Methane on Mars

Brian Shiro
Department of Space Studies, University of North Dakota, Grand Forks, ND 58202, USA 10 September 2007

Abstract Detections of small amounts of methane in the atmosphere of Mars have prompted much speculation on the possible sources of the gas since it is a potential biomarker. This paper reviews the current understanding of methane on Mars, including the details of its detection, distribution, and possible sources and sinks. Although the existence of biological life cannot be ruled out with current methane measurements, other plausible non-biological explanations are presented. These include geochemical alteration reactions such as serpentinization and outgassing from methane clathrate hydrate deposits. More accurate and precise measurements of methane and other trace species in future missions to Mars will address the question of life on Mars.

I.

Introduction Most terrestrial methane is the product of biological processes, and recent detections of

methane in the Martian atmosphere have prompted speculation of a possible biogenic origin. This paper reviews the methane detected and the major abiogenic and biogenic processes that could account for it. Future missions to Mars should be targeted to answer whether the methane observed is from geological or biological sources. II. Methane Observations In 2004, three teams independently announced the discovery of trace amounts of methane (CH4) on Mars. Using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope at Mauna Kea Observatory, Krasnopolsky et al. (2004) observed a 10±3 ppb (parts per billion) global mean methane mixing ratio in the Martian atmosphere. Formisano et al. (2004) used the Planetary Fourier Spectrometer (PFS) aboard the Mars Express orbiter to determine a global mean methane abundance of 10±5 ppb with possible variations of 0-30 ppb from orbit-orbit over the
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planet. Mumma et al. (2004; 2005) reported detection of methane in two localized areas on Mars with maximum values of 250 ppb from the NASA Infrared Telescope Facility (IRTF) Cryogenic Echelle Spectrograph (CSHELL) and 60 ppb from the Phoenix spectrograph at the Gemini South Observatory, but the work remains unpublished and requires confirmation. However, Encrenaz et al. (2005) found no evidence of a localized source of methane in excess of 70 ppb. Encrenaz (2007) tried to verify the results of Mumma et al. (2004; 2005) by searching for high methane spots with PFS but found no evidence for methane and established upper limits of 20 ppb and 50 ppb in the two areas where Mumma et al. had detected 60 ppb and 250 ppb. The mean global methane mixing ratio determined by Encrenaz (2007) using PFS was 20±10 ppb, which is generally in agreement with Krasnopolsky et al. (2004) and Formisano et al. (2004). Other studies of minor constituents in the Martian atmosphere have not detected methane but did establish upper limits on the methane level as 20 parts per billion (ppb) from the Mariner 9 infrared spectrometer (Maguire 1977), 70±50 ppb from the Fourier transform spectrometer at the Kitt Peak National Observatory (Krasnopolsky et al. 1997), 50 ppb from the Short-Wavelength Spectrometer of the Infrared Space Observatory (Lellouch et al. 2000), and 20 ppb (morning side) to 70 ppb (evening side) from the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility at Mauna Kea Observatory (Encrenaz et al. 2005). III. Methane Lifetime To understand the production rate required of potential methane sources, one must first know how it is destroyed. The primary loss mechanisms for methane are photolysis by ultraviolet light in the upper atmosphere (70-90 km altitude) and oxidation near the Martian surface. Assuming a methane abundance of 10 ppb, Krasnopolsky et al. (2004) used data from photochemical models of the Martian atmosphere to estimate the total lifetime of methane as 340 years, which corresponds to 270 tons lost per year (t y-1). Wong et al. (2003) modeled methane chemistry in the Martian atmosphere and estimated a lifetime of 670 years, which is equivalent to a 126 t y-1 loss (Formisano et al. 2004; Atreya et al. 2007). The short methane lifetime of a few hundred years means that methane levels must be actively replenished in order to maintain the level observed today. IV. Methane Distribution
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Both Formisano et al. (2004) and Mumma et al. (2004; 2005) claimed to have detected spatial variability in methane. This has prompted much speculation on how a non-uniform methane distribution could exist in the Martian atmosphere. The time scales of horizontal and vertical mixing of methane in the lower Martian atmosphere are only 10 days and 0.5 years, respectively (Krasnopolsky et al. 2004). These times are much lower than the 370 or 670 year methane lifetime estimates. Therefore, methane should be uniformly well mixed throughout the Martian atmosphere. If spatial variations in methane do occur, they must result from either heterogeneous source production or sink removal of methane from the Martian atmosphere. Examples of heterogeneous sources include volcanoes, magmatic intrusions, hydrothermal vents, clathrate hydrate outgassing, and dispersed microbial colonies. However, given the short atmospheric mixing time, it is difficult to reconcile these examples with sustained areas of non-uniform methane distribution, although recent preliminary general circulation models suggest it is possible (Forget et al. 2005). Heterogeneous loss of methane due to near surface oxidation is another possible way to explain a non-uniform methane distribution. Electrostatic fields generated by charged sand in Martian dust devils, saltation, and other aeolian processes can produce large quantities of the oxidant hydrogen peroxide (H2O2), which scavenges organic matter from the surface of Mars and accelerates methane loss from the atmosphere in that area (Atreya et al. 2006; Delory et al. 2006; Farrell et al. 2006). The calculated abundance of H2O2 produced by such a mechanism could reach 200 times the level produced by photochemistry alone, which has been measured at the 20-40 ppb level globally (Encrenaz et al. 2004). The increased H2O2 in the local area dissociates methane at a rate 1012 times greater than normal and decreases the methane stability lifetime to about 1000 seconds, resulting in decreased methane concentrations on temporal and spatial scales of weeks and hundreds of kilometers, respectively (Farrell et al. 2006). This process could also provide an explanation for the puzzling lack of any organics observed on the surface to Mars (Atreya et al. 2007). Future high spatial resolution sampling of the Martian atmosphere should help resolve the issues related to methane’s possible heterogeneous distribution. V. Methane Sources The source of Martian methane must be currently active in order to counteract methane’s short lifetime in the Martian atmosphere. This section reviews the major mechanisms that could
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potentially supply methane on Mars. atmosphere (Section 5.6).

