Fate of organic compounds during transformation of ferrihydrite in Precambrian iron formations

The absence of organic compounds from Precambrian iron formations (IF) challenges the hypothesis of their biogenic origin. Here we address the fate of adsorbed organic compounds during transformation from ferrihydrite to hematite. We determined the binding energy between hematite and common molecular terminations found in extracellular polymeric substances and biofilms: carboxylic, alcohol and phosphate functional groups. We found that the bond between hematite and alcohol group is approximately 2 times stronger than the bond between hematitecarboxyl and -phosphate groups. We transformed synthetic ferrihydrite to hematite in presence of glycerol, which has a high density of alcohol groups and measured the amount of mineral associated glycerol before and after the transformation. We show that the transformation releases glycerol highlighting that organic compounds adsorbed at precursor ferrihydrite could be desorbed already during the process of IF sedimentation and diagenesis. Our results suggest that the absence of organic compounds in IF should not be used as evidence against their biogenic origin.

[1]  F. Pirajno,et al.  Minimal biomass deposition in banded iron formations inferred from organic matter and clay relationships , 2019, Nature Communications.

[2]  S. Kerisit,et al.  Mechanistic insight into biopolymer induced iron oxide mineralization through quantification of molecular bonding , 2019, Nanoscale advances.

[3]  K. Sand,et al.  Prebiotic RNA polymerisation: energetics of nucleotide adsorption and polymerisation on clay mineral surfaces. , 2017, Chemical communications.

[4]  A. Bekker,et al.  Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history , 2017 .

[5]  J. Grate,et al.  Developing a molecular picture of soil organic matter–mineral interactions by quantifying organo–mineral binding , 2017, Nature Communications.

[6]  A. Kappler,et al.  Primary hematite in Neoarchean to Paleoproterozoic oceans , 2015 .

[7]  J. Rosenqvist,et al.  Surface potential at the hematite (001) crystal plane in aqueous environments and the effects of prolonged aging in water , 2013 .

[8]  A. Noy,et al.  Interpreting the widespread nonlinear force spectra of intermolecular bonds , 2012, Proceedings of the National Academy of Sciences.

[9]  T. Hiemstra,et al.  A surface structural model for ferrihydrite I: Sites related to primary charge, molar mass, and mass density , 2009 .

[10]  A. Kappler,et al.  Physiology of phototrophic iron(II)-oxidizing bacteria: implications for modern and ancient environments. , 2008, FEMS microbiology ecology.

[11]  Y. Cudennec,et al.  The transformation of ferrihydrite into goethite or hematite, revisited , 2006 .

[12]  D. Newman,et al.  Deposition of banded iron formations by anoxygenic phototrophic Fe(II)-oxidizing bacteria , 2005 .

[13]  C. Klein Some Precambrian banded iron-formations (BIFs) from around the world: Their age, geologic setting, mineralogy, metamorphism, geochemistry, and origins , 2005 .

[14]  Peter J. Eng,et al.  Structure and reactivity of the hydrated hematite (0001) surface , 2004 .

[15]  J. Banfield,et al.  Microbial Polysaccharides Template Assembly of Nanocrystal Fibers , 2004, Science.

[16]  R. Kukkadapu,et al.  Secondary Mineralization Pathways Induced by Dissimilatory Iron Reduction of Ferrihydrite Under Advective Flow , 2003 .

[17]  D. G. Adams,et al.  Cyanobacterial viability during hydrothermal biomineralisation , 2000 .

[18]  Carel J. van Oss,et al.  Hydrophobicity and hydrophilicity of biosurfaces , 1997 .

[19]  Charles M. Lieber,et al.  Force Titrations and Ionization State Sensitive Imaging of Functional Groups in Aqueous Solutions by Chemical Force Microscopy , 1997 .

[20]  U. Schwertmann,et al.  Effect of pH on the Formation of Goethite and Hematite from Ferrihydrite , 1983 .

[21]  R. Garrels,et al.  Genesis of Precambrian Iron-Formations and the Development of Atmospheric Oxygen , 1973 .

[22]  M. Hendry,et al.  Transformation of two-line ferrihydrite to goethite and hematite as a function of pH and temperature. , 2011, Environmental science & technology.

[23]  A. Kappler,et al.  Role of Microorganisms in Banded Iron Formations , 2010 .