CoChat
Sign Up
Cited by 115Origins and Evolution of LifePaleontology and Stratigraphy of FossilsAstro and Planetary Science

Abiotic ammonium formation in the presence of Ni-Fe metals and alloys and its implications for the Hadean nitrogen cycle

Open access
Smirnov, Alexander, Hausner, Douglas, Laffers, Richard, Strongin, Daniel R, Schoonen, Martin AA·2008·Geochemical Transactions
DOI 10.1186/1467-4866-9-5PMC PMC2430951
Open this paper in CoChat — free accountOpen PDF

Abstract

Experiments with dinitrogen-, nitrite-, nitrate-containing solutions were conducted without headspace in Ti reactors (200 degrees C), borosilicate septum bottles (70 degrees C) and HDPE tubes (22 degrees C) in the presence of Fe and Ni metal, awaruite (Ni80Fe20) and tetrataenite (Ni50Fe50). In general, metals used in this investigation were more reactive than alloys toward all investigated nitrogen species. Nitrite and nitrate were converted to ammonium more rapidly than dinitrogen, and the reduction process had a strong temperature dependence. We concluded from our experimental observations that Hadean submarine hydrothermal systems could have supplied significant quantities of ammonium for reactions that are generally associated with prebiotic synthesis, especially in localized environments. Several natural meteorites (octahedrites) were found to contain up to 22 ppm Ntot. While the oxidation state of N in the octahedrites was not determined, XPS analysis of metals and alloys used in the study shows that N is likely present as nitride (N3-). This observation may have implications toward the Hadean environment, since, terrestrial (e.g., oceanic) ammonium production may have been supplemented by reduced nitrogen delivered by metal-rich meteorites. This notion is based on the fact that nitrogen dissolves into metallic melts.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1186/1467-4866-9-5

Cites

9 of 9 references verified0 citation errors · 0 not checkable

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • Native Fe±0 is an effective catalyst of N2 reduction under hydrothermal conditions.

    “However, simulated hydrothermal conditions of 300°C and high pressure readily convert nitrite into NH3 [63], and under very mild conditions, FeS minerals can reduce N2 to NH3 at yields approaching 0.1 per cent [64], whereby native Fe±0 is also an effective catalyst of N2 reduction under hydrothermal conditions [65], recalling once again awaruite as an indicator of serpentinization [25].”

    From Early bioenergetic evolution (2013) · cites this paper as [65]

    The Results (Dinitrogen reduction; page not available) report that Fe⁰ was associated with the most NH₄⁺ production from N₂ among the tested metals at 200°C. The Discussion (Dinitrogen reduction; page not available) treats the surface-mediated mechanism as a hypothesis and notes that Fe⁰ oxidizes and its surface becomes passivated. The experiments therefore support Fe⁰-assisted N₂ reduction under hydrothermal conditions, but do not establish that Fe⁰ acts as a catalyst in those conditions. (LLM, conf=0.82)