Figure 1 illustrates the interrelations of the possible

methanogenic sources, with the exception of photochemical production of methane in the

Figure 1: Potential methane sources and sinks (from Atreya et al. 2007).

5.1. Cometary Delivery of methane from exogenic sources such as carbonaceous meteorites and interplanetary dust is highly unlikely (Flynn 1996; Krasnopolsky et al. 2004), making comets the only plausible exogenous source. Assuming an impact rate of 1.6×10-8 y-1 for ecliptic comets impacting Mars (Levison et al. 2000), the mass of methane delivered by 1 km radius comets has been estimated as 1-2 t y-1 (Formisano et al. 2004; Atreya et al. 2007; Krasnopolsky 2006), which accounts for less than 1% of the necessary methane production. Kress and McKay (2004) calculated that that a single 1 km comet impact on Mars would deliver 10 Tg (teragrams) of methane (5 ppb) and suggested that methane accumulated through such impacts during the late heavy bombardment could have been a significant greenhouse gas in the early Martian atmosphere. Given the short lifetime of methane in the Martian atmosphere, it is possible that the observed methane today is the remnant of a recent cometary impact. Atreya et al. (2007) calculated the range of cometary radii that could explain the 10 ppb of methane detected on Mars today and found that a
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comet as small as 130 m striking 100 years ago to a comet as large as 360 m impacting 2000 years ago could explain the current methane levels. However, the probability of such an event actually occurring is only 0.001 (Krasnopolsky 2006). 5.2. Volcanic If volcanic outgassing is a principle source of Martian methane, volcanoes on Mars must have been active within the past few hundred years. The most recent lava flows detected on Mars date to 2-100 Myr (Hartmann and Berman 2000; Neukum et al. 2004), and no active hot spots have been detected from the Thermal Emission Imaging System (THEMIS) aboard the Mars Odyssey orbiter (Christensen et al. 2003). This suggests that Martian volcanoes are dormant today. Furthermore, the best terrestrial analog to the Tharsis shield volcanoes on Mars is Mauna Loa, which is not emitting any methane (Ryan et al. 2006). If the Martian methane were of volcanic origin, SO2 should exist in the atmosphere at the 1-10 ppb level, but it has not been detected (Encrenaz 2001; Krasnopolsky 2005). Thus, volcanism is a highly unlikely source of current Martian methane. 5.3. Hydrothermal Serpentinization of ultramafic silicates such as olivine can form methane at depths where geothermal gradients allow CO2–containing liquid water to exit (Oze and Sharma 2005; Atreya et al. 2007). On Earth, these reactions typically occur in environments at temperatures and pressures too high (and therefore too deep) to fall within the stable zone for liquid water in the Martian subsurface. However, recent discovery of low temperature serpentinization in terrestrial oceans suggests that proper temperatures can be reached within the 4-15 km depth zone for stable liquid water in the Martian subsurface (Oze and Sharma 2005). Krasnopolsky (2006) investigated the reaction rate in the zone proposed by Oze and Sharma (2005) and determined that only the lower half of the 4-15 km layer can form methane if CO2 exists there. Methane synthesis could also occur in hydrothermal fluids interacting with basaltic rock at temperatures less than 150°C above magmatic intrusions. Lyons et al. (2005) calculated the

