Exciting extraterrestrial eclogites

Eclogites are beautiful rocks that on Earth are associated with the process of subduction – where pieces of crust sink into the deep mantle region. A recent paper by Makoto Kimura and 5 other Japanese authors, describes the first ever evidence of eclogitic rocks found beyond Earth, formed within an unusually large asteroid now found only as tiny pieces.

ZS Unit Aosta valley, glaucophane bearing eclogite (scanned thin section 50x30mm) showing that glaucophane may be stable under eclogite facies, together with omphcite + grt _ rutile

A terrestrial eclogite in thin-section

Our authors were studying samples of a meteorite1 called a chondrite. It contains numerous small fragments (“clasts”) of different types. The paper focuses on a single set of clasts that contain distinctive eclogitic minerals – omphacite and pyrope-rich garnet. The sample also contains more typical minerals such as olivine and orthopyroxene. All of the Sodium and Aluminium within the sample is found within the garnet and omphacite – indicative of formation under high pressure. Based on the black arts of geothermobarometry our authors estimate formation under conditions of 2.8–4.2 GPa and 940–1080 °C.

On earth, eclogitic minerals are associated with subduction because this is a process that makes rocks experience high pressures and provides mechanisms for getting them back to the surface where we can enjoy then. This meteorite sample formed in a different world 2 – so there is no need to infer subduction on another body, but it is still remarkable (comment added later). To quote the paper: “It is believed that meteorites formed in small asteroidal bodies under very low-pressure conditions, except for the high pressures produced during secondary impact events, as recorded in features such as shock veins.” But these high-pressure minerals do not appear to have been formed in a shock vein, but within the interior of an unusually large asteroidal body (that was later smashed into pieces).

How large a body would this need to be? On earth, pressures like this are found at 100km depth. Does this mean the asteroid could have been 100km in radius? No. The pressure is caused by the weight of the rocks above and so relates to the gravitational pull of the entire body. The smaller the body, the lower the force of gravity. Back of the envelope calculations suggest that in order to achieve these pressures, the asteroid would need to have a radius of 1000s of kilometres – getting into planet territory. By comparison, the pressure at the core of our (unusually large) moon has been estimated to be 4.5GPa 3, which is only slightly higher than the upper pressure estimate from these samples.

This study is based on a tiny fragment of rock – only three thin sections. But from this, we can infer there once existed a huge piece of rock, now smashed into countless fragments. All thanks to our understanding the way minerals behave under different conditions.

Update: I do like Twitter. Various geotweeps found this story as interesting as I did. @lockwooddewit has long suspected that some types of meteorite (such as kamacite Fe-Ni ones) “suggest major differentiated body existed“. Pieces of eclogitic mantle would be consistent with this. Ryan Brown (@glacialtill) pointed out that “we know planets were differentiating w/in the first few million years of the soar system- few survived though“.

One thing that struck me my untutored eye was how remarkable it would be that a large body could form and be destroyed and the only trace be a tiny fragment in one meteorite. Andrew Alden (@aboutgeology) points out in a post that there is an obvious candidate – Theia – “the “Mars-sized object” that is thought to have collided with Earth, way back in the Hadean Eon, to create the mess that formed the Moon.

One striking thing about the paper is the lack of speculation  about the source of this material – the guessing all comes from me and the folks mentioned above. The last paragraph suggests there is more to come from Kimura et al. – “The precursor materials of the clasts, and the genetic relationships between the clasts and the host CR chondrite, are not yet clear. We are now measuring the isotopic and trace element compositions of the clasts, which will shed light on this issue.”  Studies like this have a great record of tracing events from the early solar system. I look forward to their next paper.

