[4495-13] © 2001 SPIE - The International Society for Optical Engineering Proceedings of SPIE, SPIE-The International Society for Optical Engineering, "Instruments, Methods, and Missions for Astrobiology IV". 29 July - 3 August 2001, San Diego, California, USA Rock Varnish As A Habitat For Extant Life On Mars Barry E. DiGregorio Cardiff Centre for Astrobiology, Cardiff, UK [email protected] ABSTRACT Many of the rocks on the surface of Mars that have been imaged by the Viking and Mars Pathfinder Landers display dark shiny surface coatings resembling Mn-rich terrestrial rock varnish. On our planet, these thin (5 um – 1 mm) coatings can be the result of a combination of various weathering processes combined with microbial precipitation of mineral oxides over a wide variety of geographical locations but most commonly in those with arid and semi-arid conditions. Terrestrial Mn-rich rock varnish is produced by a wide variety of microorganisms including epilithic and edolithic cyanobacteria, bacteria and microcolonial fungi. As these microorganisms absorb trace amounts of Mn and Fe from atmospheric dust, rain and fog, they slowly precipitate “reddish” iron and “brown to black” manganese oxides as well as magnetite particles. These microbial communities then produce secretions that cement the Mn/Fe mix together with clay particles in a process involving time periods of perhaps thousands of years for a thin 5 um layer. Mn-rich rock varnish has been found to form on the surfaces of undisturbed desert fragments and even sand grains. Both Mn and Fe would serve as a UV shield for any microflora residing beneath and within the layers of varnish thus protecting against high UV irradiation, dissication, and widely varying temperature extremes. Recent research on rock varnish has led to the discovery that some microbial communities that produce dark ferromanganese varnishes also precipitate biogenic magnetite. In view recent independent evidence put forth by D. McKay and E.I. Friedmann et al for indigenous biogenic magnetite-chains in ALH 84001 along with meteorological models showing the possibility for small quantities of liquid water on the surface of Mars in combination with data obtained from the Viking LR experiment 27 years ago, recommendations are made to elucidate on whether or not the shiny dark-coatings covering some Martian rocks have been produced by living or extinct microbial communities. Keywords: rock varnish, desert varnish, fog desert, endolithic, stromatolites, rock coatings, Mars Pathfinder, Viking Lander, cyanobacteria, microcolonial fungi INTRODUCTION: ORIGIN, CHARACTERISTICS AND OCCURRENCE OF TERRESTRIAL ROCK VARNISH Prior to the oxygen levels required to form a sufficient solar UV ozone shield in Earth’s atmosphere during the Proterozoic Eon 2.5 to 0.55 Ga ago it is thought that Archean stromatolite and microbial mat forming communities were limited to shallow water environments (1). The early Archean atmosphere was largely CO2 but gradually acquired free oxygen that was released through the photosynthetic activities of algae and cyanobacteria. The banded iron formations are considered strong evidence that the oxygen levels were extremely low during the Proterozoic, otherwise these iron deposits would have never made it to the oceans unoxidized. However, as oxygen levels in the atmosphere gradually began to accumulate it would have poisoned the same anaerobic microbial communities producing it had it not combined with iron deposits on land to form the well known red beds 1.8 billion years ago. This would allow evolution time to develop the eukaryotic cell and aerobic metabolism. The emergence of life on the barren rocky landscape in the form of simple microbial communities is often estimated to be during the Ordovician Period 490 m.y. ago (2). This suggests that the amount of oxygen necessary to photo-dissociate into O3 and produce a biologically protective ozone layer would not have allowed the development of life on land until the late Ordovician. However, it was noted by Olson and Pierson that ferric iron strongly absorbs UV in the harmful wavelengths of 220-270 nm (3). These authors also noted that ferrous iron absorbs harmful UV too, but less strongly. The oldest known sedimentary rocks are from the Ishua Superacrustals and date from 3.8 Ga years ago that contain the banded iron formations in which 30% of the iron is ferric. Beverly K. Pierson et al demonstrated that relatively low concentrations of ferric iron (0.034 to 0.34 ppt) could act as an effective ozone shield in sediments 1 to 3 mm thick (4). However, Sagan et al reported in 1968 that a terrestrial microorganisms brought to Mars by spacecraft could become sequestered in ferric