methane released from a 10 km × 10 km × 1 km dike cooling from 870 K to 520 K over 104 y and found that it could supply enough methane at a rate sufficient to maintain the observed levels in the Martian atmosphere. However, Krasnopolsky (2006) pointed out that the 80°C surface temperature from such a dike should easily be visible with THEMIS. The lack of any such contemporaneous

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thermal anomaly on Mars makes this proposed production mechanism unlikely. 5.4. Biological More than 90% of terrestrial methane has a biological origin (e.g., Atreya et al. 2007), so it is natural to question whether the Martian methane might also originate from biological processes, either today or in the past. This proposition has far-reaching implications for the existence of life on Mars, and as such it has gained widespread attention since the 2004 detections of methane in the Martian atmosphere. The low surface temperature and pressure, CO2 atmosphere, and high incident UV flux on the Martian surface makes the present surface environment on Mars inhospitable to life as we know it (Max and Clifford 2000). Thus, if life survives on Mars today, it is likely sequestered in subterranean environments. Subterranean chemolithotrophic microbial ecosystems are common on Earth. Methanogenic bacteria in these environments consume H2 and/or CO and produce methane as a product of their metabolism (Weiss et al. 2000; Chapelle et al. 2002; Krasnopolsky et al. 2004). Such communities could also have evolved in subsurface Martian aquifers and still thrive today (Boston et al. 1992; Fisk and Giovannoni 1999; Max and Clifford 2000). The Martian atmosphere contains a ready supply of CO and H2 to diffuse through the regolith into subsurface aquifers that could potentially support life. However, the long diffusion times required mean that these species would be oxidized by minerals in the soil, severely limiting the thickness of the Martian biogenic layer to about 100 m (Weiss et al. 2000; Krasnopolsky et al. 2004). Abundant H2 may also be available in localized areas via hydration of ultramafic silicates (Atreya et al. 2007), thus providing possible oases for life. Atreya et al. (2007) point out that methane-consuming organisms (methanotrophs) on Mars could present another methane loss mechanism (see Section III). Present methane observations on Mars cannot prove or disprove the existence of extant or extinct life. Furthermore, some abiogenic methane sources can be difficult to distinguish from biogenic ones (Lollar et al. 2006; Fiebig et al. 2007). The best way to discriminate between biological and geochemical sources of Martian methane is to measure the isotopic fractionation of
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CH4 and CH3D relative to CO2 and HDO, respectively (Nair et al. 2005). Life on Earth evolved to C. Precise measurement of the 12C/13C and D/H ratios will require methane detection capabilities

