Curiosity rover hints at the carbon cycle on Mars

The Mars Science Laboratory carried by the Curiosity rover is still functioning 10 years after a jetpack lowered Curiosity onto the surface of Gale crater. It includes a system aimed at scooping and drilling samples of soil and rock from the sedimentary strata deposited in the lake that once filled the crater about 3.5 to 3.8 billion years ago. The system on the rover is also capable of analysing the samples in various ways. A central objective of the mission was to obtain data on oxygen and carbon isotopes in carbon dioxide and methane released by heating samples, which uses a miniature mass spectrometer. In early 2022 a paper on Martian carbon isotopes was published in the Proceedings of the National Academy of Sciences (PNAS) that I have only just found (House, C.H. et al. 2022. Depleted carbon isotope compositions observed at Gale crater, Mars. Proceedings of the National Academy of Sciences, v. 119, article e2115651119; DOI: 10.1073/pnas.2115651119). PNAS deemed it to be one of the 12 most important of its articles during 2022.

Oblique view of Curiosity’s landing site in Gale crater on Mars, from which the rover has traversed the lower slopes of Mount Sharp. Credit: NASA-Jet Propulsion Laboratory

Carbon isotopic analyses chart the type and degree of fractionation between carbon’s two stable isotopes 12C and 13C. This is expressed by their relative abundances to one another in a sample and in a reference standard, signified by δ13C. The measure is a natural tracer of both inorganic and biological chemical processes: hence the potential importance of the paper by Christopher House and colleagues from the University of California, San Diego. The thin atmosphere of Mars contains both CO2 and traces of CH4, so a carbon cycle is part and parcel of the planet’s geochemical functioning. The ‘big question’ is: Did that involve living processes at any stage in the distant past and even now? Carbon held in various forms within Mars’s ancient rocks and soils may provide at least a hint, one way of the other. At the very least it should say something about the Martian carbon cycle.

House et al. focus on methane released by heating 22 samples drilled from sandstones and mudstones traversed by Curiosity up a slope leading from the floor of Gale crater towards its central peak, Mount Sharp.  The sampled sedimentary rocks span a 0.5 km thick sequence. Carbon in the expelled methane has δ13C values that range from -137 to +22 ‰ (per mil). Samples from six possibly ancient exposed surfaces were below -70 ‰. This depletion in 13C is similar to the highly negative δ13C that characterises carbon-rich sediments on Earth that were deposited at the Palaeocene-Eocene boundary. That anomaly is suspected to have resulted from releases of methane from destabilised gas hydrate on the sea floor during the Palaeocene–Eocene Thermal Maximum. Organic photosynthesis takes up ‘light’ 12C in preference to 13C, thereby imparting low δ13C to organic matter. In the case of the Mars data that might seem to point to the lake that filled Gale crater 3.5 to 3.8 billion years ago has contained living organisms of some kind. Perhaps on exposed surfaces of wet sediment primitive organisms consumed methane and inherited its δ13C. Some Archaean sediments of about the same age on Earth show similar 13C depletion associated with evidence for microbial mats that are attributed to the activities of such methanotrophs.

Before exobiologists become too excited, no images of possible microbial mats in Gale crater sediments have been captured by Curiosity. Moreover, there are equally plausible scenarios with no recourse to once-living organisms that may account for the carbon-isotope data,. Extreme depletion in 13C is commonly found in the carbon within meteorites, almost certainly inherited from the interstellar dust from which they accreted. It is estimated that the solar system passes through giant molecular clouds every 100 Ma or so: the low δ13C may be inherited from interstellar dust. Alternatively, because Mars has an atmosphere almost entirely composed or CO2 – albeit thin at present – various non-biological chemical reactions driven by sunlight or electrically charged particles may have reduced that gas to form methane and other compounds based on C-H bonds. Carbon dioxide still in Mars’s atmosphere is highly enriched in 13C, suggesting that earlier abiotic reduction may have formed 13C-depleted methane that became locked in sediments. Yet such an abundant supply of inorganic methane may have encouraged the evolution of methanotrophs, had life emerged on early Mars. No one knows …

It’s becoming a cliché that, ‘We may have to await the return of samples from the currently active Perseverance rover, or a crewed mission at some unspecifiable time in the future. The Curiosity carbon-isotope data keep the lamp lit for those whose livelihoods have grown around humans going to the Red Planet.