    Experimental — accuracy not yet measured

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Cites

Flagged first, then by citations

Research works printed but not linked: 78

  1. Hennet RJC Holm NG Engel MH Abiotic synthesis of amino acids under hydrothermal conditions and the origin of life - A perpetual phenomenon Naturwissenschaften 1992 79 361 365 1522920 10.1007/BF01140180 · DOI
  2. Marshall WL Hydrothermal synthesis of amino acids Geochim Cosmochim Ac 1994 58 2099 2106 10.1016/0016-7037(94)90288-7 · DOI · Paper page
  3. Summers DP Sources and sinks for ammonia and nitrite on the early earth and the reaction of nitrite with ammonia Orig Life Evol Biosph 1999 29 33 46 10077867 10.1023/A:1006517823004 · DOI
  4. Summers DP Chang S Prebiotic ammonia from reduction of nitrite by iron(II) on the early Earth Nature 1993 365 630 632 11540245 10.1038/365630a0 · DOI
  5. Summers DP Ammonia formation by the reduction of nitrite/nitrate by FeS: Ammonia formation under acidic conditions Orig Life Evol Biosph 2005 35 299 312 16228644 10.1007/s11084-005-2040-1 · DOI
  6. Eugster HP Munoz J Ammonium micas - Possible sources of atmospheric ammonia and nitrogen Science 1966 151 683 686 17813793 10.1126/science.151.3711.683 · DOI
  7. Schrauzer GN Guth TD Photolysis of water and photoreduction of nitrogen on titanium dioxide J Am Chem Soc 1977 99 7189 7193 10.1021/ja00464a015 · DOI
  8. Schrauzer GN Strampach N Hui LN Palmer MR Salehi J Nitrogen photo-reduction on desert sands under sterile conditions P Natl Acad Sci USA 1983 80 3873 3876 10.1073/pnas.80.12.3873 PMC394157 16593330 · DOI
  9. Ranjit KT Viswanathan B Photocatalytic reduction of nitrite and nitrate ions over doped TiO2 catalysts J Photoch Photobio A 1997 107 215 220 10.1016/S1010-6030(97)00025-7 · DOI
  10. Schoonen MAA Xu Y Nitrogen reduction under hydrothermal vent conditions: Implications for the prebiotic synthesis of C-H-O-N compounds Astrobiology 2001 1 133 141 12467117 10.1089/153110701753198909 · DOI
  11. Dörr M Kassbohrer J Grunert R Kreisel G Brand WA Werner RA Geilmann H Apfel C Robl C Weigand W A possible prebiotic formation of ammonia from dinitrogen on iron sulfide surfaces Angew Chem Int Ed Engl 2003 42 1540 1543 12698495 10.1002/anie.200250371 · DOI · Paper page
  12. Kelley DS Fruh-Green GL Abiogenic methane in deep-seated mid-ocean ridge environments: Insights from stable isotope analyses J Geophys Res-Planet 1999 104 10439 10460 10.1029/1999JB900058 · DOI
  13. Mevel C Serpentinization of abyssal peridotites at mid-ocean ridges CR Geosci 2003 335 825 852 10.1016/j.crte.2003.08.006 · DOI
  14. Dick HJB Terrestrial nickel-iron from Josephine peridotite, its geologic occurrence, associations, and origin Earth Planet Sc Lett 1974 24 291 298 10.1016/0012-821X(74)90107-1 · DOI
  15. Ahmed Z Bevan JC Awaruite, iridian awaruite, and a new Ru-Os-Ir-Ni-Fe alloy from the Sakhakot-Qila Complex, Malakand-Agency, Pakistan Mineral Mag 1981 44 225 230 10.1180/minmag.1981.044.334.17 · DOI
  16. Alt JC Shanks III WC Stable isotope compositions of serpentinite seamounts in the Mariana forearc: Serpentinization processes, fluid sources and sulfur metasomatism Earth Planet Sc Lett 2006 242 272 285 10.1016/j.epsl.2005.11.063 · DOI
  17. Beard JS Hopkinson L A fossil, serpentinization-related hydrothermal vent, Ocean Drilling Program Leg 173, Site 1068 (Iberia Abyssal Plain): Some aspects of mineral and fluid chemistry J Geophys Res-Planet 2000 105 16527 16539 10.1029/2000JB900073 · DOI
  18. Kasting JF Earth's early atmosphere Science 1993 259 920 926 11536547 10.1126/science.11536547 · DOI · Paper page
  19. Navarro-Gonzalez R McKay CP Nna-Mvondo D A possible nitrogen crisis for Archaean life due to reduced nitrogen fixation by lightning Nature 2001 412 61 64 11452304 10.1038/35083537 · DOI · Paper page