References

Many thanks to @TriclinicFlow (Konstantinos) for alerting me to this paper:

Kimura M., Sugiura N., Mikouchi T., Hirajima T., Hiyagon H. & Takehana Y. (2013). Eclogitic clasts with omphacite and pyrope-rich garnet in the NWA 801 CR2 chondrite, American Mineralogist, 98 (2-3) 387-393. DOI:

A deeper look at the geology of diamonds

The geology of diamonds is fascinating in itself, but they also give insights into wider geological processes and history. Up until 1725, diamonds were only known from India. That all changed when Brazilians panning river sediments for gold, instead found diamonds. Recent studies of inclusions in Brazilian diamonds give insights into what was going on deep under Brazil back when it was part of Gondwanaland.

Most diamonds form at relatively shallow depths in the mantle (a ‘mere’ 150km or so) – we know this from studying little pieces of mineral (“inclusions”) found within them. The Juina kimberlite province in Brazil is notable as it contains inclusions formed at great depths in the earth. These diamonds formed below the earth’s surface layer (the lithosphere) in a region called the aesthenosphere. This portion of the earth, between the lithosphere and the metallic core, forms the majority of the volume of the earth. Rocks within the aesthenosphere are constantly flowing in massive convection currents. The convection patterns periodically cause large upwellings of material called mantle plumes. We can never reach the aesthenosphere, but diamond inclusions give us ways of understanding it better.

As described by Ben Harte of the University of Edinburgh and Steve Richardson of Cape Town the Juina suite of diamonds contain three sets of inclusions. The ultrabasic set of inclusions contains MgSi-perovskite and ferropericlase exotic minerals that are the high-pressure equivalents of minerals like olivine and pyroxene. These minerals are thought to have formed at depths of around 660km.

Image courtesy of Ben Harte, University of Edinburgh

‘Eclogitic’ diamond inclusion from Brazil, showing garnet with exsolved pyroxene from majoritic garnet. Image courtesy of Ben Harte, University of Edinburgh

The second suite of inclusions contains a special sort of garnet, called majorite. In ‘normal’ low-pressure garnet, silica is in ‘4-fold coordination’ – it is surrounded by 4 oxygen. In majoritic garnet silica is in both 4 and 6-fold coordination. This change is caused by extreme pressures that favour more compact crystal structures – majoritic garnet is therefore indicative of extreme depths. The change in coordination changes the mineral composition – the garnet forms a ‘solid-solution’ with pyroxene. For the sample pictured above, after the majorite was formed, at some point on its journey back to the surface it changed back to normal garnet and pyroxene, a process called exsolution that leaves the two minerals intimately intertwined.

The third suite consists of a set of Ca-rich minerals with names like Ca-perovskite, titanite 1, wahlstromite and ‘phase Egg’2.

Using a variety of evidence, Harte & Richardson identify where each suite of diamonds formed. The majorite suite formed at depths of 250-450km. Their chemistry shows they didn’t form from the mantle itself, but from oceanic crust (basalt or gabbro) which suggests they formed in a subducting slab. The ultrabasic suite formed from more typical mantle material, but the authors believe it formed from the mantle part of a subducting slab. They link diamond formation with reactions that occur only in hydrated peridotite around the upper-lower mantle boundary at 660km depth. Hydrated peridotite is only found in oceanic slabs, where sea-water enters them along fractures.

The paper paints a picture of diamonds forming in a sinking slab. Isotope evidence fits this too. The majoritic diamonds contain ‘light carbon’ that has passed through the process of photosynthesis. The Ca-rich inclusions give us an insight into the processes that brought the diamonds back to the surface. They formed from carbonated rocks in the slab, perhaps calcareous oozes. Trace element evidence suggests these diamonds formed from carbonatitic magmas formed from the melting of these carbonated rocks. These diamonds formed at depths of 300 to 600 km. The melting of the carbonated rocks and the process that mixed the 3 suites of diamonds and brought them to the surface are all linked: a mantle plume.

