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Iron–sulfur world hypothesis

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Title: Iron–sulfur world hypothesis  
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Iron–sulfur world hypothesis

The iron–sulfur world hypothesis is a set of proposals for the origin of life and the early evolution of life advanced in a series of articles between 1988 and 1992 by Günter Wächtershäuser, a Munich patent lawyer with a degree in chemistry, who had been encouraged and supported by philosopher Karl R. Popper to publish his ideas. The hypothesis proposes that early life may have formed on the surface of iron sulfide minerals, hence the name.[1][2][3][4][5] It was developed by retrodiction from extant biochemistry in conjunction with chemical experiments.


  • Origin of life 1
    • Pioneer organism 1.1
    • Nutrient conversions 1.2
    • Synthetic reactions 1.3
  • Early evolution 2
    • Cellularization 2.1
    • Proto-ecological systems 2.2
  • References 3

Origin of life

Pioneer organism

Wächtershäuser proposes that the earliest form of life, termed "pioneer organism", originated in a volcanic hydrothermal flow at high pressure and high (100 °C) temperature. It had a composite structure of a mineral base with catalytic transition metal centers (predominantly citric acid cycle. Accelerated catalysts expanded the metabolism and new metabolic products further accelerated the catalysts. The idea is that once such a primitive autocatalytic metabolism was established, its intrinsically synthetic chemistry began to produce ever more complex organic compounds, ever more complex pathways and ever more complex catalytic centers.

The fundamental idea of abiogenesis, according to the iron–sulfur world hypothesis can be simplified in the following brief characterization: Pressurize and heat a water flow with dissolved volcanic gases (e.g. carbon monoxide, ammonia and hydrogen sulfide) to 100 °C. Pass the flow over catalytic transition metal solids (e.g. iron sulfide and nickel sulfide). Wait and locate the formation of catalytic metallo-peptides.

Nutrient conversions

The water gas shift reaction (CO + H2O → CO2 + H2) occurs in volcanic fluids with diverse catalysts or without catalysts.[6] The combination of ferrous sulfide and hydrogen sulfide as reducing agents in conjunction with pyrite formation – FeS + H2S → FeS2 + 2H+ + 2e (or H2 instead of 2H+ + 2e) – has been demonstrated under mild volcanic conditions.[7][8] This key result has been disputed.[9] Nitrogen fixation has been demonstrated for the isotope 15N2 in conjunction with pyrite formation.[10] Ammonia forms from nitrate with FeS/H2S as reductant.[11] Methylmercaptan [CH3-SH] and carbon oxysulfide [COS] form from CO2 and FeS/H2S,[12] or from CO and H2 in the presence of NiS.[13]

Synthetic reactions

Reaction of carbon monoxide (CO) and hydrogen sulfide (H2S) in the presence of nickel sulfide and iron sulfide generates the methyl thioester of acetic acid [CH3-CO-SCH3] and presumably thioacetic acid (CH3-CO-SH) as the simplest activated acetic acid analogues of acetyl-CoA. These activated acetic acid derivatives serve as starting materials for subsequent exergonic synthetic steps.[13] They also serve for energy coupling with endergonic reactions, notably the formation of (phospho)anhydride compounds.[14]

Reaction of nickel hydroxide with hydrogen cyanide (HCN) (in the presence or absence of ferrous hydroxide, hydrogen sulfide or methyl mercaptan) generates nickel cyanide, which reacts with carbon monoxide (CO) to generate pairs of α-hydroxy and α-amino acids: e.g. glycolate/glycine, lactate/alanine, glycerate/serine; as well as pyruvic acid in significant quantities.[15] Pyruvic acid is also formed at high pressure and high temperature from CO, H2O, FeS in the presence of nonyl mercaptan.[16] Reaction of pyruvic acid or other α-keto acids with ammonia in the presence of ferrous hydroxide or in the presence of ferrous sulfide and hydrogen sulfide generates alanine or other α-amino acids.[17] Reaction of α-amino acids in aqueous solution with COS or with CO and H2S generates a peptide cycle wherein dipeptides, tripeptides etc. are formed and subsequently degraded via N-terminal hydantoin moieties and N-terminal urea moieties and subsequent cleavage of the N-terminal amino acid unit.[18][19][20]

Proposed reaction mechanism for reduction of CO2 on FeS: Ying et al. (2007) have proved that direct transformation of mackinawite (FeS) to pyrite (FeS2) on reaction with H2S till 300 °C is not possible without the presence of critical amount of oxidant. In the absence of any oxidant, FeS reacts with H2S up to 300 °C to give pyrrhotite. Farid et al. have proved experimentally that mackinawite (FeS) has ability to reduce CO2 to CO at temperature higher than 300 °C. They claimed surface of FeS is oxized which on reaction with H2S gives pyrite (FeS2). It is expected that CO reacts with H2O in the Drobner experiment to give H2.

