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At least 73 records · Page 4

Integrated Microchemical Analysis System Using DS2 Penetrator Technology for the Enantiomeric Detection of Amino Acids

Any strategy for investigating whether abiotic and/or biotic organic molecules are present on Mars and the search for biosignatures should focus on compounds which are readily synthesized under plausible prebiotic conditions, play an essential role in biochemistry as we know it and have properties such as chirality (handedness) which can be used to distinguish between abiotic vs. biotic origins (1). Amino acids are one of the few compound classes that fulfill all these requirements. They are synthesized in high yields in prebiotic simulation experiments, are one of the more abundant types of organic compounds present in carbonaceous meteorites and only the L-enantiomers are used in the proteins and enzymes in life on Earth.

Frank J Grunthaner↗

Meteors: A Delivery Mechanism of Organic Matter to The Early Earth

All potential exogenous pre-biotic matter arrived to Earth by ways of our atmosphere, where much material was ablated during a luminous phase called 1. meteors" in rarefied flows of high (up to 270) Mach number. The recent Leonid showers offered a first glimpse into the elusive physical conditions of the ablation process and atmospheric chemistry associated with high-speed meteors. Molecular emissions were detected that trace a meteor's brilliant light to a 4,300 K warm wake rather than to the meteor's head. A new theoretical approach using the direct simulation by Monte Carlo technique identified the source-region and demonstrated that the ablation process is critical in the heating of the meteor's wake. In the head of the meteor, organic carbon appears to survive flash heating and rapid cooling. The temperatures in the wake of the meteor are just right for dissociation of CO and the formation of more complex organic compounds. The resulting materials could account for the bulk of pre-biotic organic carbon on the early Earth at the time of the origin of life.

Jenniskens, Peter↗

The Next Generation MOD: A Microchip Amino Acid Analyzer for Detecting Extraterrestrial Life

The MOD (Mars Organic Detector) instrument which has selected for the definition phase of the BEDS package on the 2005 Mars Explorer Program spacecraft is designed to simply detect the presence of amino acids in Martian surface samples at a sensitivity of a few parts per billion (ppb). An additional important aspect of amino acid analyses of Martian samples is identifying and quantifying which compounds are present, and also distinguishing those produced abiotically from those synthesized by either extinct or extant life. Amino acid homochirality provides an unambiguous way of distinguishing between abiotic vs. biotic origins. Proteins made up of mixed D- and L-amino acids would not likely have been efficient catalysts in early organisms because they could not fold into bioactive configurations such as the a-helix. However, enzymes made up of all D-amino acids function just as well as those made up of only L-amino acids, but the two enzymes use the opposite stereoisomeric substrates. There are no biochemical reasons why L-amino acids would be favored over Damino acids. On Earth, the use of only L-amino acids in proteins by life is probably simply a matter of chance. We assume that if proteins and enzymes were a component of extinct or extant life on Mars, then amino acid homochirality would have been a requirement. However, the possibility that Martian life was (or is) based on D-amino acids would be equal to that based on L-amino acids. The detection of a nonracemic mixture of amino acids in a Martian sample would be strong evidence for the presence of an extinct or extant biota on Mars. The finding of an excess of D-amino acids would provide irrefutable evidence of unique Martian life that could not have been derived from seeding the planet with terrestrial life (or the seeding of the Earth with Martian life). In contrast, the presence of racemic amino acids, along with non-protein amino acids such as alpha-aminoisobutyric acid and isovaline, would be indicative of an abiotic origin, although we have to consider the possibility that the racemic amino acids were generated from the racemization of biotically produced amino acids.

Mathies, R. A.↗

Mars Hematite Site: Potential for Preservation of Microfossils

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of pre-biotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3) have been identified from orbit by thermal emission spectrometry. The largest such deposit, in Sinus Meridiani, is a strong candidate landing site for one of the twin Mars Exploration Rovers, scheduled to launch in 2003. The Martian hematite site may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists for preserving microscopic evidence of life in ecosystems that deposit iron oxides. Terrestrial hematite deposits proposed as possible analogs for the hematite sites on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We are engaged in a systematic effort to document the evidence of life preserved in iron oxide deposits from each of these environments.

