An infrared study of modern and paleo-filamentous bacteria from Rio Tinto, Spain

The Rio Tinto River Basin in southwestern Spain is a natural acidic (pH ~2.3) drainage system that supports a diversity of acid tolerant bacteria and eukaryotes with iron and sulfur- oxidizing prokaryotes performing chemolithotrophy and supporting anaerobic respiration [1, 2]. River terrace deposits formed over the past 2 Myr have preserved remnants of this unique biosphere, particularly microbial filaments, which provide templates for iron sulphate and iron oxide precipitation [1, 2]. This process of permineralization causes organic material to become trapped within a mineral matrix and preserved over geological time. This study analysed cultured filamentous bacteria, modern biofilms and sediments, and river terrace deposits spanning 2.1 Myr to assess the preservation of organics in this extreme environment over time, and the ability to correlate them with a contemporary culture. Filamentous bacteria are preserved within optically translucent nanophase to crystalline jarosite and goethite within all samples. The cultures contained 1 μm diameter filaments, some partially encrusted with iron oxides with visible cell walls, and others completely free of iron oxides, that are morphologically comparable to those preserved in the Rio Tinto rock record. Organic compounds (e.g. aliphatic hydrocarbons, amides and carboxylic acids) were detected at various levels within the culture and river terraces using mid-IR spectroscopy. Rio Tinto is a natural laboratory allowing living cells to be studied and correlated to morphological and biomolecular fossils in the geological record. These deposits will provide predictive tools for biomarker studies that may be extended to analogous environments on ancient Earth or even Mars. [1] Fernández-Remolar et al. (2005) Earth Planet Sci Lett 240,149-167. [2] Fernández-Remolar & Knoll (2008) Icarus 194,72-85

Oxalate formation under the hyperarid conditions of the Atacama desert as a mineral marker to provide clues to the source of organic carbon on Mars

In this study, we report the detection and characterization of the organic minerals weddellite (CaC2O4 · 2H2O) and whewellite (CaC2O4 · H2O) in the hyperarid, Mars-like conditions of the Salar Grande, Atacama desert, Chile. Weddellite and whewellite are commonly of biological origin on Earth and have great potential for preserving records of carbon geochemistry and possible biological activity on Mars if they are present there. Weddellite and whewellite have been found as secondary minerals occurring inside the lower detrital unit that fills the Salar Grande basin. The extremely low solubility of most oxalate minerals inhibits detection of oxalate by ion chromatography (IC). Crystalline oxalates, including weddellite and whewellite, were detected by X-ray diffraction (XRD). The association of weddellite with surface biota and its presence among subsurface detrital materials suggest the potential of a biological origin for Salar Grande weddellite and whewellite. In this regard, biological activity is uniquely capable of concentrating oxalates at levels detectable by XRD. The complementary detection of oxalate-bearing phases through IC in the upper halite-rich unit suggests the presence of a soluble oxalate phase in the basin that is not detected by XRD. The formation, transport, and concentration of oxalate in the Salar Grande may provide a geochemical analogue for oxalate-bearing minerals recently suggested to exist on Mars

Mineralogical In-situ Investigation of Acid-Sulfate Samples from the Rio Tinto River, Spain, with a Portable XRD/XRF Instrument

A field campaign was organized in September 2006 by Centro de Astobiologica (Spain) and Washington University (St Louis, USA) for the geological study of the Rio Tinto river bed sediments using a suite of in-situ instruments comprising an ASD reflectance spectrometer, an emission spectrometer, panoramic and close-up color imaging cameras, a life detection system and NASA's CheMin 4 XRD/XRF prototype. The primary objectives of the field campaign were to study the geology of the site and test the potential of the instrument suite in an astrobiological investigation context for future Mars surface robotic missions. The results of the overall campaign will be presented elsewhere. This paper focuses on the results of the XRD/XRF instrument deployment. The specific objectives of the CheMin 4 prototype in Rio Tinto were to 1) characterize the mineralogy of efflorescent salts in their native environments; 2) analyze the mineralogy of salts and oxides from the modern environment to terraces formed earlier as part of the Rio Tinto evaporative system; and 3) map the transition from hematite-dominated terraces to the mixed goethite/salt-bearing terraces where biosignatures are best preserved

