it to retain gaseous and liquid water, while the Moon’s lower escape velocity let them leak away so that only mineralogically bound water could be retained.

Whizz-bang hypothesis for the Younger Dryas bites the dust

Such has been the urge to leap on the impact theory of Earth system change, that virtually every drastic event recorded in the geological timescale has been linked by someone or other to the effects of bombardment by extraterrestrial objects. The most recent concerns the Younger Dryas and the extinction of the mammoths (see Whizz-bang view of Younger Dryas and Impact cause for Younger Dryas draws flak in EPN July 2007 and May 2008). The hypothesis stemmed from reports of an association of tiny magnetic spherules, soot and purported nanodiamonds and fullerenes (carbon molecules bonded into ‘geodesic’ spheres) with the onset of the Younger Dryas, the roughly coincident disappearance of Clovis tools and the demise of several large North American mammal species, including mammoths. Regular columnist for Science magazine, Richard Kerr, reports that independent searches for all the evidential materials at the sites where they were said to occur have drawn unrelieved blanks (Kerr, R.A. 2010. Mammoth-killer impact flunks out , Science, v. 329, p. 1140-1141). Nonetheless, the core supporters of the hypothesis are clinging to their guns.

Whizz-bang hypothesis for the Younger Dryas bites the dust

Such has been the urge to leap on the impact theory of Earth system change, that virtually every drastic event recorded in the geological timescale has been linked by someone or other to the effects of bombardment by extraterrestrial objects. The most recent concerns the Younger Dryas and the extinction of the mammoths (see Whizz-bang view of Younger Dryas and Impact cause for Younger Dryas draws flak in EPN July 2007 and May 2008). The hypothesis stemmed from reports of an association of tiny magnetic spherules, soot and purported nanodiamonds and fullerenes (carbon molecules bonded into ‘geodesic’ spheres) with the onset of the Younger Dryas, the roughly coincident disappearance of Clovis tools and the demise of several large North American mammal species, including mammoths. Regular columnist for Science magazine, Richard Kerr,  reports that independent searches for all the evidential materials at the sites where they were said to occur have drawn unrelieved blanks (Kerr, R.A. 2010. Mammoth-killer impact flunks out , Science, v. 329, p. 1140-1141). Nonetheless, the core supporters of the hypothesis are clinging to their guns.

Carbonates on Mars

Ancient valley systems, huge water-carved gorges and sedimentary deposits signify with little room for doubt that early in its history Mars was wet; it must therefore have been warm. A thick CO2-rich atmosphere seems obligatory to give the kind of greenhouse warming that prevented Earth from freezing over when the young Sun was weaker than now. The question is, where did the CO2 go so that the planet became chilled? Gravity on Mars is sufficient to have retained the gas, unlike water vapour that dissociates to hydrogen and oxygen, of which hydrogen easily escapes even a much stronger gravitational field. A consensus is developing that it resides in carbonate minerals. The other likely greenhouse gas is sulfur dioxide, for whose drawdown there is ample evidence in the form of sulfates detected from orbit and by surface rovers. Carbonates have a relatively simple, and unique spectrum of reflected solar radiation, with an absorption feature at a wavelength around 2.3 micrometres. Carbonates have been detected on Mars using orbital hyperspectral imaging, but only in patches. The NASA rovers rely on serendipity for any discovery, yet Spirit did stumble on a large carbonate-rich outcrop identified by its on-board Mössbauer spectrometer (Morris, R.V. and 12 others 2010. Identification of carbonate-rich outcrops on Mars by the Spirit rover. Science, v. 329, p. 421-424). It appears to be a Fe-Mg variety in association with olivines, and carbonate makes up to 34 % of part of the outcrop. The texture is granular, yet the area abounds with evidence for hydrothermal activity in the form of sulfates and silica-rich materials, implying that some kind of circulation system deposited the carbonates. The associated olivine is odd, as that mineral is prone to rapid breakdown to serpentines in the presence of water.

The discovery of carbonate rock does help the CO2 early greenhouse theory and the fate of the warming gas, but aside from the fact the identification has been done at vast distance does it rank with geoscience that can be accomplished on Earth? It is a small piece in the jigsaw of Mars’s climatic evolution, but cannot resolve the issue of drawdown of greenhouse gas. The real drama there lay in the finding of abundant signs of water erosion on many scales set against today’s surface hyperaridity; evidence for glaciation and subsurface water ice in apparently large volumes. Earth had to have had a thick CO2-rich atmosphere at the same time as that of Mars, but we are still not sure where all that carbon ended up in the early Precambrian, despite limestones and carbon-rich mudstones dating back to 3.4 Ga: as we cannot quantify that aspect of Earth’s history, neither can we expect an early answer for Mars. Indeed, what is the benefit set against the cost?