Allen, Carlton C.↗

Preliminary Assessment of Mars Exploration Rover Landing Site Predictions

Selection of the Mars Exploration Rover (MER) landing sites took place over a three year period in which engineering constraints were identified, 155 possible sites were downselected to the final two, surface environments and safety considerations were developed, and the potential science return at the sites was considered. Landing sites in Gusev crater and Meridiani Planum were selected because they appeared acceptably safe for MER landing and roving and had strong morphologic and mineralogical indicators of liquid water in their past and thus appeared capable of addressing the science objectives of the MER missions, which are to determine the aqueous, climatic, and geologic history of sites on Mars where conditions may have been favorable to the preservation of evidence of possible pre-biotic or biotic processes. Engineering constraints important to the selection included: latitude (10 N-15 S) for maximum solar power; elevation (<-1.3 km) for sufficient atmosphere to slow the lander; low horizontal winds, shear and turbulence in the last few kilometers to minimize horizontal velocity; low 10-m scale slopes to reduce airbag spinup and bounce; moderate rock abundance to reduce abrasion or stroke-out of the airbags; and a radar-reflective, load-bearing and trafficable surface safe for landing and roving that is not dominated by fine-grained dust. In selecting the MER landing sites these engineering constraints were addressed via comprehensive evaluation of surface and atmospheric characteristics from existing remote sensing data and models as well as targeted orbital information acquired from Mars Global Surveyor and Mars Odyssey. This evaluation resulted in a number of predictions of the surface characteristics of the sites, which are tested in this abstract. Relating remote sensing signatures to surface characteristics at landing sites allows these sites to be used as ground truth for the orbital data, is essential for selecting and validating landing sites for future missions, and is required for correctly interpreting the surfaces and materials globally present on Mars.

Golombek, M.↗

Probabilistic Classification Using Elemental Abundance Distributions and Lossless Image Compression in Apollo 17 Lunar Dust Samples from Mare Serenitatis

We have previously outlined a strategy for the detection of fossils [Storrie-Lombardi and Hoover, 2004] and extant microbial life [Storrie-Lombaudi and Hoover, 20051 during robotic missions to Mars using co-registered structural and chemical signatures. Data inputs included image lossless compression indices to estimate relative textural complexity and elemental abundance distributions. Two exploratory classification algorithms (principal component analysis and hierarchical cluster analysis) provide an initial tentative classification of all targets. Nonlinear stochastic neural networks are then trained to produce a Bayesian estimate of algorithm classification accuracy. The strategy previously has been successful in distinguishing regions of biotic and abiotic alteration of basalt glass from unaltered samples. [Storrie-Lombardi and Fisk, 2004; Storrie-Lombardi and Fisk, 2004] Such investigations of abiotic versus biotic alteration of terrestrial mineralogy on Earth are compromised by .the difficulty finding mineralogy completely unaffected by the ubiquitous presence of microbial life on the planet. The renewed interest in lunar exploration offers an opportunity to investigate geological materials that may exhibit signs of aqueous alteration, but are highly unlikely to contain contaminating biological weathering signatures. We here present an extension of our earlier data set to include lunar dust samples obtained during the Apollo 17 mission. Apollo 17 landed in the Taurus-Littrow Valley in Mare Serenitatis. Most of the rock samples from this region of the lunar highlands are basalts comprised primarily of plagioclase and pyroxene and selected examples of orange and black volcanic glass. SEM images and elemental abundances (C6, N7, O8, Na11, Mg12, Al13, Si14, P15, S16, Cll7, K19, Ca20, Fe26) for a series of targets in the lunar dust samples are compared to the extant cyanobacteria, fossil trilobites, Orgueil meteorite, and terrestrial basalt targets previously discussed. The data set provides a first step in producing a quantitative probabilistic methodology for geobiological analysis of returned lunar samples or in situ exploration.