A plume of hotter mantle from greater depths passed through the subducted slab, captured diamonds as it went. Once it reached the lithosphere beneath the Amazonian craton it initiated the production of kimberlite magmas which took some diamonds on the final journey to the surface. In a post written with Nicola Cayzer (also at Edinburgh), Ben Harte took a closer look at some of the eclogitic inclusions that were originally majoritic garnet and now a mixture of pyroxene and garnet. Assuming that patterns of composition are controlled by diffusion means that information on the speed of processes can be deduced (geospeedometry).  They estimate the diamonds rose at a rate of 1.3m a year through the upper mantle. Within 2 orders of magnitude – the likely error of the estimates – this matches theoretical estimates of mantle flow rate (1-100 cm a year).

Focussing on a single suite of diamonds allows the authors to make links with regional geological history. The sinking slab in which the first diamonds formed was created 200-180 million years ago. It sank along a subduction zone along the edge of Gondwanaland. This zone is still active along the Pacific margin of South America. The Ca-rich inclusions formed at 101Ma, as the plume punched through the subducted slab. Finally the kimberlite erupted 93 million years ago.

What of the slab in which the diamonds formed? It is still down there in the mantle. Since we know plate movements since that time, we can guess where it is – the South Atlantic. Oceanic basalts in the south Atlantic have an unusual isotopic and trace element composition, known as the DUPAL anomaly. The presence of this slab, containing sedimentary rocks, may explain the geochemical patterns of lavas erupting today.

 References

Harte, B., & Richardson, S. (2012). Mineral inclusions in diamonds track the evolution of a Mesozoic subducted slab beneath West Gondwanaland Gondwana Research, 21 (1), 236-245 DOI: 10.1016/j.gr.2011.07.001

Harte, B., & Cayzer, N. (2007). Decompression and unmixing of crystals included in diamonds from the mantle transition zone Physics and Chemistry of Minerals, 34 (9), 647-656 DOI: 10.1007/s00269-007-0178-2

A harder look at the geology of diamonds

My recent post about diamonds was a rapid romp through some of the most marvellous things earth scientists have discovered about them. In the interests of keeping the casual reader engaged I left out many things. If this left you with some nagging questions, I hope they’ll be answered here.

How in earth do they know that?

Much of the information we gain from diamonds comes from inclusions within them. The minerals that are included must be at least as old as the diamond – how else could they get there? This means that either they are older and were swallowed up by a growing diamond, or they formed at the same time as the diamond. Some inclusions have flat sides that are oriented parallel to the the crystal structure of the diamond around them, suggesting they grew at the same time. Evidence like this justifies talking about the age of the diamond when in fact we can only directly date the age of the inclusion.

The most dramatic claim for diamonds is that some of them contain carbon that was once part of a living organism. Remarkable claims require remarkable evidence – how can we say such a thing?

Diamonds from life

“Our bodies are startdust; our lives are sunlight”1. All life on earth2 depends on photosynthesis for energy. Photosynthesis is a process that captures energy from sunlight, storing it in the form of carbohydrates. This involves capturing carbon from carbon dioxide (releasing the oxygen into the atmosphere). A key enzyme called rubisco, working deep within the photosynthetic machinery, converts carbon dioxide containing carbon-12 in preference to that containing carbon-13. The carbon that ends up as carbohydrate is then richer in carbon-12. This ‘light carbon’ signature is found in living things and their non-living remains. Organic carbon in sediments has 3 percent more carbon-12 than carbonates (limestones) do.

A set of diamonds, called the eclogite-suite has unusually light carbon isotopes. Showing that this is derived from organic carbon requires us to consider other possibilities. There is a well understood carbon cycle near the earth’s surface – carbon is regularly exchanged between atmosphere, crust and the oceans. This means carbon isotope ratios give a consistent value against which the photosynthetic fractionation can clearly be seen. In the earth’s mantle, the carbon cycle is less well understood. Other processes exist that change isotopic ratios. Also there is no reason to assume that ‘primordial’ carbon, that has always been in the mantle, has a consistent isotopic ratio. Maybe portions of the mantle have always contained extremely light carbon?