oxide dust particles on Mars that would shield them from impinging solar UV and then would be distributed by winds across the planet (5). Sagan suggested terrestrial organisms protected in this manner might contaminate the surface of Mars over a period of time. These examples serve to illustrate the possibility that microbial incursions onto dry land may have begun much sooner than the establishment of a substantial ozone layer in the late Ordovician, if the microorganisms were protected by ferric or ferrous iron dust. According to the theory of succession of life on Earth, before vascular plants could evolve and establish themselves onto dry land, microbial communities such as lichens, and edolithic algae would have had to populate the rocky surface and interiors of rocks. These microbes would then secrete organic acids and enzymes that over a period of hundreds to thousands of years would corrode or oxidize the rock components breaking the rock down to a mix of minerals and organic matter. Thus, the first soils appeared. However, it may well be that manganese precipitating fungi and bacteria protected from solar UV by low concentrations of ferric iron were the first land inhabitants. They would have been distributed globally from sea spray and dust carried by strong winds. Eventually the dust would settle out of the atmosphere onto rock surfaces, and the fungi and bacteria would begin precipitating Mn slowly building thinly protective layers (5 um – 1 mm) or microstromatolite structures called “rock varnish”. Rock varnish consists of Fe and Mn oxides 20-30%, clay minerals 60%, and oxides of other trace elements. The varnish layers have a laminated texture alternating from dark to light colored laminae that strongly resemble stromatolites (6). Krinsley and Dorn et al in 1990 reported that rock varnish layers are porous and permeable and can contain cracks that allow fluid to percolate into them (7). The sedimentation rate for a Mn and Fe-rich rock varnish coating can take over a thousand years or more for just a few microns (8). For this reason, rocks on which rock varnish is found must remain undisturbed for thousands or hundreds of thousands of years for a complete coating to form. This makes rock varnish an attractive paleobiomarker because as the individual layers form they trap atmospheric dust and organic materials. Dorn (9) found that as desert sands sweep across rocks covered with rock varnish, that the varnish can be eroded away in part or completely. If the wind and sand abrasion fail to remove all the varnish new varnish will begin to grow. This would also make rock varnish a useful tool or indicator for past aeolian activity. Rock varnish has been found on a variety of rocks such as coarse-grained granites, limestones, sandstones, and quartzites. However rocks such as limestone rarely can support thick rock varnish coatings because they erode more quickly than the rock varnish can form. The Mn and Fe minerals of rock varnish are not indigenous to the rock substrate itself and the fact that the underlying rock is devoid of any Mn or Fe demonstrate these minerals are brought in by winds, rain, dew or fog. Dorn and Oberlander also made the important distinction that dark biologically oxidized Mn-rich rock varnish only occurs on rocks with a slightly acidic or neutral pH while non-biological mechanisms for manganese oxidation operate strictly in highly alkaline environments where the pH is over 9 (10). Dark Mn- rich rock varnish does not occur below the soil line although orange colored Fe varnish often does. This peculiar difference in coloration would in part lead to the discovery that microorganisms are involved in the Mn-rich varnish process. It should also be noted that terrestrial inorganic coatings such as silica glaze interfingered with rock varnish produce a more lustrous look. The term “rock varnish” has replaced previous terminology such as “desert varnish”, “desert patina”, “weathering crust”, desert lacquer” and “desert rind” because it is now recognized to occur in almost all terrestrial environments, but most commonly in arid and semi-arid climates. Mn-rich rock varnish has also been documented in the cold dry desert of Antarctica (11). The first scientific data supporting that rock varnish hinted at a biological origin dates back to White in 1924 (12) and then Laudermilk in 1931 (13). The formation of rock varnish begins with small botryoidal nucleation centers of Mn-oxidizing bacteria, fungi, or algae that bloom and grow outward to cover the exposed rock surfaces. In extensive laboratory studies from rock varnish samples gathered from several regions around the world Krumbein and Jens in 1981 were able to culture 17 strains