Storrie-Lombardi, Michael C.↗

The Science from Spirit and Opportunity

This slide presentation shows views from the Mars rovers, Spirit and Opportunity. Included are views of the takeoff, and descent on to Mars. The science objective of these missions are to determine the water, climate, and geologic history of two sites on Mars where evidence has been preserved for past and persistent liquid water activity that may have supported biotic or pre-biotic processes. There are also shots of the Athena Science Payload with views of the instrumentation. Also presented are graphs showing Mossbauer Spectra of varions martian rocks.

Spirit↗

Heavy Ion Formation in Titan's Ionosphere: Magnetospheric Introduction of Free Oxygen and a Source of Titan's Aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with approx.2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (CCR) and the ablation of incident meteoritic dust from Enceladus' E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms CnHx. There could also be hollow shells of carbon atoms, such as C60, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H(2+) and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N(2+), N(+) and CH(4+) can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O(+) can interact with abundant CH4 contributing to the CO and CO2 observed in Titan's atmosphere. If an exogenic keV O(+) ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's "warm ponds" on Titan.

Sittler, E. C., Jr.↗

Field Characterization of the Mineralogy and Organic Chemistry of Carbonates from the 2010 Arctic Mars Analog Svalbard Expedition by Evolved Gas Analysis

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return. The Sample Analysis at Mars (SAM) [1] instrument suite, which will be on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser mass spectrometer (TLS); all will be applied to analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-MS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples [e.g., 2]. Field-portable versions of CheMin were used during AMASE. AMASE 2010 focused on two sites that represented biotic and abiotic analogs. The abiotic site was the basaltic Sigurdfjell vent complex, which contains Mars-analog carbonate cements including carbonate globules which are excellent analogs for the globules in the ALH84001 martian meteorite [e.g., 3, 4]. The biotic site was the Knorringfjell fossil methane seep, which featured carbonates precipitated in a methane-supported chemosynthetic community [5]. This contribution focuses on EGA-MS analyses of samples from each site, with mineralogy comparisons to CheMin team results. The results give insight into organic content and organic-mineral associations, as well as some constraints on the minerals present.

McAdam, A. C.↗

delta C-13 Analysis of Mars Analog Carbonates Using Evolved Gas Cavity - Ringdown Spectrometry on the 2010 Arctic Mars Analog Svalbard Expedition (AMASE)

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two distinct geologic settings on Svalbard, using instrumentation and techniques in development for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return (MSR). The Sample Analysis at Mars (SAM) instrument suite, which will fly on MSL, was developed at Goddard Space Flight Center (GSFC), together with several partners. SAM consists of a quadrupole mass spectrometer (QMS), a gas chromatograph CGC), and a tunable laser spectrometer (TLS), which all analyze gases created by evolved gas analysis (EGA). The two sites studied represent "biotic" and "abiotic" analogs; the "biotic" site being the Knorringfjell fossil methane seep, and the "abiotic" site being the basaltic Sigurdfjell vent complex. The data presented here represent experiments to measure the carbon isotopic composition of carbonates from these two analogs using evolved gas analysis coupled with a commercial cavity ringdown CO2 isotopic analyzer (Picarro) as a proxy for the TLS on SAM.

Stern, J. C.↗

Does Terrestrial Drought Explain Global CO2 Flux Anomalies Induced by El Nino?

