Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

[1]  J. Peña.  Mechanisms of nickel sorption by a bacteriogenic birnessite , 2010 .

[2]  Philip E. Bourne,et al.  History of biological metal utilization inferred through phylogenomic analysis of protein structures , 2010, Proceedings of the National Academy of Sciences.

[3]  William V. Boynton,et al.  Wet Chemistry experiments on the 2007 Phoenix Mars Scout Lander mission: Data analysis and results , 2010 .

[4]  J. Bargar.  Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ , 2009 .

[5]  G. Sposito,et al.  Structural model for the biogenic Mn oxide produced by Pseudomonas putida , 2006 .

[6]  James K. McCarthy,et al.  Geomicrobiology of manganese(II) oxidation. , 2005, Trends in microbiology.

[7]  B. Tebo,et al.  Structural characterization of biogenic Mn oxides produced in seawater by the marine bacillus sp. strain SG-1 , 2005 .

[8]  B. Tebo,et al.  Structural Influences of Sodium and Calcium Ions on the Biogenic Manganese Oxides Produced by the Marine Bacillus Sp., Strain SG-1 , 2005 .

[9]  U. Bergmann,et al.  Biotic and abiotic products of Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1 , 2005 .

[10]  E. D. Crozier,et al.  The structure of the manganese oxide on the sheath of the bacterium Leptothrix discophora: An XAFS study , 2004 .

[11]  P. Heaney,et al.  Neutron and synchrotron X-ray diffraction study of the structures and dehydration behaviors of ramsdellite and “groutellite” , 2004 .

[12]  Karen J. Murray,et al.  Biogenic manganese oxides: Properties and mechanisms of formation , 2004 .

[13]  V. Pecoraro,et al.  Structural, spectroscopic, and reactivity models for the manganese catalases. , 2004, Chemical reviews.

[14]  John R. Bargar,et al.  Characterization of the manganese oxide produced by Pseudomonas putida strain MnB1 , 2003 .

[15]  Q. Feng,et al.  Structure of synthetic Na-birnessite: Evidence for a triclinic one-layer unit cell , 2002 .

[16]  B. Tebo,et al.  Localization of Mn(II)-oxidizing activity and the putative multicopper oxidase, MnxG, to the exosporium of the marine Bacillus sp. strain SG-1 , 2002, Archives of Microbiology.

[17]  B. Tebo,et al.  Enzymatic Manganese(II) Oxidation by a Marine α-Proteobacterium , 2001, Applied and Environmental Microbiology.

[18]  B. Tebo,et al.  cumA Multicopper Oxidase Genes from Diverse Mn(II)-Oxidizing and Non-Mn(II)-OxidizingPseudomonas Strains , 2001, Applied and Environmental Microbiology.

[19]  J. González-Rodríguez,et al.  Electron Paramagnetic Resonance of MnO2 Powders , 2001 .

[20]  J. Kirschvink,et al.  Paleoproterozoic snowball earth: extreme climatic and geochemical global change and its biological consequences. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[21]  D. Huber,et al.  EPR linewidths in La1-xCaxMnO3: 0?x?1 , 1999 .

[22]  D. Huber.  Analysis of electron paramagnetic resonance experiments in colossal magnetoresistance materials , 1998 .

[23]  T. Armbruster,et al.  Hydrogen Bonding and Jahn–Teller Distortion in Groutite,α-MnOOH, and Manganite,γ-MnOOH, and Their Relations to the Manganese Dioxides Ramsdellite and Pyrolusite☆ , 1997 .

[24]  B. Weckhuysen,et al.  Characterization of Al2O3-Supported Manganese Oxides by Electron Spin Resonance and Diffuse Reflectance Spectroscopy , 1997 .

[25]  J. Hoch,et al.  Genetic analysis of the marine manganese-oxidizing Bacillus sp. strain SG-1: protoplast transformation, Tn917 mutagenesis, and identification of chromosomal loci involved in manganese oxidation , 1993, Journal of bacteriology.

[26]  Bruce M. Jakosky,et al.  The planet Mars - From antiquity to the present , 1992 .

[27]  V. R. Baker,et al.  Ancient oceans, ice sheets and the hydrological cycle on Mars , 1991, Nature.

[28]  J. Pilbrow,et al.  Transition Ion Electron Paramagnetic Resonance , 1990 .

[29]  J. Post,et al.  Chalcophanite, ZnMn 3 O 7 .3H 2 O; new crystal-structure determinations , 1988 .

[30]  K. Nealson,et al.  Manganese oxidation in pH and O2 microenvironments produced by phytoplankton. , 1988, Limnology and oceanography.

[31]  A. Manceau,et al.  Structure of Mn and Fe oxides and oxyhydroxides: A topological approach by EXAFS , 1988 .

[32]  M. Carr.  Water on Mars , 1987, Nature.

[33]  L. F. Adams,et al.  Influence of Manganese on Growth of a Sheathless Strain of Leptothrix discophora , 1985, Applied and environmental microbiology.

[34]  H. Ehrlich.  Geomicrobiology, Fourth Edition, , 1981 .

[35]  J. Longo,et al.  Magnetic properties of the mixed-valence compounds CaMn3O6 and CaMn4O8☆ , 1980 .

[36]  J. Longo,et al.  Preparation and magnetic properties of manganite , 1979 .

[37]  George R. Rossman,et al.  The manganese- and iron-oxide mineralogy of desert varnish , 1979 .

[38]  G. Rossman,et al.  Desert Varnish: The Importance of Clay Minerals , 1977, Science.

[39]  A. Barouch,et al.  Electron paramagnetic resonance in compounds of transition elements , 1974 .

[40]  E. A. Harris.  EPR of Mn2+ pairs in MgO and CaO , 1972 .

[41]  A. Abragam,et al.  Electron paramagnetic resonance of transition ions , 1970 .

[42]  P. Anderson,et al.  Exchange Narrowing in Paramagnetic Resonance , 1953 .

[43]  C. Kittel,et al.  Theory of Antiferromagnetic Resonance , 1951 .

[44]  J. H. Van Vleck,et al.  The Dipolar Broadening of Magnetic Resonance Lines in Crystals , 1948 .