Diamonds and the deep carbon cycle

When considering the fate of the element carbon and CO2, together with all their climatic connotations, it is easy to forget that they may end up back in the Earth’s mantle from which they once escaped to the surface. In fact all geochemical cycles involve rock, so that elements may find their way into the deep Earth through subduction, and they could eventually come out again: the ‘logic’ of plate tectonics. Teasing out the various routes by which carbon might get to mantle is not so easily achieved. Yet one of the ways it escapes is through the strange magma that once produced kimberlite intrusions, in the form of pure-carbon crystals of diamond that kimberlites contain. A variety of petrological and geochemical techniques, some hinging on other minerals that occur as inclusions, has allowed mineralogists to figure out that diamonds may form at depths greater than about 150 km. Most diamonds of gem quality formed in unusually thick lithosphere beneath the stable, and relatively cool blocks of ancient continental crust known as cratons, which extends to about 250 km. But there are a few that reflect formation depths as great as 800 km that span two major discontinuities in the mantle (at 410 and 660 km depth). These transition zones are marked by sudden changes in seismic speed due to pressure-induced transformations in the structure and density of the main mantle mineral, olivine.

Diamond crystal containing a garnet and other inclusions (Credit: Stephen Richardson, University of Cape Town, South Africa)

Carbon-rich rocks that may be subducted are not restricted to limestones and carbon-rich mudstones. Far greater in mass are the basalts of oceanic crust. Not especially rich in carbon when they crystallised as igneous rocks, their progress away from oceanic spreading centres exposes them to infiltration by ocean water. Once heated, aqueous fluids cause basalts to be hydrothermally altered. Anhydrous feldspars, pyroxenes and olivines react with the fluids to break down to hydrated-silicate clays and dissolved metals. Dissolved carbon dioxide combines with released calcium and magnesium to form pervasive carbonate minerals, often occupying networks of veins. So there has been considerable dispute as to whether subducted sediments or igneous rocks of the oceanic crust are the main source of diamonds. Diamonds with gem potential form only a small proportion of recovered diamonds. Most are only saleable for industrial uses as the ultimate natural abrasive and so are cheaply available for research. This now centres on the isotopic chemistry of carbon and nitrogen in the diamonds themselves and the various depth-indicating silicate minerals that occur in them as minute inclusions, most useful being various types of garnet.

The depletion of diamonds in ‘heavy’ 13C once seemed to match that of carbonaceous shales and the carbonates in fossil shells, but recent data from carbonates in oceanic basalts reveals similar carbon, giving three possibilities. Yet, when their nitrogen-isotope characteristics are taken into account, even diamonds that formed at lithospheric depths do not support a sedimentary source (Regier, M.E. et al. 2020. The lithospheric-to-lower-mantle carbon cycle recorded in superdeep diamonds. Nature, v. 585, p. 234–238; DOI: 10.1038/s41586-020-2676-z). That leaves secondary carbonates in subducted oceanic basalts as the most likely option, the nitrogen isotopes more reminiscent of clays formed from igneous minerals by hydrothermal processes than those created by weathering and sedimentary deposition. However, diamonds with the deepest origins – below the 660 km mantle transition zone – suggest yet another possibility, from the oxygen isotopes of their inclusions combined with those of C and N in the diamonds. All three have tightly constrained values that most resemble those from pristine mantle that has had no interaction with crustal rocks. At such depths, unaltered mantle probably contains carbon in the form of metal alloys and carbides. Regier and colleagues suggest that subducted slabs reaching this environment – the lower mantle – may release watery fluids that mobilise carbon from such alloys to form diamonds. So, I suppose, such ultra-deep diamonds may be formed from the original stellar stuff that accreted to form the Earth and never since saw the ‘light of day’.

Evidence for comet impact in the Sahara Desert

The desert surface of the remote Sahara of SW Egypt and adjacent Libya is strewn with silica-rich glass over an area of up to 6500 km2.  Pale yellow in colour and translucent, the glass clearly attracted Pleistocene hunter gatherers who manufactured edged tools  from it. Pieces cut en cabouchon are also found in pharaonic jewellery, including an item found in the tomb of Tutankhamun. Evidence for its formation at very high temperature is the melting temperature of pure silica around 2000°C and the presence of baddeleyite, a breakdown product of zircon. The glass fragments are undoubtedly the product of shock heating of desert sand or the local Nubian Sandstone of Cretaceous age by some kind of extraterrestrial impact. Fission-track dating suggests the glass formed around 29 Ma ago. A possible source is a 30 km wide crater on the Gilf Kebir Plateau made famous by Michael Ondaatje’s novel The English Patient that was centered on Pleistocene rock art discovered at the Cave of Swimmers in the Nubian Sandstone.

Tutanhkamun pendant with Wadjet
Scarab cut from Libyan Desert Glass in a pendant from the tomb of Tutanhkamun (credit: Wikipedia)

Neither the crater nor the glass strewn field yields meteoritic material despite several expeditions but the platinum-group metal content of the glass indicates an impact origin. Some specimens include enigmatic, graphite-rich banding. However, recently a South African-French team studied a strange, irregular 30 g fragment picked up in 1996 by an Egyptian postgraduate student collecting samples from the strewn field. He discovered that the dark fragment contained diamond by using X-ray diffraction. The dominant element in the fragment is carbon with less than 5% silicates and the new study used a battery of geochemical tests that confirmed the presence of abundant tiny diamonds (Kramers, J.D. and 13 others 2013. Unique chemistry of a diamond bearing pebble from the Libyan Desert Glass strewn field, SW Egypt: Evidence for a shocked comet fragment. Earth and Planetary Science Letters, v. 382, p. 21-31).