See also: Harvey, P. 2010. Carbonates and Martian climate. Science, v. 329, p. 400-401.

Wet Moon, dry Moon

Regular readers will remember my remarkable though very reluctant conversion to the notion that there may be water on Mars. My stubborn reaction had been against the background that shrouded the hypothesis with a certain desperation; the need of any future crewed mission to Mars for a water supply and thereby one of hydrogen fuel, plus the determination of the whole Mars-oriented community to justify such a mission by hyping ‘xenobiology’ on the ‘Red Planet’. A similar desperation claoked the search for surface water on the Moon, although one more dominated by the ‘Everest’ syndrome: since the boot prints and flags appeared, everyone wants to go. The Moons internal water is an entirely different kettle of fish. The hypothesis of the Moon’s formation by condensation from an incandescent mass flung into orbit after a planet – planet collision involving the Earth has the corollary that the lunar mantle ought to be bone dry: and so it seemed to be from bulk analyses of rocks brought back by the Apollo missions. In fact, there are a number of possibilities to explain vanishingly small amounts of internal water: the Moon is made of impactor that happened to be dry rather than terrestrial material; Earth and Moon are a mix of both and both Earth and impactor started out dry, but the Earth later received its water from comets; low pressure condensation of the Moon ruled out water entering itss silicate minerals and so on. Then water was found in apatite grains from lunar maria basalts (see Moon rocks turn out to be wetter and stranger in May 2010 issue of EPN). Within a couple of months we are back to the dry-as-an-alco’s-throat view (Sharp, Z.D. et al. 2010. The chlorine isotope composition of the Moon and implications for an anhydrous mantle. Science, v. 329, p. 1050-1053). Both terrestrial and meteoritic chlorine isotopes are in remarkably consistent proportions, but lunar rocks show an 25 times greater spread by comparison. To cut a long and complicated discussion short, such a range could only have formed if chlorides of a variety of metals were vaporised from lunar magmas each having its own effect on fractionation of Cl isotopes. In turn, combination of chlorine with metal ions requires virtually no hydrogen ions and therefore vanishingly little water in the moon, otherwise chlorine would have been combined in HCl and not subject to any fractionation when that volatilised on eruption. So that seems settled, then…

Wet Moon, dry Moon

Regular readers will remember my remarkable though very reluctant conversion to the notion that there may be water on Mars. My stubborn reaction had been against the background that shrouded the hypothesis with a certain desperation; the need of any future crewed mission to Mars for a water supply and thereby one of hydrogen fuel, plus the determination of the whole Mars-oriented community to justify such a mission by hyping ‘xenobiology’ on the ‘Red Planet’. A similar desperation claoked the search for surface water on the Moon, although one more dominated by the ‘Everest’ syndrome: since the boot prints and flags appeared, everyone wants to go. The Moons internal water is an entirely different kettle of fish. The hypothesis of the Moon’s formation by condensation from an incandescent mass flung into orbit after a planet – planet collision involving the Earth has the corollary that the lunar mantle ought to be bone dry: and so it seemed to be from bulk analyses of rocks brought back by the Apollo missions. In fact, there are a number of possibilities to explain vanishingly small amounts of internal water: the Moon is made of impactor that happened to be dry rather than terrestrial material; Earth and Moon are a mix of both and both Earth and impactor started out dry, but the Earth later received its water from comets; low pressure condensation of the Moon ruled out water entering itss silicate minerals and so on. Then water was found in apatite grains from lunar maria basalts (see Moon rocks turn out to be wetter and stranger in May 2010 issue of EPN). Within a couple of months we are back to the dry-as-an-alco’s-throat view (Sharp, Z.D. et al. 2010. The chlorine isotope composition of the Moon and implications for an anhydrous mantle. Science, v. 329, p. 1050-1053). Both terrestrial and meteoritic chlorine isotopes are in remarkably consistent proportions, but lunar rocks show an 25 times greater spread by comparison. To cut a long and complicated discussion short, such a range could only have formed if chlorides of a variety of metals were vaporised from lunar magmas each having its own effect on fractionation of Cl isotopes. In turn, combination of chlorine with metal ions requires virtually no hydrogen ions and therefore vanishingly little water in the moon, otherwise chlorine would have been combined in HCl and not subject to any fractionation when that volatilised on eruption. So that seems settled, then…