of manganese and iron precipitating fungi and 28 strains of bacteria. All these microflora shared in their ability to precipitate manganese oxide. Furthermore, Krumbein and Jens found endolithic fungi and cyanobacteria had bored pits in the rock substrate below layers of Mn-rich rock varnishes. These same researchers documented that exposed desert pavements also accumulate the same Mn-rich rock varnish coatings precipitated by microorganisms (14). Other interesting investigations by El-Baz and Prestal presented to the 11th Lunar and Planetary Science Conference in 1980 revealed that sand grains from the Southwestern desert of Egypt were coated with reddish to dark brown oxide coatings, indicating rock varnish on individual sand grains (15). Raymond et al in 1992 compared the Mn-rich layers of rock varnish to microstromatolites (Figure 1) and described bacteria, fungi and organic matter within the layers (16) (Figure 2). Dorn and Oberlander also previously described the active precipitation and concentration of Mn within rock varnish coatings (17). There are generally two classifications of rock varnish 1) Rock varnish found in semi-arid to arid environments in weakly acidic or weakly alkaline soil conditions that have Mn- and Fe-rich coatings 2) Fe-rich but Mn-poor rock varnish. The ratio of Fe to Mn determine the color of the varnish, with Mn-rich varnishes giving a brown, black or grey (lead color) while the Fe-rich/Mn-poor variety display orange and reddish coloration’s. The shinny effect observed on rocks coated with Mn-rich rock varnishes are produced by the thickness of the coating and varying concentrations of Fe, Mn, and clay minerals (18). One of the most recent important observations regarding rock varnish was the detection of magnetite components within various layers. Arvidson et al participated in the 1997 Lavic Lake (Mojave Desert) Field tests using the Rocky 7 prototype Mars Rover which carried a Iron-nuclear Magnetic Resonance (57Fe-NMR) Spectrometer (19). The 57Fe-NMR instrument was developed by Soon Sam Kim of the Jet Propulsion Laboratory and while using it in-situ discovered magnetite in rock varnish. Independent work by Rocco Mancinelli of NASA Ames Research Center along with colleagues Melisa White and Christine Sawyer presented evidence at the May 7, 1997 annual meeting for the American Society of Microbiology that they found magnetite-producing bacteria in samples of Death Valley rock varnish. They determined this by growing the bacteria from the rock varnish scrapings under laboratory conditions (20). E.I. Friedmann et al demonstrated the presence of magnetite crystal chains, previously considered the missing evidence for biological magnetite in the Martian meteorite ALH 84001 (21). The mineralogical analysis of five other SNC Martian meteorites has revealed an average Mn oxide concentration of 0.48% relative to the 0.1 concentration of Mn found in Earth’s crust. Analysis of the soils at the Mars Pathfinder landing site by the Alpha Proton X-ray Spectrometer showed FeO/MnO oxides were 29.2% by weight. These intriguing figures beg the following questions: 1) Do Martian rocks and soils have coatings of biologically produced rock varnish on them? 2) Are the environmental conditions on Mars today capable of supporting extant microbial communities needed to produce rock varnish? FOG DESERTS Lying west of the Andes Mountains in northern Chile is the Atacama Desert, one of the driest deserts in the world. Average precipitation here is only 1 cm/yr. from winter fogs and dew. These winter fogs frequently blanket the coastal deserts and act as an effective block to solar UV radiation. They are produced when cold north-flowing ocean currents that dominate along the coastlines of Chile and Peru prevent winds from picking up enough moisture to produce rain. Daily temperatures can vary between 0 degrees C to 25 degrees C. To the untrained eye, the Atacama Desert appears as a stark lifeless expanse of sand, dust and rocks. At the microscopic level however, a wide range of living microorganisms such as bacteria, actinomycetes, fungi and algae can be found thriving in a variety of environments: Endedaphic microorganisms are found in crusts on the soil surface, hypolithic microbes survive on stones, while lythophytes such as chasmolithic algae live inside rock fissures and endolithic algae penetrate into the pore spaces of rocks. Dusky-brown to black ferromanganese coatings produced by Mn-fixing bacteria drape and sometimes completely obscure the rock surfaces and desert pavement of the Atacama. At times the condensate from winter fogs is sufficient enough to moisten soil to depths of a millimeter or two. Also, because of the relative high