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’.

Soluble iron, black smokers and climate


Phytoplankton bloom in the Channel off SW England (Landsat image)

At present the central areas of the oceans are wet deserts; too depleted in nutrients to support the photosynthesising base of a significant food chain. The key factor that is missing is dissolved divalent iron that acts as a minor, but vital, nutrient for phytoplankton. Much of the soluble iron that does help stimulate plankton ‘blooms’ emanates from the land surface in wind blown dust (Palaeoclimatology September 2011) or dissolved in river water. A large potential source is from hydrothermal vents on the ocean floor, which emit seawater that has circulated through the basalts of the oceanic crust. Such fluids hydrate the iron-rich mafic minerals olivine and pyroxene, which makes iron available for transport. The fluids originate from water held in the muddy, organic-rich sediments that coat the ocean floor, and have lost any oxygen present in ocean-bottom water. Their chemistry is highly reducing and thereby retains soluble iron liberated by crustal alteration to emanate from hydrothermal vents. Because cold ocean-bottom waters are oxygenated by virtue of having sunk from the surface as part of thermohaline circulation, it does seem that ferrous iron should quickly be oxidised and precipitated as trivalent ferric compounds soon after hydrothermal fluids emerge. However, if some was able to rise to the surface it could fertilise shallow ocean water and participate in phytoplankton blooms, the sinking of dead organic matter then effectively burying carbon beneath the ocean floor; a ‘biological pump’ in the carbon cycle with a direct influence on climate. Until recently this hypothesis had little observational support. Continue reading “Soluble iron, black smokers and climate”

Carbon dioxide burial: an analogy of some pitfalls

Schematic showing both terrestrial and geologi...
geological sequestration of carbon dioxide emissions from a coal-fired power plant.  (Photo credit: LeJean Hardin and Jamie Payne Wikipedia)

Of all the ‘geoengineering’ approaches that may offer some relief from global warming pumping CO2 into deep sedimentary rocks, through carbon capture and storage (CCS) is one that most directly intervenes in the natural carbon cycle. In fact it adds an almost wholly  anthropogenic route to the movement of carbon. It is difficult if not impossible for natural processes to ‘pump’ gases downwards except when they are dissolved in water and most often through the conversion of CO2 to solid carbonates or carbohydrates that are simply buried on the ocean floor. Artificially producing carbonate or organic matter on a sufficient scale to send meaningful amounts of anthropogenic carbon dioxide to long-term rock storage is pretty much beyond current technology, but gas sequestration seems feasible, if costly. The main issues concern making sure geological traps are ‘tight’ enough to prevent sufficient leakage to render the exercise of little use and to understand the geochemical effects of large amounts of buried gas that would inevitably move around to some extent.

The geochemistry is interesting as reactions of CO2 with rock and subsurface water are inevitable. The most obvious is that solution in water releases hydrogen ions to create weakly acidic fluids: on the one hand that might be a route for precipitation of carbonate and more secure carbon storage, through reaction with minerals (see, but another possibility is increasing solution of minerals that might eventually cause a trap to leak. A counterpart of pH change is the release of electrons, whose acceptance in chemical reactions creates reducing conditions. The most common minerals to be affected by reducing reactions are the iron oxides, hydroxides and sulfates that often coat sand-sized grains in sedimentary rocks, or occur as accessory minerals in igneous and metamorphic rocks. Iron in such minerals is in the Fe-3 valence state (ferric iron from which an electron has been lost through oxidation) which makes them among the least soluble common materials, provided conditions remain oxidising. Flooding sedimentary rocks with CO2 inevitably produces a commensurate flow of electrons that readily interact with Fe-3. The oxidised product Fe-2 (ferrousiron) is soluble in water, and so reduction breaks down iron-rich grain coatings. Much the same happens with less abundant manganese oxides and hydroxides. One important concern is that iron hydroxide (FeO.OH or goethite) has a molecular structure so open that it becomes a kind of geochemical sponge. Goethite may lock up a large range of otherwise soluble ions, including those of arsenic and some toxic metals. Should goethite be dissolved by reduction that toxic load moves into solution and can migrate.