Carbonates on Mars

Ancient valley systems, huge water-carved gorges and sedimentary deposits signify with little room for doubt that early in its history Mars was wet; it must therefore have been warm. A thick CO2-rich atmosphere seems obligatory to give the kind of greenhouse warming that prevented Earth from freezing over when the young Sun was weaker than now. The question is, where did the CO2 go so that the planet became chilled? Gravity on Mars is sufficient to have retained the gas, unlike water vapour that dissociates to hydrogen and oxygen, of which hydrogen easily escapes even a much stronger gravitational field. A consensus is developing that it resides in carbonate minerals. The other likely greenhouse gas is sulfur dioxide, for whose drawdown there is ample evidence in the form of sulfates detected from orbit and by surface rovers. Carbonates have a relatively simple, and unique spectrum of reflected solar radiation, with an absorption feature at a wavelength around 2.3 micrometres. Carbonates have been detected on Mars using orbital hyperspectral imaging, but only in patches. The NASA rovers rely on serendipity for any discovery, yet Spirit did stumble on a large carbonate-rich outcrop identified by its on-board Mössbauer spectrometer (Morris, R.V. and 12 others 2010. Identification of carbonate-rich outcrops on Mars by the Spirit rover. Science, v. 329, p. 421-424). It appears to be a Fe-Mg variety in association with olivines, and carbonate makes up to 34 % of part of the outcrop. The texture is granular, yet the area abounds with evidence for hydrothermal activity in the form of sulfates and silica-rich materials, implying that some kind of circulation system deposited the carbonates. The associated olivine is odd, as that mineral is prone to rapid breakdown to serpentines in the presence of water.

The discovery of carbonate rock does help the CO2 early greenhouse theory and the fate of the warming gas, but aside from the fact the identification has been done at vast distance does it rank with geoscience that can be accomplished on Earth? It is a small piece in the jigsaw of Mars’s climatic evolution, but cannot resolve the issue of drawdown of greenhouse gas. The real drama there lay in the finding of abundant signs of water erosion on many scales set against today’s surface hyperaridity; evidence for glaciation and subsurface water ice in apparently large volumes. Earth had to have had a thick CO2-rich atmosphere at the same time as that of Mars, but we are still not sure where all that carbon ended up in the early Precambrian, despite limestones and carbon-rich mudstones dating back to 3.4 Ga: as we cannot quantify that aspect of Earth’s history, neither can we expect an early answer for Mars. Indeed, what is the benefit set against the cost?

See also: Harvey, P. 2010. Carbonates and Martian climate. Science, v. 329, p. 400-401.

Moon rocks turn out to be wetter and stranger

Since the original analyses of lunar rock samples brought back by the Apollo astronauts is has been widely accepted that they are almost totally anhydrous. Some even contain pristine metallic iron with not a trace of rust after more than 4 billion years. So, therefore, the entire Moon should be bone dry, except for possible rimes of ice preserved in deeply shadowed polar craters. This lack of water is one line of evidence used to support the Moon’s origin in a stupendous collision between the early Earth and a smaller companion planet shortly after their accretion. The event may have depleted volatile elements and compounds in the incandescent vaporised rock from which the Moon is believed to have condensed. There are traces of water in glass spherules from lunar dust, but that might have come from the impactors that blasted them from craters. But at this year’s Lunar and Planetary Science Conference – the fortieth since the first Apollo landing – evidence for water in lunar minerals was presented (Hand, E. 2010. Old rocks drown dry Moon theory. Nature, v. 464, p. 150-151). The water is in apatite grains that occur as crystals in lunar maria basalts, so must have come from the Moon’s mantle through partial melting. Modelling suggests tens of thousand time more water in the lunar interior than believed previously, albeit still much less than in the Earth. Equally surprising is the water’s isotopic composition: it has a much greater proportion of deuterium (2H) relative to hydrogen (1H) than does water in terrestrial igneous rocks. The giant impact hypothesis suggests that the proportions should be the same in both bodies. One possibility is that a fortuitous comet delivered water to a dried-out hot moon soon after it has coalesced from and orbiting incandescent cloud. Hopefully a full publication will appear soon.