humidity near the coastal range, biologically significant quantities of water are available as dew from the June to August winter nights. Although the dew formed during the night is largely evaporated at sunrise, the near-surface soil moisture can remain relatively high during the cold winter months. During periods of fogs solar UV can be significantly attenuated. Given that terrestrial fog and dew alone can sustain large populations of microorganisms in desert soil and rocks make the extensive low lying fogs on the planet Mars intriguing areas to search for similar microbial desert inhabitants including those that produce rock varnish. Pollack et al first reported on Martian ground fogs at both Viking 1 and 2 landing sites that were separated by 4,000 km in different geographical locations (22). Their observation period ran from mid-July 1976 to February of 1977 as Mars was changing seasons from early summer to midfall. It was concluded at the time that ground fogs composed of water ice particles formed before sunrise and quickly dissipated during the late morning. The fogs were present at both landing sites during the length of their observation period. In 1997 Moore et al noted that the Viking Lander 2 footpad collector head temperatures reached 273 degrees K and above along with atmospheric pressures exceeding 7 millibars (23). Moore and his colleagues first commented that it was possible that brief periods of liquid water (wetting events) might exist during times when conditions at the landing site exceeded the triple point of water. Rock and soil temperature measurements were made using the Viking Orbiter IRTM instrument from 1976-1979 by Principal Investigator Terry Z. Martin. He stated that some surface IRTM temperature data from the equatorial regions reached highs of 300 -310 degrees K (24). In 1995 Hannu Savijarvi presented a model of diurnal moisture cycle and soil properties at the Viking 1 landing site based on nighttime fogging and frosting of the Viking cameras (25). Savijarvi then calculated that cold nighttime temperatures led to saturation of water vapor and surface fog with humidities at 100% during the night and dropping off below 1% in the afternoon. However, the issue of a diurnal moisture cycle would not be fully addressed again until 1998 when Levin and Levin first published a model for the diurnal presence of biologically significant quantities of liquid water over large areas on Mars (26). Since then others have constructed similar moisture cycle models with the most striking being published by Lobitz et al that combined both Viking pressure, temperature and Mars Global Surveyor MOLA data to suggest liquid water would be stable over the northern lowlands equatorward to about 40 degrees (27). The authors cited that the southwestern portion of Utopia Planitia could have liquid water as much as 34% of the Martian year if it were present. This model supports that low laying fogs observed from the Viking orbiters in regions near the valley networks such as Labyrinthus Noctis, might produce seasonal wetting events due to fog. The Mariner 9 and Viking orbiter images also confirmed fogs forming in the southern hemisphere, especially in the Hellas and Argyre basins, Solis Planum, Sinus Sabeus, and in numerous low laying craters (28). These observations call into question the possibility that summer Martian ground fogs can wet rocks and moisten soils similar as fogs do in the Atacama Desert. ARE MARTIAN ROCKS COVERED BY ROCK VARNISH? The first mention of rock stains or patinas on Mars, came from Alan B. Binder et al who described the geology of the Viking 1 landing site as having partly stained outcrops, rock fragments, and finer material (29). He and his colleagues attributed this staining to chemical weathering analogous to terrestrial deserts. In 1979 E.L. Strickland III noted that the surfaces and sides of many rocks at both Viking landing sites were identical in color to the duricrust. Strickland then went on to state the colors on most of the rocks at both Viking 1 and 2 landing sites suggested deposition by environmental processes, rather than mineralogical variations within the underlying rock (30). In 1996 prior to the Mars Pathfinder mission to Mars, E.A. Guinness et al showed that coated rocks at the Viking landing sites had high reflectance in the forward scattering direction (specular reflection) similar to varnished rock surfaces found in terrestrial deserts (Figures 3 & 4). This abstract also revealed that rocks at both Viking 1 and 2 landing sites appeared to show dark shiny coatings under different sun angles, but most commonly after sunrise (31). They concluded that the rock coatings on Mars might make the measurement