A hint of life on Mars

We can be certain that life was around on Planet Earth around 3.5 billion years ago, if not before, because unmetamorphosed sedimentary rocks of that age from Western Australia in which stromatolites occur contain a black to brownish, structureless material known as kerogen. The material is a hodgepodge of organic compounds that form during the breakdown of proteins and carbohydrates in living matter. It is the source material for petroleum compounds when kerogen-rich rocks are heated during burial. The vast bulk of organic compounds preserved on Earth are in the form of ancient kerogen, whose mass exceeds that of the living biosphere by about 10 thousand times. A good sign that it does represent ancient life lies in sedimentary kerogen’s depletion in ‘heavy’ 13C compared with 12C (negative values of δ13C), because in metabolising carbon dioxide living cells preferentially use the lighter of these two isotopes. Conceivably, 13C can be removed from inorganic carbon by metamorphic processes, so low values of δ13C in metasediments from West Greenland might be organically derived or, equally, they might not.

At the time of writing, geoscientists specialising in Martian matters had become excited by some results from the geochemical system aboard the surviving functional NASA rover. Curiosity has slowly been making its way up Mount Sharp at the centre of Gale Crater near to Mars’s equator. Analysis of high-resolution images taken from orbit suggest that the rocks forming the mountain are sediments. the lowest and oldest strata are suspected to have been deposited in a crater lake when conditions were warmer and wetter on Mars, about 3 billion years ago. Curiosity was equipped with a drill to penetrate and sample sediment unaffected by ultraviolet radiation that long ago would have destroyed any hydrocarbons exposed at the surface. In late 2016, before the rover had reached the lake sediments, the drill’s controller broke down. Since then, Curiosity had moved on to younger, less promising sediments. More than a year later mission engineers fixed the problem and the rover backtracked to try again. Heating the resulting samples to almost 900°C yields any volatile components as a gas to a mass spectrometer, results from which give clues to the molecules released.

‘Selfie’ of Curiosity rover en route to Mount Sharp. (Credit: NASA)

The Sample Analysis at Mars (SAM) team report a range of thiophenic, aromatic and aliphatic molecules of compounds of carbon, hydrogen and sulfur (Eigenbrode, J.L and 21 others 2018. Organic matter preserved in 3-billion-year-old mudtsones at Gale crater, Mars. Science, v. 360, p. 1096-1101; doi:10.1126/science.aas9185). The blend of pyrolysis products closely resembles those which form from heated terrestrial kerogens and coals, but also from pyrolysis of carbonaceous chondrite meteorites. So, the presence of Martian kerogen is not proven. But the results are so promisingly rich in hydrocarbons that another weapon in SAM’s armoury will be deployed, dissolving organic compounds directly from the drill cuttings. This may provide more convincing evidence of collagen. Yet only when samples are returned to labs on Earth will there be a chance to say one way or the other that there was once life on Mars. The results reported in Science’s 8 June issue will surely add weight to the clamour for the Mars 2020 sample-return mission to be funded. Whether or not there is life on Mars demands a great deal more investment still…

A fully revised edition of Steve Drury’s book Stepping Stones: The Making of Our Home World can now be downloaded as a free eBook

Trapping Martian life forms

No matter how optimistic exobiologists might be, the current approaches to discovering whether or not Mars once hosted life or, the longest shot of all, still does are almost literally hit or miss. First the various teams involved try to select a target area using remotely sensed data to see if rocks or regolith have interacted with water; generally from the presence or absence of clay minerals and /or sulfates that hydrous alteration produces on Earth. Since funding is limited the sites with such ingredients are narrowed down to the ‘best’ – in the case of NASA’s Curiosity rover to Gale Crater  where a thick sequence of sediments shows occasional signs of clays and sulfates. But a potential site must also be logistically feasible with the least risk of loss to the lander. Even then, all that can be achieved in existing and planned mission is geochemical analysis of drilled and powdered samples. Curiosity’s ambition is limited to assessing whether the conditions for life were present. Isotopic analysis of any carbon content to check for mass fractionation that may have arisen from living processes is something for a future ESA mission.

Neither approach is likely to prove the existence now or in far-off times of Martian life, though scientists hope to whet the appetite of those holding the purse strings. Only return of rock samples stands any realistic chance of giving substance to the dreams of exobiologists. But what to collect? A random soil grab or drill core is highly unlikely to provide satisfaction one way or the other. Indeed only incontrovertible remains of some kind of cellular material can slake the yearning. Terrestrial materials might provide a guide to (probably) robotic collectors. Kathleen Benison and Francis Karmanocky of West Virginia University have followed this up by examining sulfates from one of the least hospitable places on Earth; the salt flats of the high Andes of Chile (Benison, K.C. & Karmanocky, F.J. 2014. Could microorganisms be preserved in Mars gypsum? Insights from terrestrial examples. Geology, v. 42, p. 615-618).