Bleached zone with carbonate-oxide core in Jurassic Entrada Sandstone, Green River, Utah. (Image: Max Wigley, University of Cambridge)

Except where deep, carbonated groundwater leaks to the surface in springs – the famous Perrier brand of mineral water is an example – it is difficult to judge what is happing to gases and fluids at depth. But their long-past activity can leave signatures in sedimentary rocks exhumed to the surface. Most continental sandstones, formed either through river or wind action, are strongly coloured by iron minerals simply because of strongly oxidising conditions at the Earth’s surface for the past two billion years or more. Should reducing fluids move through the, the iron is dissolved and leached away to leave streaks and patches of bleached sandstone in otherwise red rocks. In a few cases an altogether more pervasive bleaching of hundreds of metres of rock marks the site of massive fluid-leakage zones. Terrestrial Mesozoic sedimentary sequences in the Green River area of Utah, USA exhibit spectacular examples, easily amenable to field and lab study (Wigley, M. et al. 2012. Fluid-mineral reactions and trace metal mobilization in an exhumed natural CO2 reservoir, Green River, Utah. Geology, v. 40, p. 555-558). There the bleaching rises up through the otherwise brown and yellow sandstones, cutting across the bedding. In the bleached zone, secondary calcite fills pore spaces. At the contact with unbleached sandstone there are layers of carbonate and metal oxides, enriched in cobalt, copper, zinc, nickel, lead, tin, molybdenum and chromium: not ores but clear signs confirming the general model of reductive dissolution of iron minerals and movement of metal-rich fluid. Carbon isotopes from the junction are richer in 13C than could be explained by the gas phase having been methane, and confirm naturally CO2 – rich fluids.

So, Green River provides a natural analogue for a carbon capture and storage system, albeit one that leaked so profusely it would be a latter day disaster zone. In that sense the site will help in deciding where not to construct CCS facilities.

Massive event in the Precambrian carbon cycle

English: Cyanobacteria
Cyanobacteria: earliest producers of oxygen in the Precambrian. Image via Wikipedia

The entire eukaryote domain of life, from alga to trees and fungi to animals, would not exist had it not been for the emergence of free oxygen in the oceans and atmosphere about 2.4 billion years ago; thanks in large part to the very much simpler photosynthetic blue-green bacteria. The chemistry behind this boils down to organisms being able to transfer electrons from elements and compounds in the inorganic world to build organic molecules incorporated in living things. Having lost electrons the inorganic donors become oxidised, for instance ferrous iron (Fe2+ or Fe-2) becomes ferric iron (Fe3+ or Fe-3) and  sulfide ions (S2-) become sulfate (SO42-) and the organic products that receive electrons principally involve reduction of carbon, on the OilRig principal – Oxidation involves loss of electrons, Reduction involves gain. Since the Great Oxygenation Event (GOE), ferric iron and sulfate ions now account for 75% of oxidation of the lithosphere and hydrosphere while free oxygen (O2) is a mere 2-3 % (Hayes, J.M. 2011. Earth’s redox history. Science. V. 334, p. 1654-1655; an excellent introduction to the geochemistry involved in the GOE and the carbon cycle). Free oxygen is around today only because more of it is produced than is consumed by its acting to oxidize ferrous iron and sulfide ions supplied mainly by volcanism, and carbon-rich material exposed to surface processes by erosion and sediment transport.

Eukaryote life has never been snuffed out for the last two billion years or so, but it has certainly had its ups and downs. To geochemists taking the long view oxygen might well seem to have steadily risen, but that is hardly likely in the hugely varied chemical factory that constitutes Earth’s surface environments, involving major geochemical cycles for carbon, iron, sulfur, nitrogen, phosphorus and so on, that all inveigle oxygen into reactions. Tabs can be kept on one of these cycles – that involving carbon – through the way in which the proportions of its stable isotopes vary in natural systems. If all geochemistry was in balance all the time, all materials that contain carbon would show the same proportions of 13C and 12C as the whole  Earth, but that is never the case. Living processes that fix carbon in organic compounds favour the lighter isotope, so they show a deficit of 13C relative to 12C signified by negative values of δ13C. The source of the carbon, for instance CO2 dissolved in sea water, thereby becomes enriched in 13C to achieve a positive value of δ13C, which may then be preserved in the form of carbonates in, for instance, fossil shells that ended up in limestones formed at the same time as organic processes were favouring the lighter isotope of carbon. Any organic carbon compounds that ocean-floor mud buried before they decayed (became oxidised) conversely would add their negative δ13C to the sediment. Searching for δ13C anomalies in limestones and carbonaceous mudrocks has become a major means of charting life’s ups and downs, and also what has happened to buried organic carbon through geological time.