A recent study in Geology (see reference below) provides further evidence that light carbon in eclogite-suite diamonds is indeed organic carbon. Looking at diamonds and their inclusions, the paper shows an anti-correlation between low carbon isotope ratios (‘light carbon’) and anomalously high  oxygen isotope ratios. The oxygen isotope pattern is interpreted as being caused by alteration of hot oceanic crust (basalt) by sea-water circulating through it. Just as with the carbon, there are other possible explanations for the oxygen signal. Showing a strong association between the two isotopic signals is important as it is exactly what you would expect if the material came from subducted oceanic crust. Other explanations for the isotope patterns wouldn’t predict the correlation between them. That some diamonds made are from subducted critters is not just a beautiful idea: it’s probably true as well.

Ancient sulphur

Another interesting isotopic signature affects sulphur isotopes and indicates they were affected by UV radiation in an oxygen poor atmosphere – conditions that only occurred on the surface of the early earth. This pattern of isotopes is different from ‘light carbon’ as it isn’t related to the mass of the isotopes – it’s know as mass-independent fraction (MIF). As a very recent paper in Nature reveals traces of MIF are found in other material brought up from the deep earth – sulphide grains in lavas produced from a mantle plume. This backs up the diamond evidence in that it shows that ancient crustal material was subducted into the deep earth.  It goes further however, as the lava is only 20 million years old, suggesting that some ancient subducted crust is still down there.

Another recent study involving MIF in sulphur adds a twist. The MIF signal has been used to date the ‘great oxygenation event’, an important milestone in earth history when photosynthesising critters finally managed to increase oxygen levels in the atmosphere. It turns out that as well as persisting in diamonds, the MIF signal can survive a sedimentary cycle – sediments formed in an oxygen atmosphere may still contain a MIF signal derived from older eroded rocks. This is important as sediments containing a MIF signal are the best way to date the onset of Oxygen in the atmosphere. Its now clear that such signals need to be used with care.

There’s more great research on diamonds, tracking their movements and relating them to plate tectonics, but I’ll save some for another day.

REFERENCES
Schulze, D., Harte, B., , ., Page, F., Valley, J., Channer, D., & Jaques, A. (2013). Anticorrelation between low 13C of eclogitic diamonds and high 18O of their coesite and garnet inclusions requires a subduction origin Geology, 41 (4), 455-458 DOI: 10.1130/G33839.1

Cratons – old and strong

Cratons are pieces of continents that have been stable for a over a billion years. As earth’s plates drift along, mountains periodically rise and fall, plate boundaries appear and disappear. But cratons are like great-grandmothers at family gatherings, while younger crust moves excitedly around them, they sit quietly, occasionally remarking on how different things were when they were young.

Every continent has cratonic areas, notably the core of North America, Scandinavia, Siberia, India and most of Australia. They may be covered by a thin shawl of sediment, but often they expose ‘basement’ rocks such as gneiss. Economically they are very important – most of the world’s diamonds come from cratonic areas as do many other valuable deposits.

craton world map

Cratons are stable because they are strong. The geology of the Himalayas illustrates this – the modern day plate  boundary between Indian and Asia is at the southern edge of the Himalayas. The cratonic Indian plate is barely deformed, in great contrast to the vast pile of deformed soft young crust in the Tibetan Plateau to the north.

Cratonic crust is strong, being unusually cold and dry, but that is only part of the picture. Continental crust is the upper portion of continental lithosphere. It’s lithosphere that puts the plates into plate tectonics, it’s a rigid layer on the earth’s surface, as opposed to the hot flowing mantle that lies beneath (the asthenosphere). Lithosphere consists of the crust and an underlying layer of mantle that has  become ‘stuck on’. This layer of lithospheric mantle can be 2 to 3 times thicker than the crust above and so contributes a great deal to the strength and stability of continental lithosphere.

It turns out that the lithospheric mantle beneath cratons is unusual. In oceanic crust, as it ages it cools and eventually it sinks down into the mantle again. It is thought that continental lithospheric mantle can fall off as well, but in cratons this doesn’t happen. Finding out why is an interesting challenge but before we start that journey, a brief interlude….