The El Nino Southern Oscillation is the dominant year-to-year mode of global climate variability. El Nino effects on terrestrial carbon cycling are mediated by associated climate anomalies, primarily drought, influencing fire emissions and biotic net ecosystem exchange (NEE). Here we evaluate whether El Nino produces a consistent response from the global carbon cycle. We apply a novel bottom-up approach to estimating global NEE anomalies based on FLUXNET data using land cover maps and weather reanalysis. We analyze 13 years (1997-2009) of globally gridded observational NEE anomalies derived from eddy covariance flux data, remotely-sensed fire emissions at the monthly time step, and NEE estimated from an atmospheric transport inversion. We evaluate the overall consistency of biospheric response to El Nino and, more generally, the link between global CO2 flux anomalies and El Nino-induced drought. Our findings, which are robust relative to uncertainty in both methods and time-lags in response, indicate that each event has a different spatial signature with only limited spatial coherence in Amazonia, Australia and southern Africa. For most regions, the sign of response changed across El Nino events. Biotic NEE anomalies, across 5 El Nino events, ranged from -1.34 to +0.98 Pg Cyr(exp -1, whereas fire emissions anomalies were generally smaller in magnitude (ranging from -0.49 to +0.53 Pg C yr(exp -1). Overall drought does not appear to impose consistent terrestrial CO2 flux anomalies during El Ninos, finding large variation in globally integrated responses from 11.15 to +0.49 Pg Cyr(exp -1). Despite the significant correlation between the CO2 flux and El Nino indices, we find that El Nino events have, when globally integrated, both enhanced and weakened terrestrial sink strength, with no consistent response across events

Schwalm. C. R.↗

Monitoring Regional Forest Disturbances across the US with near Real Time MODIS NDVI Products Resident to the ForWarn Forest Threat Early Warning System

Forest threats across the US have become increasingly evident in recent years. Sometimes these have resulted in regionally evident disturbance progressions (e.g., from drought, bark beetle outbreaks, and wildfires) that can occur across multiyear durations and have resulted in extensive forest overstory mortality. In addition to stand replacement disturbances, other forests are subject to ephemeral, sometimes yearly defoliation from various insects and varying types and intensities of ephemeral damage from storms. Sometimes, after prolonged severe disturbance, signs of recovery in terms of Normalized Difference Vegetation Index (NDVI) can occur. The growing prominence and threat of forest disturbances in part have led to the formation and implementation of the 2003 Healthy Forest Restoration Act which mandated that national forest threat early warning system be developed and deployed. In response, the US Forest Service collaborated with NASA, DOE Oakridge National Laboratory, and the USGS Eros Data Center to build and roll-out the near real time ForWarn early warning system for monitoring regionally evident forest disturbances. Given the diversity of disturbance types, severities, and durations, ForWarn employs multiple historical baselines that are used with current NDVI to derive a suite of six forest change products that are refreshed every 8 days. ForWarn employs daily quarter kilometer MODIS NDVI data from the Aqua and Terra satellites, including MOD13 data for deriving historical baseline NDVIs and eMODIS 7 NDVI for compiling current NDVI. In doing so, the Time Series Product Tool and the Phenological Parameters Estimation Tool are used to temporally de-noise, fuse, and aggregate current and historical MODIS NDVIs into 24 day composites refreshed every 8 days with 46 dates of products per year. The 24 day compositing interval enables disturbances to be detected, while minimizing the frequency of residual atmospheric contamination. Forest change products are computed versus the previous 1, previous 3, and all previous years in the MODIS record for a given 24 day interval. Other "weekly" forest change products include one computed using an adaptive length compositing method for quicker detection of disturbances, two others that adjust for seasonal fluctuations in normal vegetation phenology (e.g., early versus late springs). This overall approach enables forest disturbance dynamics from a variety of regionally evident biotic and abiotic forest disturbances to be viewed and assessed through the calendar year. The change products are also being utilized for forest change trend analysis and for developing regional forest overstory mortality products. ForWarn's forest change products are used to alert forest health specialists about new forest disturbances. Such alerts are also typically based on available Landsat, aerial, and ground data as well as communications with forest health specialists and previous experience. ForWarn products have been used to detect and track many types of regional disturbances to multiple forest types, including defoliation from caterpillars and severe storms, as well as mortality from both biotic and abiotic agents (e.g., bark beetles, drought, fire, anthropogenic clearing). ForWarn offers products that could be combined with other geospatial data on forest biomass to assess forest disturbance carbon impacts within the conterminous US.