of underlying rock chemistry difficult for Mars Pathfinder APXS. Numerous attempts have been made using remote sensing in the near infrared with instruments on the Marniner 9 and Viking Orbiters to try and obtain information on the mineralogy of Martian rocks and soils. However, interference by the spectral signatures of atmospheric dust, aerosols, CO2 molecules and water vapor have all made this work extremely difficult. The Thermal Emission Spectrometer aboard Mars Global Surveyor has fared no better. According to J.G. Ward et al thermal infrared spectral signatures of desert varnish and silica-glaze cooling rinds are so similar, that if it is on Mars it requires a different method of detection to differentiate between them (32). Because of the dust coatings found to be covering all the rocks at the Mars Pathfinder landing site in 1997, chemical analysis by the APXS and near-infrared reflectance measurements were reduced significantly. Kraft et al suggest in their paper that data about the coatings covering the MPF rocks seem to be similar to terrestrial rock varnish (33). Multispectral analysis of the rocks at Mars Pathfinder as reported by McSween et al were essentially non-conclusive (34). In a 1999 article written for NEW SCIENTIST, McSween stated that rocks at the MPF site were so difficult to analyze because of the coatings covering the rocks, that he suggested on a future Mars landers a mechanism designed to scrape-off dust and rock coatings to expose the underlying rock surfaces for examination (35). Because of its orbit and position as the fourth planet in the solar system, the incident solar radiation reaching Mars is approximately 44% less than the Earth. This makes the atmospheric density and pressure of the near-surface environment of Mars comparable to the terrestrial atmosphere at 30,000 meters (100,000 feet) (36). However, since Mars’ orbit is elliptical this can vary by a factor of two. Therefore obtaining data about the ultraviolet (UV) flux at the surface of Mars is crucial to understanding how any life might be able to survive there. As mentioned previously in the introduction of this paper, the current terrestrial biosphere is shielded by the ozone (O3) layer which filters out the Hartley bands in the 200-300 nm range and the Huggins bands from 300-360 nm. Since Mars has a variable ozone abundance of only 2% that of Earth, it receives a higher flux of UV. How much UV reaches the surface unattenuated is a question that needs to be addressed over a period of different Martian seasons and conditions with future spacecraft landers. It is well known that CO2 is an excellent absorber of UV in the wavelengths < 204 nm and provides an effective shield below ~ 190 nm. Since Mars has < 50 times more CO2 than the terrestrial atmosphere that can change dramatically by 25% with the onset of winter, further studies on the variability of UV intensity will need to be conducted (37). Dust suspended in the Martian atmosphere would also absorb and scatter UV effectively, however, observations made by Philip James and Steven Lee et al using the Hubble Space Telescope 1995-1997 have reported that the dust can settle out of the atmosphere nearly completely at times (38). Clouds, low laying fogs, and snow all would act to temporarily attenuate UV as well. Thus it is conceivable that an ongoing combination of these meteorological events could filter out biologically harmful solar UV for significant periods of time so that well-adapted Martian microorganisms could take advantage of times of low UV flux to carry out their life processes. Also, just as it does on Earth, any biologically produced Mn-rich and Fe rock varnish on Mars would offer UV protection to the microflora residing within and beneath the varnished layers (39). During these periods of low UV flux perhaps due to persistent dust, clouds, and fogs, Martian microbes would then add new layers to the outer portions of the rock varnish. Evidence returned by the Apollo 12 crew from the surface of the Moon revealed that a species of Streptococcus mitis survived on a layer of insulted foam inside the Surveyor III lunar probe which remained on the Moon a period of 2 ½ years (40). Mileikowsky et al have calculated that the maximum time a Martian meteorite ejected from the surface of Mars could reside in the vacuum of space and still maintain viable spores is 100,000 years (41) due to ionizing radiation. If this estimate is accurate, then endolithic spores sequestered within Martian rock varnish could become viable anytime conditions would allow. CONCLUSIONS AND RECOMMENDATIONS It is completely plausible that life developed on Mars roughly the same time period as Earth, or perhaps even before. The