Geochemical interlude

My feelings about geochemistry have changed over time. As a doctoral student I was exiled out into an annex 10 minutes from the main department because a new piece of geochemical apparatus required a lab to be expanded, swallowing our little rock-filled office. I could relate to metamorphic petrology and analysis of mineral chemistry, but the isotope stuff, seemingly requiring months of juggling Hydrofluoric acid to get a couple of data points, left me cold. Years later, with a broader, wiser perspective I find myself marvelling at the way isotope geochemistry leads to so much awesome science.

There are two flavours of isotope geochemistry, stable and radiogenic. Many chemical isotopes are unstable and over time spontaneously turn into different elements, the bits left over being thrown out as matter and energy – radiation. For geologists, this real-life alchemy, known as radioactive decay, is mostly used to tell how old something is. The rate of radioactive decay is constant, so measuring the current abundance of isotopes and working backwards tells you the time elapsed since an event happened. Getting from measurements to age involves assumptions about the sample which may be incorrect – my own research successfully predicted a published age was incorrect. Nevertheless modern geochemists have a wide range of extremely robust and accurate techniques at their disposal. Datable events include a crystal forming from a magma or growing in a metamorphic rock, a surface being exposed to the atmosphere, a critter growing, a mineral cooling below a particular temperature, when magma was extracted from melting rock, even the age of ground water.

Stable isotope geochemistry relies on the fact that two isotopes of the same element, for example Hydrogen and Deuterium, are not precisely the same. Most physical and chemical processes treat them identically, but some do not, the slight different in mass means slight differences between isotopes. For example during evaporation of water the lighter H216O will vaporise first, creating a difference in isotopic composition between the water vapour and the remaining liquid. This phenomena of isotopic fractionation affects water in other ways, such that there is a relationship between fossil oxygen isotopes (in ice or fossil sea shells) and the temperature of the sea they came from. This tremendously useful technique is just one example of the seemingly magical way tiny differences in the physics of atoms can shed light on diverse geological problems. There are many other applications, but the technique shines most when we have very little other evidence to go on. Research into the formation of the earth and moon relies heavily on studies of arcane isotopes. We have only limited information about lithospheric mantle from beneath cratons (remember them?) and isotope geochemistry tells us many interesting things…

Back to the cratons

A recent review by Cin-Ty A. Lee, Peter Luffi, and Emily J. Chin of Rice University focuses on the creation and destruction of continental mantle (I’ll mostly discuss creation).

If lithospheric mantle beneath cratons was the same composition as the rest of the mantle then over time it would cool and become denser and unstable. A consensus has emerged that it does not because at some point in the past it was involved in melting and up to half of its volume was removed. The rock left behind after the melt flowed away is known as depleted peridotite and it is stronger and more buoyant than normal mantle, so it remains stable for billions of years.

Fragments of mantle peridotite in lava

Fragments of mantle peridotite in lava.

Pieces of continental lithosphere do reach the surface, sometimes as huge slabs such as at Ronda in Spain. Some weird volcanic deposits start at mantle depths and bring up pieces of the surrounding rocks. Sometimes they contain diamonds, but also pieces of the lithospheric mantle. Armed with these samples, geochemists have applied a massive array of techniques.

The geochemistry of melting rock is well understood and it allows us to infer many things about the conditions under which it happens. For example comparing ancient with modern samples, we can tell that older samples melted at higher temperatures (1,500 to 1,700◦C 1,300 to 1,500◦C) and saw more melt extraction (50 to 30% versus <30%). This is consistent with the fact that the early earth was hotter.

Melting is affected by pressure as well as temperature – deeper mantle rocks contain different minerals (at these pressures, garnet at depth, spinel above) which melt in subtly different ways. Cratonic peridotites melted at shallow depths (90km) but were later moved deeper (180km).