Spruce, Joseph P.↗

Potential of Pest and Host Phenological Data in the Attribution of Regional Forest Disturbance Detection Maps According to Causal Agent

Near real time forest disturbance detection maps from MODIS NDVI phenology data have been produced since 2010 for the conterminous U.S., as part of the on-line ForWarn national forest threat early warning system. The latter has been used by the forest health community to identify and track many regional forest disturbances caused by multiple biotic and abiotic damage agents. Attribution of causal agents for detected disturbances has been a goal since project initiation in 2006. Combined with detailed cover type maps, geospatial pest phenology data offer a potential means for narrowing the candidate causal agents responsible for a given biotic disturbance. U.S. Aerial Detection Surveys (ADS) employ such phenology data. Historic ADS products provide general locational data on recent insect-induced forest type specific disturbances that may help in determining candidate causal agents for MODIS-based disturbance maps, especially when combined with other historic geospatial disturbance data (e.g., wildfire burn scars and drought maps). Historic ADS disturbance detection polygons can show severe and extensive regional forest disturbances, though they also can show polygons with sparsely scattered or infrequent disturbances. Examples will be discussed that use various historic disturbance data to help determine potential causes of MODIS-detected regional forest disturbance anomalies.

Spruce, Joseph↗

VESGEN Mapping of Bioactive Protection against Intestinal Inflammation: Application to Human Spaceflight and ISS Experiments

Challenges to successful space exploration and colonization include adverse physiological reactions to micro gravity and space radiation factors. Constant remodeling of the microvasculature is critical for tissue preservation, wound healing, and recovery after ischemia. Regulation of the vascular system in the intestine is particularly important to enable nutrient absorption while maintaining barrier function and mucosal defense against micro biota. Although tremendous progress has been made in understanding the molecular circuits regulating neovascularization, our knowledge of the adaptations of the vascular system to environmental challenges in the intestine remains incomplete. This is in part because of the lack of methods to observe and quantify the complex processes associated with vascular responses in vivo. Developed by GRC as a mature beta version, pre-release research software, VESsel GENeration Analysis (VESGEN) maps and quantifies the fractal-based complexity of vascular branching for novel insights into the cytokine, transgenic and therapeutic regulation of angiogenesis, lymphangiogenesis and microvascular remodeling. Here we demonstrate that VESGEN can be used to characterize the dynamic vascular responses to acute intestinal inflammation and mucosal recovery from in vivo confocal microscopic 3D image series. We induced transient intestinal inflammation in mice by DSS treatment and investigated whether the ability of the pro biotic yeast Saccharomyces boulardii (Sb) to protect against intestinal inflammation was due to regulation of vascular remodeling. A primary characteristic of inflammation is excessive neovascularization (angiogenesis) resulting in fragile vessels prone to bleeding. Morphological parameters for triplicate specimens revealed that Sb treatment greatly reduced the inflammatory response of vascular networks by an average of 78%. This resulted from Sb inhibition of vascular endothelial growth factor receptor signaling, a major angiogenesis signaling pathway. It needs to be determined whether pro biotic yeast represents a promising approach to GI protection in space. GRC performed only the VESGEN post-testing analysis.