In-situ Mössbauer Spectroscopy with MIMOS II at Rio Tinto, Spain

The Rio Tinto, located in southwest Spain, exhibits a nearly constant, acidic pHvalue along its course. Due to the formation of sulfate minerals, Rio Tinto is considered a potential analogue site for sulfate-rich regions on Mars, in particular at the landing site of the Mars Exploration Rover Opportunity, where the ferric sulfate mineral jarosite was identified with Opportunity's Mössbauer spectrometer. Primary and secondary mineralogy was investigated in situ with portable Raman and Mössbauer spectrometers at four different Rio Tinto sampling sites. The two techniques analyse different sample portions due to their specific field of view and sampling depth and provide complementary mineralogical information

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposit At Rio Tinto, Spain: Implications For Extant Life On Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth's largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors

Mars Sulfate Formation Sourced in Sulfide-Enriched Subsurface Fluids: The Rio Tinto Model

The extensive evidence for sulfate deposits on Mars provided by analyses of MER and Mars Express data shows that the sulfur played an essential role in the geochemical cycles of the planet, including reservoirs in the atmosphere, hydro-sphere and geosphere. Overall the data are consistent with a fluvial/lacustrine-evaporative origin of at least some of the sulfate deposits, with mineral precipitation through oversaturation of salty acidic fluids enriched in sulfates. This scenario requires reservoirs of sulfur and associated cations, as well as an acidic and oxidizing hydrochemistry which could be provided by surface and subsurface catching of meteoric waters resulting in the presence of sulfur-bearing gases and steam photochemistry. In this work we suggest a new scenario for the extensive generation of sulfates in Mars based on the observation of seasonal changes in the redox and pH of subsurface waters enriched in sulfur that supply the acidic Mars process analog of Rio Tinto. This model considers the long-term subsurface storage of sulfur during most of Noachian and its release from the late Noachian to Hesperian time through weathering by meteoric fluids that would acidify and oxidize the sulfur bearing compounds stored in the subsurface

Coupled C, H, N, S and Fe biogeochemical cycles operating in the continental deep subsurface of the Iberian Pyrite Belt

Microbial activity is a major contributor to the biogeochemical cycles that make up the life support system of planet Earth. A 613 m deep geomicrobiological perforation and a systematic multi-analytical characterization revealed an unexpected diversity associated with the rock matrix microbiome that operates in the subsurface of the Iberian Pyrite Belt (IPB). Members of 1 class and 16 genera were deemed the most representative microorganisms of the IPB deep subsurface and selected for a deeper analysis. The use of fluorescence in situ hybridization allowed not only the identification of microorganisms but also the detection of novel activities in the subsurface such as anaerobic ammonium oxidation (ANAMMOX) and anaerobic methane oxidation, the co-occurrence of microorganisms able to maintain complementary metabolic activities and the existence of biofilms. The use of enrichment cultures sensed the presence of five different complementary metabolic activities along the length of the borehole and isolated 29 bacterial species. Genomic analysis of nine isolates identified the genes involved in the complete operation of the light-independent coupled C, H, N, S and Fe biogeochemical cycles. This study revealed the importance of nitrate reduction microorganisms in the oxidation of iron in the anoxic conditions existing in the subsurface of the IPBFP7 Ideas: European Research Council, Grant/Award Number: ERC Advanced Grant #250-35

Scientific Goals and Objectives for the Human Exploration of Mars: 1. Biology and Atmosphere/Climate