A most interesting time to examine C-isotopes and the carbon cycle is undoubtedly the period immediately following the GOE, in the Palaeoproterozoic Era (2500 to 1600 Ma). From around 2200 to 2060 Ma the general picture is roughly constant, high positive values of δ13C (~+10‰): more organic carbon was being buried than was being oxidised to CO2. However, in drill cores through the Palaeoproterozoic of NW Russia carbonate carbon undergoes a sharp decline in its heavy isotope to give a negative δ13C  (~-14‰) while carbon in organic-rich sediments falls too (to~-40‰): definitely against the general  trend (Kump, L.R. et al. 2011. Isotopic evidence for massive oxidation of organic matter following the Great Oxidation Event. Science. V. 334, p. 1694-1696). Oxygen isotopes in the carbonates affected by the depletion in ‘heavy’ carbon show barely a flicker of change: a clear sign that the 13C δ13C deficit is not due to later alteration by hydrothermal fluids, as can sometimes cause deviant δ13C in limestones. It is more likely that a vast amount of organic carbon, buried in sediments or dissolved in seawater was oxidised to CO2 faster than biological activity was supplying dead material to be buried or dissolved. In turn, the overproduction of carbon dioxide dissolved in seawater to affect C-isotopes in limestones. Such an event would have entailed a sharp increase in oxygen production to levels capable of causing the oxidation (~ 1% of present levels). Yet this was not the time of the GOE (2400 Ma) but 300-400 Ma later. A possible explanation is a burst in oxygen production by more photosynthetic activity, perhaps by the evolution of chloroplast-bearing eukaryotes much larger than cyanobacteria.

The ultra-deep carbon cycle

A scattering of "brilliant" cut diam...
Image via Wikipedia

The presence of diamonds in the strange, potassium-rich, mafic to ultramafic igneous rocks known as kimberlites clearly demonstrates that there is carbon in the mantle, but it could have come from either biogenic carbon having moved down subduction zones or the original meteoritic matter that accreted to form the Earth. Both are distinct possibilities for which evidence can only be found within diamonds themselves as inclusions. There is a steady flow of publications focussed on diamond inclusions subsidised to some extent by companies that mine them (see Plate tectonics monitored by diamonds in EPN, 2 August 2011). The latest centres on the original source rocks of kimberlites and the depths that they reached (Walter, M.J. and 8 others 2011. Deep mantle cycling of oceanic crust: evidence from diamonds and their mineral inclusions. Science, v. 334, p. 54-57). The British, Brazilian and US team analysed inclusions in diamonds from Brazil, finding assemblages that are consistent with original minerals having formed below the 660 km upper- to lower-mantle seismic boundary and then adjusting to decreasing pressure as the kimberlite’s precursor rose to melt at shallower levels. The minerals – various forms of perovskite stable at deep-mantle pressures – from which the intricate composites of several lower-pressure phases exsolved suggest the diamonds originated around 1000 km below the surface; far deeper than did more common diamonds. Moreover, their geochemistry suggests that the inclusions formed from deeply subducted basalts of former oceanic crust.

Previous work on the carbon isotopes in ‘super-deep’ diamonds seemed to rule out a biogenic origin for the carbon, suggesting that surface carbon does not survive subduction into the lower mantle. In this case, however, the diamonds are made of carbon strongly enriched in light 12C relative to 13C, with δ13C values of around -20 ‰ (per thousand), which is far lower than that found in mantle peridotite and may have been subducted organic carbon. If that proves to be the case it extends the global carbon cycle far deeper than had been imagined, even by the most enthusiastic supporters of the Gaia hypothesis.