early exchange of planetary debris during the late bombardment period would have allowed viable microbial spores from the Earth to reach Mars, and vise versa. If Mars had the liquid water necessary to create the extensive dry tributary and drainage systems observed today, then there is no reason to think that Martian life would not have flourished and quickly evolved. However, perhaps due to a catastrophic impact(s) event(s) that dissipated its thicker atmosphere and abundant liquid water millions or billions of years ago, life on Mars would have had to struggle and find every possible niche to survive. Without pools of liquid water to sequester them, Martian life forms would have to adapt to conditions of dry land and derive their water requirements directly from atmospheric sources. This would mean living under dust layers in the soil, within rocks, and constructing biogenic rock coatings. The Labeled Release (LR) experiment on both the Viking 1 and 2 landers conducted nine soil tests on the surface of Mars in two locations separated by thousands of kilometers. The LR used a variety of experimental test conditions that would lead the Principal Investigator to conclude active metabolism of microorganisms on Mars (42). Surprisingly, little has been done to date by the scientific community to elucidate on this extremely important matter. Since rock coatings have been observed at both Viking landing sites and the Mars Pathfinder landing site, it is reasonable to assume that rock coatings on Mars are a globally ubiquitous phenomenon. Given the importance that the discovery of biologically produced rock varnish on Mars would have on astrobiology, immediate measures should be taken to plan spacecraft landers with appropriately equipped instruments capable of rendering a conclusion. The next opportunity to examine the rock coatings on Mars is with the Beagle 2 lander scheduled to touch down in December of 2003. Beagle 2 will land in Isidis Planitia a sedimentary basin 10 degrees north of the equator. Fortunately, Beagle 2 is equipped with several key scientific instruments (flown for the first time on any Mars mission) necessary to shed light on the issue of rock varnish, they are: 1) XRD spectrometer 2) Mossbauer spectrometer 3) microscope 4) Gas Analysis Package 5) and rock corer (43). A typical scenario to examine the rock coatings on Mars for extant or extinct microorganisms would be the following: A) Select several target rocks with dark shinny coatings on them and use the coring device to extract rock coatings from shallow samples. B) Examine the core samples by microscope and seek any morphology of laminations indicative of microstromatolites (rock varnish). Also observe cross sections for evidence of the size and shape for bacteria (cigar shaped and rounded forms) and fragments of cell-wall casts . C) Look for evidence of organic material entrapped within the individual laminae with GAP. D) Try and determine the Mn-Fe ratio of the samples by XRD. E) Use the Beagle 2 Mossbauer spectrometer to determine oxidation sate of minerals in the rock varnish samples. One other important issue to consider is that many of the rocks on Mars may actually be meteorites and therefore their analysis would not any shed light on the mineralogy of Mars. 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The Viking Labeled Release Experiment and Life on Mars, in Instruments, Methods, and Missions for the Investigation of Extraterrestrial Microorganisms, Proc. Internat. Soc. for Opt. Engnrg., Proc. Series, 3111, p. 146-161. 43. M.R. Sims, C.T. Pillinger, I.P. Wright, G. et al., 2000. Instrumentation on Beagle 2: The Astro-Biology Lander on ESA’s 2003 Mars Express Mission, SPIE Proceedings, 4137, p36-47. FIGURES Figure 1 Backscattered electron microscope sequence of Mn-concentrating bacteria from rock varnish samples found covering basalt from the Ashikule Basin in Tibet. The basalts in this region are dominated by silica glaze with pockets of Mn-rich varnish. Note layered stromatolite appearance of the sample. Dark and light layers represent variations in the Mn/Fe ratio indicating altering conditions of deposition. Figure 2 Rock varnish from Kitt Peak, Arizona shown in two different perspectives: left is secondary electron microscopy, right: backscattered electrons. Both images show botryoidal micromorphologies associated with Mn-oxidizing microorganisms. Figure 3 Early morning front-lighted view from the Viking 1 lander showing dark coatings on rocks. Compare same scene with afternoon lighting in figure 4. Figure 4 Same Viking 1 lander scene and viewing angle as Figure 3 but only under afternoon lighting conditions.
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