To prepare for the exploration of Mars by humans, as outlined in the new national vision for Space Exploration (VSE), the Mars Exploration Program Analysis Group (MEPAG), chartered by NASA's Mars Exploration Program (MEP), formed a Human Exploration of Mars Science Analysis Group (HEM-SAG), in March 2007. HEM-SAG was chartered to develop the scientific goals and objectives for the human exploration of Mars based on the Mars Scientific Goals, Objectives, Investigations, and Priorities.1 The HEM-SAG is one of several humans to Mars scientific, engineering and mission architecture studies chartered in 2007 to support NASA s plans for the human exploration of Mars. The HEM-SAG is composed of about 30 Mars scientists representing the disciplines of Mars biology, climate/atmosphere, geology and geophysics from the U.S., Canada, England, France, Italy and Spain. MEPAG selected Drs. James B. Garvin (NASA Goddard Space Flight Center) and Joel S. Levine (NASA Langley Research Center) to serve as HEMSAG co-chairs. The HEM-SAG team conducted 20 telecons and convened three face-to-face meetings from March through October 2007. The management of MEP and MEPAG were briefed on the HEM-SAG interim findings in May. The HEM-SAG final report was presented on-line to the full MEPAG membership and was presented at the MEPAG meeting on February 20-21, 2008. This presentation will outline the HEM-SAG biology and climate/atmosphere goals and objectives. A companion paper will outline the HEM-SAG geology and geophysics goals and objectives

Identification of Hydrated Sulfates Collected in the Northern Rio Tinto Valley by Reflectance and Raman Spectroscopy

OMEGA recently identified spectral signatures of kieserite, gypsum, and other polyhydrated sulfates at multiple locations on the surface of Mars [1,2]. The presence of sulfates was confirmed through in situ spectroscopy by MER Opportunity [3]. An approach to validate these interpretations is to collect corresponding spectral data from sulfate-rich terrestrial analog sites. The northern Rio Tinto Valley near Nerva, Spain, is a good Martian analog locale because it features extensive seasonal sulfate mineralization driven by highly acidic waters [4]. We report on mineralogical compositions identified by field VNIR spectroscopy and laboratory Raman spectroscopy

Mossbauer mineralogy of rock, soil, and dust at Meridiani Planum, Mars: Opportunity's journey across sulfate-rich outcrop, basaltic sand and dust, and hematite lag deposits

The Mössbauer (MB) spectrometer on Opportunity measured the Fe oxidation state, identified Fe-bearing phases, and measured relative abundances of Fe among those phases at Meridiani Planum, Mars. Eight Fe-bearing phases were identified: jarosite (K,Na,H3O)(Fe,Al)(OH)6(SO4)2, hematite, olivine, pyroxene, magnetite, nanophase ferric oxides (npOx), an unassigned ferric phase, and metallic Fe (kamacite). Burns Formation outcrop rocks consist of hematite-rich spherules dispersed throughout S-rich rock that has nearly constant proportions of Fe3+ from jarosite, hematite, and npOx (29%, 36%, and 20% of total Fe). The high oxidation state of the S-rich rock (Fe3+/FeT ~ 0.9) implies that S is present as the sulfate anion. Jarosite is mineralogical evidence for aqueous processes under acid-sulfate conditions because it has structural hydroxide and sulfate and it forms at low pH. Hematite-rich spherules, eroded from the outcrop, and their fragments are concentrated as hematite-rich soils (lag deposits) on ripple crests (up to 68% of total Fe from hematite). Olivine, pyroxene, and magnetite are primarily associated with basaltic soils and are present as thin and locally discontinuous cover over outcrop rocks, commonly forming aeolian bedforms. Basaltic soils are more reduced (Fe3+/FeT ~ 0.2–0.4), with the fine-grained and bright aeolian deposits being the most oxidized. Average proportions of total Fe from olivine, pyroxene, npOx, magnetite, and hematite are 33%, 38%, 18%, 6%, and 4%, respectively. TheMB parameters of outcrop npOx and basaltic-soil npOx are different, but it is not possible to infer mineralogical information beyond octahedrally coordinated Fe3+. Basaltic soils at Meridiani Planum and Gusev crater have similar Fe-mineralogical compositions.Additonal co-authors: P Gütlich, E Kankeleit, T McCoy, DW Mittlefehldt, F Renz, ME Schmidt, B Zubkov, SW Squyres, RE Arvidso