Evaporite minerals from Andean salars precipitated from extremely acidic and highly saline lake water originating from weathering of surrounding volcanoes. Oddly few researchers have sought cellular life trapped in crystals of salt or gypsum, the two most common minerals in the high-elevation salt pans. Fluid inclusions in sedimentary halite (NaCl) crystals from as far back as the Triassic are known to contain single-celled extremophile prokaryotes and eukaryotes, but gypsum is more likely to be found on Mars. Benison and Karmanocky document a variety of cellular material from Chilean gypsum that has been trapped in the solid mineral itself or in fluid inclusions. This is the most likely means of fossilisation of Martian life forms, if they ever existed. The salar gypsum contain cells that can be cultured and thereby revived since several species can remain dormant for long periods. The authors suggest that transparent cleavage fragments of Martian gypsum could be examined at up to 2000x magnification on future Mars landers. Finding convincing cells would see dancing in exobiology labs, and what if they should move…

Are Martian clays magmatic in origin?

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Artist’s Concept of Curiosity’s touchdown(credit: Wikipedia)

The remote detection of spectral features in the infrared that suggest abundant clay minerals on the surface of Mars is the basis for a widely-held view that Mars may once have had moist climatic conditions that encouraged life to form (see The Martian ‘sexy beast’ in September 2012  EPN). The presence of clays, along with suggestive landforms, has also been used to speculate that Mars once harboured long-lived lakes and perhaps even a huge ocean on its northern hemisphere, between 3.7 to 4.1 Ga. It was the clays that pitched the recently arrived Curiosity (aka Mars Exploration)Rover at the Gale crater and its central Aeolis Mons. The latter, also known as Mount Sharp, preserves about 5 km of layered rocks, the lowest of which are clay-rich and hypothesised to be sediments laid down in a lake that filled the crater. Provided Curiosity operates according to plan, we will know soon enough whether or not the layered rocks of Mount Sharp are indeed sediments, but a soon-to-be-published article suggests another explanation than weathering for the production of abundant clay minerals on Mars (Meunier, A. et al. 2012. Magmatic precipitation as a possible origin of Noachian clays on Mars. Nature Geoscience, published online 9 September 2012; DOI: 10.1038/NGEO1572).

Focusing the 100-millimeter Mastcam [detail]
Layered rocks on the flanks of Mount Sharp in Gale crater from Curiosity’s Mastcam (NASA Goddard via Flickr)
The French-US team provides evidence from terrestrial lavas that abundant iron- and magnesium-rich clays, known as smectites, may form at a late stage during crystallization of magma. If magma contains water – and most magmas do – as more and more anhydrous silicates crystallise during cooling water builds up in the remaining liquid. Once silicate crystallisation is complete there remains a watery fluid capable of reacting with some of the silicates to form clay minerals; a process often referred to as pneumatolysis. How much clay is formed depends on the initial water content of the magma. Pneumatolysisoperates on hot lava, whereas weathering occurs at ambient temperature provided the climate is able to support liquid water at the surface. Mars is currently far too cold for that, and ideas of a wet surface environment earlier in the planet’s history demand an explanation for a much warmer climate. Clay minerals do not appear to be present in Mars’s younger rocks, so Meunier and colleagues suggest that as the planet’s mantle evolved early water-rich magmas were gradually replaced by ones with less water: interior Mars was gradually de-gassed and its magmas lost the ability to alter minerals that crystallised from them.

Now, clay minerals are extremely resistant to change except through high-temperature metamorphism. Once formed they can be blown around – Mars has probably always been a very windy place – to end up in aeolian sediments that are plentiful on Mars.  Also, if occasionally water flowed on the surface perhaps by subsurface water venting suddenly, fine-grained pneumatolytic clays would easily be picked up, concentrated as flow speed lessened and deposited in waterlain sedimentary layers.  A dilemma that faces the Curiosity science team is what significance to assign to clays in sediment layers, when they no longer provide unequivocal evidence of weathering.  But will the resistant layers on Mount Sharp turn out to be pneumatolytically altered lava flows?
Note added 28 September 2012: The first scientific triumph of the Curiosity Rover is imagery of sediments in what had been suggested to be an alluvial fan washed into Gale crater. They show gravels with rounded pebbles.