Conceivably, the diamonds could have formed by shock metamorphism of a coal seam or other carbonaceous sediments at the site of an impact – the K-T boundary layer formed by the huge Chicxulub impact contains nano-diamonds. However none of the chemical characteristics, including noble gas isotopic proportions and those of carbon, match terrestrial organic matter. Nor do they match carbonaceous chondrite meteorites that could have been another potential source, in its case an impactor of that composition. Instead, much evidence suggests the fragment is chemically akin to interplanetary dust and dust from the coma of comet 81P/Wild2 captured by NASDA’s Stardust mission in 2004. A plausible explanation, therefore, for the glass strewn field is an airburst explosion of a comet nucleus above the Sahara, the particle being a shocked fragment of the comet itself.

Plate tectonics monitored by diamonds

eclogite
Norwegian Eclogite. Image by kevinzim via Flickr

For more than 30 years a debate has raged about the antiquity of plate tectonics: some claim it has always operated since the Earth first acquired a rigid carapace not long after a molten state following formation of the Moon; others look to the earliest occurrences of island-arc volcanism, oceanic crust thrust onto continents as ophiolite complexes, and to high-pressure, low-temperature metamorphic rocks. The earliest evidence of this kind has been cited from as far apart in time as the oldest Archaean rocks of Greenland (3.9 Ga) and the Neoproterozoic (1 Ga to 542 Ma). A key feature produced by plate interactions that can be preserved are high-P, low-T rocks formed where old, cool oceanic lithosphere is pulled by its own increasing density into the mantle at subduction zones to form eclogites and blueschists. In the accessible crust, both rock types are unstable as well as rare and can be retrogressed to different metamorphic mineral assemblages by high-temperature events at lower pressures than those at which they formed. Relics dating back to the earliest subduction may be in the mantle, but that seems inaccessible. Yet, from time to time explosive magmatism from very deep sources brings mantle-depth materials to the surface in kimberlite pipes that are most commonly found in stabilised blocks of ancient continental crust or cratons. Again there is the problem of mineral stability when solids enter different physical conditions, but there is one mineral that preserves characteristics of its deep origins – diamond. Steven Shirer and Stephen Richardson of the Carnegie Institution of Washington and the University of Cape Town have shed light on early subduction by exploiting the relative ease of dating diamonds and their capacity for preserving other minerals captured within them (Shirey, S.B. & Richardson, S.H. 2011. Start of the Wilson cycle at 3 Ga shown by diamonds from the subcontinental mantle. Science, v. 333, p. 434-436). Their study used data from over four thousand silicate inclusions in previously dated large diamonds, made almost worthless as gemstones by their contaminants. It is these inclusions that are amenable to dating, principally by the Sm-Nd method. Adrift in the mantle high temperature would result in daughter isotopes diffusing from the minerals. Once locked within diamond that isotopic loss would be stopped by the strength of the diamond structure, so building up with time to yield an age of entrapment when sampled.  The collection spans five cratons in Australia, Africa, Asia and North America, and has an age spectrum from 1.0 to 3.5 Ga. Note that diamonds are not formed by subduction but grow as a result of reduction of carbonates or oxidation of methane in the mantle at depths between 125 to 175 km. In growing they may envelop fragments of their surroundings that formed by other processes.

A notable feature of the inclusions is that before 3.2 Ga only mantle peridotites (olivine and pyroxene) are trapped, whereas in diamonds younger than 3.0 Ga the inclusions are dominated by eclogite minerals (garnet and Na-, Al-rich omphacite pyroxenes). This dichotomy is paralleled by the rhenium and osmium isotope composition of sulfide mineral inclusions. To the authors these consistent features point to an absence of steep-angled subduction, characteristic of modern plate tectonics, from the Earth system before 3 Ga. But does that rule out plate tectonics in earlier times and cast doubt on structural and other evidence for it? Not entirely, because consumption of spreading oceanic lithosphere by the mantle can take place if basaltic rock is not converted to eclogite by high-P, low-T metamorphism when the consumed lithosphere is warmer than it generally is nowadays – this happens beneath a large stretch of the Central Andes where subduction is at a shallow angle. What Shirey and Richardson have conveyed is a sense that the dominant force of modern plate tectonics – slab-pull that is driven by increased density of eclogitised basalt – did not operate in the first 1.5 Ga of Earth history. Eclogite can also form, under the right physical conditions, when chunks of basaltic material (perhaps underplated magmatically to the base of continents) founder and fall into the mantle. The absence of eclogite inclusions seems also to rule out such delamination from the early Earth system. So whatever tectonic activity and mantle convection did take place upon and within the pre-3 Ga Earth it was probably simpler than modern geodynamics. The other matter is that the shift to dominant eclogite inclusions appears quite abrupt from the data, perhaps suggesting major upheavals around 3 Ga. The Archaean cratons do provide some evidence for a major transformation in the rate of growth of continental crust around 3 Ga; about 30-40 percent of modern continental material was generated in the following 500 Ma to reach a total of 60% of the current amount, the remaining 40% taking 2.5 Ga to form through modern plate tectonics