 

Late formation of Earth’s atmosphere

Because the Earth’s mantle is rich in volatiles which escape from magmas that reach the surface, it has long been assumed that our planet’s atmosphere was self-produced by exhalation. But it turns out that noble gases in such exhalations do not match those in the atmosphere isotopically (Holland, G. et al. 2009. Meteorite Kr in Earth’s mantle suggests a late accretionary source for the atmosphere. Science, v. 326, p. 1522-1525). Greg Holland and colleagues from the Universities of Manchester and Houston measured krypton and xenon isotopes in volcanic CO2 emissions from New Mexico, and found that their proportions matched those in carbonaceous chondrites as does the Kr/Xe ratio. Those in the atmosphere are significantly different, resembling the values in the Sun. Comets may have delivered these gases after the original accretion of the Earth and the catastrophic formation of the Moon.

‘Follow the water’

Long, long ago an anonymous Roman wrote, ‘The first provision of any civilised society, after a code of law, is a reliable source of clean water’. Personally, I think the phrase ‘legalised bureaucracy’ in Latin was mistranslated to ‘code of law’. Whichever, planetary and life scientists might well like the adage for themselves: the sentiment applies nicely to active planetary tectonics and to the origin and survival of all conceivable life forms. The Earth has plenty of water at the surface and deep in the mantle. Without the second, the main mantle mineral olivine would be too stiff for the mantle to convect. Heat would build up within until magma formed in great abundance and emerged with a dreadful growl, as it did on Venus about 750 million years ago to repave the entire planet. It simply isn’t possible to think of answering the questions, ‘When did plate tectonics begin and life emerge?’ – let alone ‘How?’ – without first addressing where the Earth’s water came from and when our home world become so richly endowed.

In a very practical sense, these are the most important issues in geochemistry. Francis Albarède, of the École normale supérieure de Lyon, President of the European Association for Geochemistry and the first geochemist to deploy a multicollector, inductively coupled, plasma-source mass spectrometer, is a fitting person to review where the subdiscipline stands on them. (An MC-ICPMS is a tool for which many still yearn hopelessly.) His views appeared as a ‘Progress’ (a rare kind of Nature article) in the 29 October 2009 issue of Nature (Albarède, F. 2009. Volatile accretion history of the terrestrial planets and dynamic implications. Nature, v. 461, p. 1227-1233). The article casts doubt on the long-held views that when the Moon formed after a giant impact on the Earth, both bodies lost huge masses of volatiles, including water, and that Earth’s water-rich nature stemmed from repeated bombardment by volatile-rich comets up to about 3800 Ma.

Geochemical data are now available from a comet (Hyakutaki) and it contains twice the amount of deuterium relative to hydrogen that is in terrestrial seawater. The D/H ratio of carbonaceous chondrite meteorites is more Earth-like, and these primitive objects seem a more likely water source than comets. But did cataclysmic formation of the Earth-Moon system dehydrate both bodies and drive off other volatile matter? Planets and smaller bodies formed by gravitational accretion of solids that condensed from the initially hot gas or nebula that dominated the proto-solar system. Experiments show that condensation of the elements occurs in three discrete temperature ranges, separated by ranges in which few elements condense. Above around 1300 K the most refractory elements condensed, including oxides of some elements (Ca, Fe, Mg, Si) that now make silicate minerals, including the dominant mantle mineral olivine. Between 900-1200 K the alkali metals and some of the elements (chalcophile) that readily combine with sulfur emerged in solid form. In the third step from 500-800 K the more volatile chalcophile elements, including lead, and halogens condense, leaving four (Hg, O, N, C) that can take on solid form only below about 300 K. Interestingly, the proportions of volatile elements relative to refractory ones in the Earth, Moon and Martian meteorites are very low compared with those in carbonaceous chondrites. It is likely that volatile elements only accreted to the Inner Planets in small amounts before being swept to the outer reaches by an intense solar wind as the Sun was powering up, i.e. before nebular temperatures had fallen below about 1000 K. From that stems the inescapable conclusion that none of these planets were endowed with much water in their earliest forms.