favor 12C rather than 13C because of the lower energy required to form bonds with 12C compared to
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at 0.01 ppb levels, which will be a challenge to obtain due to the low methane abundance and could result in non-unique determinations (Krasnopolsky 2006). Another crucial test for whether life is
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extant or extinct is the chirality of organic molecules. Life on Earth favors “left-handed” molecules, but non-biological organic molecules can be either left- or right-handed. The payloads of the Mars Science Laboratory (MSL) will attempt to make these measurements for methane over one Martian year (Atreya et al. 2007; Encrenaz 2007). 5.5. Methane Clathrate Hydrates Even if methane-producing organisms are not extant today, they could have thrived during the warmer, wetter Martian past. The methane produced through any subsurface biogenic or abiogenic processes could have been stored in methane clathrate hydrate deposits in the Martian subsurface and polar caps (Chastain and Chevrier 2007). Clathrate hydrates in the Martian permafrost could be supplied both from above and below through either geological or biological processes. These could be acting as reservoirs for either ancient or active methane sources. Clathrate hydrates consist of a lattice of H2O molecules held together by hydrogen bonds that trap gas molecules under low temperature, high-pressure conditions. This structure can trap a volatile gas like methane within a stable, compact solid solution for long time periods (PrietoBallesteros et al. 2006). These reservoirs could be trapped by lithostatic pressure at depths ranging from about 10 m to 1 km (Max and Clifford 2000; Pellenbarg et al. 2003). Slow dissociation of methane from such reservoirs, possibly due to long-term climate change (Prieto-Ballesteros et al. 2006) or salinity-induced dissociation (Elwood Madden et al. 2007), could actively supply the methane abundance observed today. Krasnopolsky (2005) observed an upper limit of 1 ppb of SO 2 in the Martian atmosphere, and he argues this restricts the possible seepage levels of any gases from the Martian interior, including methane from clathrate hydrates or serpentinization reactions (Krasnopolsky 2006). Conditions at the poles are more favorable for clathrate hydrate formation, with estimated methane clathrate hydrate stability reaching depths as shallow as 2.5 m (Prieto-Ballesteros et al. 2006; Chastain and Chevrier 2007). Binary CO2/CH4 clathrate hydrates can form at even lower pressures than methane-only clathrate hyrdrates, meaning they can form very near the surface, especially at the poles (Chastain and Chevrier 2007). Current conditions prevent the active formation of methane clathrate hydrates near the surface, so if any shallow deposits do exist, they likely contain remnants of an early Martian atmosphere from a time when the atmosphere was thicker and contained more methane. Remote detection of subsurface methane clathrate hydrate deposits is difficult. The most
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effective method would be in situ drilling (Max and Clifford 2000; Chastain and Chevrier 2007), although seismic, electromagnetic, and ground penetrating radar methods have also been proposed (see references in Chastain and Chevrier 2007). Furthermore, since clathrate hydrate deposits on Mars could contain concentrated reservoirs of water, methane, and carbon dioxide, there is great potential for in situ resource utilization by future missions to Mars (Pellenbarg et al. 2003). 5.6. Photochemical Bar-Nun and Dimitrov (2006; 2007) presented experimental evidence that methane could be produced in the Martian atmosphere by photolysis of H2O in the presence of CO. They also backed up their results with thermodynamic equilibrium calculations. Krasnopolsky (2007) argued that these reactions are not justified by chemical kinetics. Bar-Nun and Dimitrov (2007) further expanded their thermodynamic calculations and showed that methane formation is possible and favored thermodynamically under Martian conditions. Additional study is required in order to determine if such methane production actually occurs on Mars. If it does, the other possible formation methods discussed above could be marginalized. VI. Summary Trace amounts of methane have been tentatively detected in the Martian atmosphere at 10 ppb levels, corresponding to lifetimes of about 300-600 years. The short lifetime of methane in the Martian atmosphere requires that the observed methane be recently produced/released or that a significant amount of methane was released in the past, and we now see the diminishing remnant of that event. Some observations suggest strong localized sources of methane up to 30 ppb or more, which is difficult to reconcile with the very short mixing time (few weeks) of methane in the Martian atmosphere. One likely explanation for the disparities could be localized oxidation of methane by H2O2 produced during transient dust storms. The origin of methane on Mars could result from a number of potential sources, which were reviewed in this paper: 1. Comets, meteorites, and interplanetary dust (highly unlikely) 2. Volcanic outgassing (not observed and likely to be very minor) 3. Hydrothermal reactions, especially serpentinization (possible, perhaps likely) 4. Biological (possible, perhaps likely)
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5. Clathrate hydrate outgassing (likely) 6. Photochemical production in atmosphere (possible, needs more study) Future precise measurements of the 12C/13C isotopic ratio should be able to verify whether methane source is biological, and determination of organic molecule chirality should settle whether any detected biosignatures come from extant or extinct life. As tantalizing as the possibility of extant life is, it is this author’s opinion that abiogenic processes probably contribute to the currently observed methane in the Martian atmosphere. Extinct life could have supplied methane in clathrate hydrate deposits, which could also contribute to the current atmospheric methane budget. VII. References

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