Early evolution

Early evolution is defined as beginning with the cellularization), the genetic machinery and enzymatization of the metabolism.


Cellularization occurs in several stages. It begins with the formation of primitive lipids (e.g. fatty acids or isoprenoid acids) in the surface metabolism. These lipids accumulate on or in the mineral base. This lipophilizes the outer or inner surfaces of the mineral base, which promotes condensation reactions over hydrolytic reactions by lowering the activity of water and protons.

In the next stage lipid membranes are formed. While still anchored to the mineral base they form a semi-cell bounded partly by the mineral base and partly by the membrane. Further lipid evolution leads to self-supporting lipid membranes and closed cells. The earliest closed cells are pre-cells (sensu Kandler) because they allow frequent exchange of genetic material (e.g. by fusions). According to Woese, this frequent exchange of genetic material is the cause for the existence of the common stem in the tree of life and for a very rapid early evolution.

Proto-ecological systems

William Martin and Michael Russell suggest that the first cellular life forms may have evolved inside alkaline hydrothermal vents at seafloor spreading zones in the deep sea.[21][22] These structures consist of microscale caverns that are coated by thin membraneous metal sulfide walls. Therefore, these structures would resolve several critical points germane to Wächtershäuser's suggestions at once:

  1. the micro-caverns provide a means of concentrating newly synthesised molecules, thereby increasing the chance of forming oligomers;
  2. the steep temperature gradients inside the hydrothermal vent allow for establishing "optimum zones" of partial reactions in different regions of the vent (e.g. monomer synthesis in the hotter, oligomerisation in the colder parts);
  3. the flow of hydrothermal water through the structure provides a constant source of building blocks and energy (chemical disequilibrium between hydrothermal hydrogen and marine carbon dioxide);
  4. the model allows for a succession of different steps of cellular evolution (prebiotic chemistry, monomer and oligomer synthesis, peptide and protein synthesis, RNA world, ribonucleoprotein assembly and DNA world) in a single structure, facilitating exchange between all developmental stages;
  5. synthesis of lipids as a means of "closing" the cells against the environment is not necessary, until basically all cellular functions are developed.

This model locates the "last universal common ancestor" (lipids as directed by genetically encoded peptides is consistent with the presence of completely different types of membrane lipids in archaea and bacteria (plus eukaryotes). The kind of vent at the foreground of their suggestion is chemically more similar to the warm (ca. 100 °C) off ridge vents such as Lost City than to the more familiar black smoker type vents (ca. 350 °C).

In an abiotic world, a acetic acid production and its eventual oxidization can be spatially organized.

In this way many of the individual reactions that are today found in central metabolism could initially have occurred independent of any developing cell membrane. Each vent microcompartment is functionally equivalent to a single cell. Chemical communities having greater structural integrity and resilience to wildly fluctuating conditions are then selected for; their success would lead to local zones of depletion for important precursor chemicals. Progressive incorporation of these precursor components within a cell membrane would gradually increase metabolic complexity within the cell membrane, whilst leading to greater environmental simplicity in the external environment. In principle, this could lead to the development of complex catalytic sets capable of self-maintenance.

Russell adds a significant factor to these ideas, by pointing out that semi-permeable mackinawite (an iron sulfide mineral) and silicate membranes could naturally develop under these conditions and electrochemically link reactions separated in space, if not in time.[23][24]