Not all samples are of peridotite, next common are pyroxenites, sometimes referred to as eclogites. Chemically these are similar to basalts formed at modern mid-ocean ridges.  Their oxygen isotopes show wide variation, such as is seen in oceanic crust following hydrothermal alteration. Other physico-chemical processes could in theory cause similar patterns, but it seems only low-temperature processes explain the patterns seen. The fact that they were once part of oceanic crust makes these pyroxenite rocks very different from the peridotites (which have only ever been part of the mantle).

Further evidence that pyroxenites were once near the surface comes from sulphur isotopes from eclogitic inclusions within diamonds. Fractionation of these isotopes occurs in ways only explained by chemical reactions high in the atmosphere. These diamonds with eclogitic inclusions themselves have carbon isotopes that are extremely ‘light’. Light carbon is a sign of life – organisms preferentially contain light carbon. In these ancient rocks, life probably means bacteria. So we can lengthen the list of “lovely things bacteria help to make” – cheese, soy sauce, wine, yogurt, healthy digestion and now certain types of diamonds.

NB for visitors from the German wikipedia page on Diamonds, I’m delighted you’re here. Here is a better reference for the science on this.

This is a wonderful thing. A bacterial mat sitting on the sea-floor billions of years ago ends up being stuffed down into a subduction zone. It enters a world of crushing pressure and extreme temperature where it is transformed utterly, its carbon forming a diamond. Later a weird eruption happens and the diamond is squirted back up to the surface for us to marvel at. Only isotope geochemistry (and some generous assumptions on my part) allows us to tell this story.

How does continental mantle form?

Our authors discuss how continental mantle forms (spoiler: we don’t really know). One model is that a large plume of hot mantle material rises up underneath a continent. This would indeed form lots of depleted peridotite (underneath a big pile of lava). However this model is inconsistent with the evidence described above – melting would be expected at greater depths (200km) than is seen.

A plume model also fails to explain the eclogitic parts of the mantle. One mechanism to explain how portions of oceanic lithosphere end up in the sub-continental mantle is that when subducted instead dropping steeply down they remain buoyant and stack up beneath the continents. In this model, the sub-continental lithosphere grows by progressive capturing and stacking of oceanic lithosphere. Its been argued that parts of the Farallon plate were captured beneath western north America in recent times. Hotter oceanic lithosphere (common in the Archean) subducts at a shallower angle and so is more likely to end up getting stuck to the base on the contintent.

This model explains the evidence for shallow melting and subsequent burial, plus the presence of former oceanic lithosphere. Indeed it predicts a larger proportion of eclogitic pyroxenite than is observed. Our authors propose a process of “viscous drainage” whereby the crustal portion of the stacked ex-oceanic lithosphere (now dense inclined sheets of garnet pyroxenite) slowly ‘drains’ down and out, leaving the peridotite ‘framework’ behind.

Models of the creation of continental crust emphasise the importance of island arcs. An oceanic island arc (where oceanic crust, subducts under oceanic) may collide with a small continent, turn into a continental island arc and ultimately become a new piece of continental crust. This mechanism will not give thick lithosphere on its own however – so some process of ‘orogenic thickening’ (squeezing it so it’s thicker) is required.

You will perhaps have sensed that the paper drifts into speculation a little. This is appropriate in a review paper and inevitable as we are on the ragged edge of what we can know about these rocks, so distant in space and time. The paper ends with a ‘future directions’ section full of as yet unanswered questions.

“How do continents form?” is a simple question to ask but we still can’t give a complete answer to it. We still don’t know the secret to great-grandma’s longevity.

 Peridotite picture from dun_deagh on Flickr under Creative Commons.
Craton map from Pearson and Wittig under Geological Society of London fair use policy.
 

PEARSON, D., & WITTIG, N. (2008). Formation of Archaean continental lithosphere and its diamonds: the root of the problem Journal of the Geological Society, 165 (5), 895-914 DOI: 10.1144/0016-76492008-003
Lee, C., Luffi, P., & Chin, E. (2011). Building and Destroying Continental Mantle Annual Review of Earth and Planetary Sciences, 39 (1), 59-90 DOI: 10.1146/annurev-earth-040610-133505