Proportions of the lead isotopes 206Pb and 204Pb from terrestrial sulfide mineral deposits define a near-perfect linear relationship with the ages of mineralisation, from which an age can be estimated for the time the element lead appeared on Earth. That age is 4400 Ma; about 110 Ma younger than the actual age of the planet, and matches apparent ages derived from I-Xe and Pu-Xe decay schemes; iodine and xenon are volatile elements. This strongly supports the idea that 500-800 K condensates arrived late, and other evidence indicates that they and water ice were delivered by carbonaceous chondrite material falling towards the Sun from far beyond the orbits of the giant planets, once the early solar wind had lessened. That is, the Earth’s oceans formed very early in its history, and the mantle gained its water from them once hydrated lithosphere could founder deep into the evolving mantle by subduction. Albarède also summarises fascinating new ideas about the different course followed by Venus and Mars from essentially the same starting point. His ‘Progress’ is not difficult to read, and by marking the start of a new consensus in planetary evolution is of vital interest to all Earth scientists

Extraterrestrial water is also the subject of a Great Quest by NASA and other space agencies, though sadly an attempt on 9 October to prove that there is ice on the lunar surface, by hurling a US$79 million spacecraft at an obscure polar crater, produced no sensible results. Ironically, a couple of weeks later, three papers appeared in Science that document passive remote sensing evidence that the Moon contains a lot more water than long assumed (the most revealing is: Pieters, C.M. and 28 others 2009. Character and spatial distribution of OH/H2O on the surface of the Moon seen by M3 on Chandrayaan-1. Science, v. 326, p. 568-572). The Apollo samples  astonished geologists when they proved to be almost completely anhydrous, any signs of minor hydration being ascribed to contamination after collection. The Moon Mineralogy Mapper (M3) aboard India’s first lunar mission Chandrayaan is a hyperspectral imaging device that operates in the visible to SWIR range of EM wavelengths (0.4 – 3.0 mm). That range includes SWIR wavelengths beyond 2.4 mm where OH, water and water ice have large absorption features that are masked in terrestrial remote sensing by the high moisture content of Earth’s atmosphere. Pieters et al. attempted to model hydroxyl and water content in the lunar surface, and discovered significant amounts (a few tenths of a percent) in the polar regions. That they got results when the Moon was fully illuminated by the Sun suggests that this is not due to ice hidden from heating in shadows, but to minerals that contain molecularly bound water and hydroxyl ions. That begs the question of how the water got there. One possibility is the late arrival of volatile condensates as above, another that it is due to hydrogen (protons) from the solar wind reducing iron in silicate minerals to metallic iron and combination with the oxygen released. Expect loud hurrahs from devotees of Star Trek and NASA because one prerequisite of civilised society seems to be there on the Moon. But judging from the bureaucracies involved in space, getting the funds to use it will not be easy.

And now; salt domes on Mars

The front cover of the August 2009 issue of Geology could be mistaken for an exaggerated oblique aerial view of part of Iran’s Zagros Mountains, well known for their dissected salt domes. It is, however, a simulation of an aerial oblique using digital elevation data from the Valles Marineris area on Mars (Adams et al. 2009. Salt tectonics and collapse of Hebes Chasma, Valles Marineris, Mars. Geology, v.  37, p. 691-694). Hebes Chasma is a roughly oval, steep-sided depression the margins of which show clear signs of some kind of erosion. However, the depression has no outlet, so looks quite bizarre by terrestrial standards: and it is not the only such feature. At its core is a pericline of material that was formerly buried deeper than the flanks of the chasma, which are pretty much horizontal. Unlike the larger, nearby Valles Marineris, Hebes Chasma cannot have formed by erosion of the surface by a huge mass of flowing water, yet 100 thousand cubic kilometres of rock has simply disappeared. Explaining such a gigantic, weird feature taxes the imagination, but the authors do come up with a hypothesis. They reckon that the 105 km3 of material became some kind of thin, briny slurry during an early Martian heating event, which drained downwards into a vast aquifer. For that to happen demands a thick, subsurface layer of dirty ice that melted, and an extremely porous substrate able to channel away the escaping muddy brine. How the pericline formed is not explained, except that it appears in a lab model made of sand, glass beads and ductile silicone polymer, when the silicone drained out through slots in the model’s base. There is plenty of evidence that the surroundings of the chasma collapsed spectacularly, and if the pericline formed by the rising of low-density material dominated by ductile salts (or ice) then it is a likely story. But where did the 100 thousand km3 of gloopy brine go? My guess it followed a secret passage to emerge into the far larger Valles Marineris… Even if there is a crewed mission to Mars, to land anywhere near Valles Marineris would be suicidal, it is so precipitous. So, this is yet another Martian mystery that will linger in a febrile kind of way.