Parsons-Wingerter, P. A.↗

Synthetic Biology and the Search for Extraterrestrial Life

Are we alone? is one of the primary questions of astrobiology, and whose answer defines our significance in the universe. Unfortunately, this quest is hindered by the fact that we have only one confirmed example of life, that of earth. While this is enormously helpful in helping to define the minimum envelope for life, it strains credulity to imagine that life, if it arose multiple times, has not taken other routes. To help fill this gap, our lab has begun using synthetic biology, the design and construction of new biological parts and systems and the redesign of existing ones for useful purposes, as an enabling technology. One theme, the Hell Cell project, focuses on creating artificial extremophiles in order to push the limits for Earth life, and to understand how difficult it is for life to evolve into extreme niches (http:2012.igem.orgTeam:Stanford-BrownHellCellIntroduction). In another project, we are re-evolving biotic functions using only the most thermodynamically stable amino acids in order to understand potential capabilities of an early organism with a limited repertoire of amino acids. This should lead to a more universal theory of the origin of life based on materials found commonly in meteorites and other pre-biotic settings.

Hell Cell↗

Lipid Decontamination Procedures for Life Detection Missions

Molecular biosignatures are key targets for current, proposed, and future life detection missions. With the high accuracy and low limit of detection (LOD) that new and future instruments will require, decontamination of life detection hardware is necessary to prevent false positives. Lipids are a molecular biosignature of interest, as they are ubiquitous to all life as we know it, can survive unaltered in the geologic record for longer than any other biomolecule (i.e. billions of years), and form through both biotic and abiotic processes. Lipids display origin-diagnostic molecular patterns that can reveal biotic or abiotic synthesis, so finding them and ascertaining their molecular features is important for potentially detecting evidence of life elsewhere. Traditional methods of decontamination, or contamination control (CC), primarily clean hardware through fabrication in sterile (cleanroom) environments, killing microbes, and removing/flushing contaminants off instrument and spacecraft components. However, research suggests that some standard cleaning methods are either unlikely to remove lipid contaminants or are incompatible with life detection instrument materials. To solve this problem, I propose to find, test, and verify a decontamination method that thoroughly cleans instruments by destroying lipid molecules, but is simultaneously compatible with major materials used in these instruments. I will study the effects of traditional CC methods (including Dry Heat Microbial Reduction and Vapor phase Hydrogen Peroxide) and experimental CC methods (Electron Beam Irradiation) on lipid molecules for application to life detection instrumentation. I will then develop a CC plan for a novel lipid detector (ExCALiBR, Extractor for Chemical Analysis of Lipid Biomarkers in Regolith) searching for lipids in either soil or icy world scenarios. This plan will uphold planetary protection regulation requirements and validate experimental analyses of in-situ life detection tests.

Decontamination↗

Biological Oxidation of Fe(II)-Bearing Smectite by Microaerophilic Iron Oxidizer Sideroxydans lithotrophicus Using Dual Mto and Cyc2 Iron Oxidation Pathways

Fe(II) clays are common across many environments, making them a potentially significant microbial substrate, yet clays are not well established as an electron donor. Therefore, we explored whether Fe(II)-smectite supports the growth of Sideroxydans lithotrophicus ES-1, a microaerophilic Fe(II)-oxidizing bacterium (FeOB), using synthesized trioctahedral Fe(II)-smectite and 2% oxygen. S. lithotrophicus grew substantially and can oxidize Fe(II)-smectite to a higher extent than abiotic oxidation, based on X-ray near-edge spectroscopy (XANES). Sequential extraction showed that edge-Fe(II) is oxidized before interior-Fe(II) in both biotic and abiotic experiments. The resulting Fe(III) remains in smectite, as secondary minerals were not detected in biotic and abiotic oxidation products by XANES and Mössbauer spectroscopy. To determine the genes involved, we compared S. lithotrophicus grown on smectite versus Fe(II)-citrate using reverse-transcription quantitative PCR and found that cyc2 genes were highly expressed on both substrates, while mtoA was upregulated on smectite. Proteomics confirmed that Mto proteins were only expressed on smectite, indicating that ES-1 uses the Mto pathway to access solid Fe(II). We integrate our results into a biochemical and mineralogical model of microbial smectite oxidation. This work increases the known substrates for FeOB growth and expands the mechanisms of Fe(II)-smectite alteration in the environment.

smectite↗