  1. ^ Wächtershäuser, Günter (1988-12-01). "Before enzymes and templates: theory of surface metabolism". Microbiol. Mol. Biol. Rev. 52 (4): 452–84.  
  2. ^ Wächtershäuser, G (January 1990). "Evolution of the first metabolic cycles". Proceedings of the National Academy of Sciences of the United States of America 87 (1): 200–4.  
  3. ^ Günter Wächtershäuser, G (1992). "Groundworks for an evolutionary biochemistry: The iron-sulphur world". Progress in Biophysics and Molecular Biology 58 (2): 85–201.  
  4. ^ Günter Wächtershäuser, G (2006). "From volcanic origins of chemoautotrophic life to Bacteria, Archaea and Eukarya". Philosophical Transactions of the Royal Society B: Biological Sciences 361 (1474): 1787–806; discussion 1806–8.  
  5. ^ Wächtershäuser, Günter (2007). "On the Chemistry and Evolution of the Pioneer Organism". Chemistry & Biodiversity 4 (4): 584–602.  
  6. ^ Seewald, Jeffrey S.; Mikhail Yu. Zolotov; Thomas McCollom (January 2006). "Experimental investigation of single carbon compounds under hydrothermal conditions". Geochimica et Cosmochimica Acta 70 (2): 446–460.  
  7. ^ Taylor, P.; T. E. Rummery; D. G. Owen (1979). "Reactions of iron monosulfide solids with aqueous hydrogen sulfide up to 160°C". Journal of Inorganic and Nuclear Chemistry 41 (12): 1683–1687.  
  8. ^ Drobner, E.; H. Huber; G. Wächtershäuser; D. Rose; K. O. Stetter (1990). "Pyrite formation linked with hydrogen evolution under anaerobic conditions". Nature 346 (6286): 742–744.  
  9. ^ Cahill, C. L.; L. G. Benning; H. L. Barnes; J. B. Parise (June 2000). "In situ time-resolved X-ray diffraction of iron sulfides during hydrothermal pyrite growth". Chemical Geology 167 (1–2): 53–63.  
  10. ^ Mark Dorr, Mark; Johannes Käßbohrer; Renate Grunert; Günter Kreisel; Willi A. Brand; Roland A. Werner; Heike Geilmann; Christina Apfel; Christian Robl; Wolfgang Weigand (2003). "A Possible Prebiotic Formation of Ammonia from Dinitrogen on Iron Sulfide Surfaces". Angewandte Chemie International Edition 42 (13): 1540–3.  
  11. ^ Blöchl, E; M Keller; G Wächtershäuser; K O Stetter (1992). "Reactions depending on iron sulfide and linking geochemistry with biochemistry". Proceedings of the National Academy of Sciences of the United States of America 89 (17): 8117–20.  
  12. ^ Heinen, Wolfgang; Anne Marie Lauwers (1996-04-01). "Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment". Origins of Life and Evolution of Biospheres 26 (2): 131–150.  
  13. ^ a b Huber, Claudia; Günter Wächtershäuser (1997-04-11). "Activated Acetic Acid by Carbon Fixation on (Fe,Ni)S Under Primordial Conditions". Science 276 (5310): 245–7.  
  14. ^ Günter Wächtershäuser; Michael W. W. Adams (1998). "The case for a hyperthermophilic, chemolithoautotrophic origin of life in an iron-sulfur world". In Juergen Wiegel (ed.). Thermophiles: The Keys to Molecular Evolution and the Origin of Life. pp. 47–57.  
  15. ^ Huber, Claudia; Günter Wächtershäuser (2006-10-27). "α-Hydroxy and α-Amino Acids Under Possible Hadean, Volcanic Origin-of-Life Conditions". Science 314 (5799): 630–2.  
  16. ^ Cody, George D.; Nabil Z. Boctor; Timothy R. Filley; Robert M. Hazen; James H. Scott; Anurag Sharma; Hatten S. Yoder (2000-08-25). "Primordial Carbonylated Iron-Sulfur Compounds and the Synthesis of Pyruvate". Science 289 (5483): 1337–40.  
  17. ^ Huber, Claudia; Günter Wächtershäuser (February 2003). "Primordial reductive amination revisited". Tetrahedron Letters 44 (8): 1695–1697.  
  18. ^ Huber, Claudia; Günter Wächtershäuser (1998-07-31). "Peptides by Activation of Amino Acids with CO on (Ni,Fe)S Surfaces: Implications for the Origin of Life". Science 281 (5377): 670–2.  
  19. ^ Huber, Claudia; Wolfgang Eisenreich; Stefan Hecht; Günter Wächtershäuser (2003-08-15). "A Possible Primordial Peptide Cycle". Science 301 (5635): 938–40.  
  20. ^ Wächtershäuser, Günter (2000-08-25). "ORIGIN OF LIFE: Life as We Don't Know It". Science 289 (5483): 1307–8.   (requires nonfree AAAS member subscription)
  21. ^ Martin, William; Michael J Russell (2003). "On the origins of cells: a hypothesis for the evolutionary transitions from abiotic geochemistry to chemoautotrophic prokaryotes, and from prokaryotes to nucleated cells". Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences 358 (1429): 59–83; discussion 83–5.  
  22. ^ Martin, William; Michael J Russell (2007). "On the origin of biochemistry at an alkaline hydrothermal vent". Philos Trans R Soc Lond B Biol Sci. 362 (1486): 1887–925.  
  23. ^ Michael Russell, Michael (2006). "First Life". American Scientist 94 (1): 32.  
  24. ^ Russell, Michael (Ed), (2010), "Origins, Abiogenesis and the Search for Life in the Universe" (Cosmology Science Publications)
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