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.
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.
If a geologist with broad interests was asked, ‘what are the oldest materials on Earth?’ she or he would probably say the Acasta Gneiss from Canada’s North West Territories at 4.03 billion years (Ga) (see: At last, 4.0 Ga barrier broken, November 2008. A specialist in the Archaean Eon might say the Nuvvuagittuq Greenstone Belt on the eastern shore of Hudson Bay (see: Archaean continents derived from Hadean oceanic crust, March 2017); arguably 4.28 Ga old. An isotope geochemist would refer to a tiny 4.4 Ga zircon grain that had been washed into the much younger Mount Narryer quartz sandstone in Western Australia (see: Pushing back the “vestige of a beginning”, January 2001). A real smarty pants would cite a 4.5 Ga old sample of feldspar-rich Lunar Highland anorthosite in the Apollo Mission archive in Houston, USA. The last is less than 100 Ma younger than the formation of the Solar System itself at 4.568 Ga. Yet there are meteorites that have fallen to Earth, which contain minute mineral grains that were incorporated into the initial dust from which the planets formed. Until recently, the best known were white inclusions in a 2 tonne meteorite that fell near Allende in Mexico; the largest carbonaceous chondrite ever found. This class of meteorite represents the most primitive material in orbit around the Sun. Its tiny inclusions contain proportions of isotopes of a variety of elements that are otherwise unknown in any other material from the Solar System and they are older. The conclusion is that these dust-sized, presolar grains originated elsewhere in the galaxy, perhaps from supernovas or red-giant stars.
Carbonaceous chondrites, as their name suggests, contain a huge variety of carbon-based compounds and they have been closely examined as possible suppliers of the precursor chemicals for the origin of life. Another large example of this class fell near the town of Murchison in Victoria, Australia in 1969. The first people to locate fragments of the 100 kg body noted a distinct smell of methylated spirits and steam rising from it: when crushed half a century later it still smells like rotting peanut butter. The Murchison meteorite has yielded signs of 14 thousand organic compounds, including 70 amino acids. It has also been a target for extracting possible presolar grains. This entails grinding small fragments and then dissolving out the carbonaceous and silicate material using various reagent to leave the more or less inert silicon carbide grains. The residue contains the most durable grains: despite being described as ‘large’ they are of the order of only 10 micrometres across. Some are made of silicon carbide; the same as the well-known abrasive carborundum. Throughout their lifetime in interstellar space the grains have been bombarded by high-energy protons and helium nuclei which move through space at nearly the speed of light – generally known as ‘cosmic rays’. When interacting with other matter they behave much like the particles in the Large Hadron Collider, being able to transmute natural isotopes into others. Measuring the relative proportions of these isotopes in material that has been bombarded by cosmic rays enables their exposure time to be estimated. In the case of the Murchison presolar grains the isotopes of choice are those of the noble gas neon (Heck, P.R. and 9 others 2020. Lifetimes of interstellar dust from cosmic ray exposure ages of presolar silicon carbide. Proceedings of the National Academy of Sciences, 201904573; DOI: 10.1073/pnas.1904573117). Analyses of 40 such grains yielded ages from 4.6 to 7.5 Ga, i.e. up to 3 billion years before the Solar System formed. They are, indeed, exotic. The highest age exceeds that of the oldest from such previously measured by 1.5 billion years
Investigations up to now suggest that dusts amount to about 1 % of interstellar matter, the rest being gases, mainly hydrogen and helium. With the formation of the planets and the parent bodies of asteroids a high proportion of presolar grains would have accreted to them to be mixed with other, more common stuff. What Heck and colleagues have discovered puts the Solar System into a broad framework of time and space. The grains must have formed at some stage in the evolution of stars older and larger than the Sun, to be blown out into the interstellar medium of the Milky Way galaxy. One possibility is that about 7 billion years ago there was a burst of star formation in a nearby sector of the galaxy. How the resulting dust made its way to the concentration of interstellar matter that eventually formed the Sun and Solar System is yet to be commented on.