  20. Nna-Mvondo D Navarro G Rafael Raulin F Coll P Nitrogen fixation by corona discharge on the early Precambrian Earth Origins Life Evol B 2005 35 401 409 10.1007/s11084-005-1972-9 16231204 · DOI
  21. Mancinelli RL McKay CP The evolution of nitrogen cycling Origins Life Evol B 1988 18 311 325 10.1007/BF01808213 11538360 · DOI
  22. Howald RA The thermodynamics of tetrataenite and awaruite: A review of the Fe-Ni phase diagram Metall Mater Trans A 2003 34A 1759 1769 10.1007/s11661-003-0142-9 · DOI
  23. Kodentsov AA van Dal MJH Cserhati C Daroczi L van Loo FJJ Permeation of nitrogen in solid nickel and deformation phenomena accompanying internal nitridation Acta Mater 1999 47 3169 3180 10.1016/S1359-6454(99)00194-9 · DOI
  24. Ech-chamikh E Essafti A Ijdiyaou Y Azizan M XPS study of amorphous carbon nitride (a-C:N) thin films deposited by reactive RF sputtering Solar Energy Materials and Solar Cells 2006 90 1420 1423 10.1016/j.solmat.2005.10.007 · DOI
  25. Jennings JR Catalytic ammonia synthesis 1991 New York, Plenum Press 476
  26. Alberty RA Thermodynamics of the nitrogenase reactions J Biol Chem 1994 269 7099 7102 8125917
  27. Howard JB Rees DC Structural basis of biological nitrogen fixation Chem Rev 1996 96 2965 2982 11848848 10.1021/cr9500545 · DOI
  28. Moody JB Serpentinization - Review Lithos 1976 9 125 138 10.1016/0024-4937(76)90030-X · DOI
  29. Reardon EJ Anaerobic corrosion of granular iron: Measurement and interpretation of hydrogen evolution rates Environ Sci Technol 1995 29 2936 22945 10.1021/es00012a008 22148199 · DOI
  30. Chen YM Li CW Chen SS Fluidized zero valent iron bed reactor for nitrate removal Chemosphere 2005 59 753 759 15811403 10.1016/j.chemosphere.2004.11.020 · DOI
  31. Cheng IF Muftikian R Fernando Q Korte N Reduction of nitrate to ammonia by zero-valent iron Chemosphere 1997 35 2689 2695 10.1016/S0045-6535(97)00275-0 · DOI
  32. Choe SH Ljestrand HM Khim J Nitrate reduction by zero-valent iron under different pH regimes Appl Geochem 2004 19 335 342 10.1016/j.apgeochem.2003.08.001 · DOI
  33. Hu HY Goto N Fujie K Effect of pH on the reduction of nitrite in water by metallic iron Water Res 2001 35 2789 2793 11456181 10.1016/S0043-1354(00)00570-4 · DOI
  34. Huang CP Wang HW Chiu PC Nitrate reduction by metallic iron Water Res 1998 32 2257 2264 10.1016/S0043-1354(97)00464-8 · DOI
  35. Huang YH Zhang TC Effects of low pH on nitrate reduction by iron powder Water Res 2004 38 2631 2642 15207593 10.1016/j.watres.2004.03.015 · DOI
  36. Huang YH Zhang TC Enhancement of nitrate reduction in Fe-0-packed columns by selected cations J Environ Eng-ASCE 2005 131 603 611 10.1061/(ASCE)0733-9372(2005)131:4(603) · DOI
  37. Huang YH Zhang TC Shea PJ Comfort SD Effects of oxide coating and selected cations on nitrate reduction by iron metal J Environ Qual 2003 32 1306 1315 12931886
  38. Alowitz MJ Scherer MM Kinetics of nitrate, nitrite, and Cr(VI) reduction by iron metal Environ Sci Technol 2002 36 299 306 11871541 10.1021/es011000h · DOI
  39. Wärna J Turunen I Salmi T Maunula T Kinetics of nitrate reduction in monolith reactor Chem Eng Sci 1994 49 5763 5773 10.1016/0009-2509(94)00331-9 · DOI
  40. Klausen J Tröber SP Haderlein SB Schwarzenbach RP Reduction of substituted nitrobenzenes by Fe(II) in aqueous mineral suspensions Environ Sci Technol 1995 29 2396 2404 10.1021/es00009a036 22280284 · DOI
  41. Weber EJ Iron-mediated reductive transformations: Investigation of reaction mechanism Environ Sci Technol 1996 30 716 7719 10.1021/es9505210 · DOI
  42. Huang YH Zhang TC Effects of dissolved oxygen on formation of corrosion products and concomitant oxygen and nitrate reduction in zero-valent iron systems with or without aqueous Fe2+ Water Res 2005 39 1751 1760 15899273
  43. Sorensen J Thorling L Stimulation by Lepidocrocite (gamma-FeOOH) of Fe(II)-dependent nitrite reduction Geochim Cosmochim Ac 1991 55 1289 1294 10.1016/0016-7037(91)90307-Q · DOI
  44. Neely JE Bertone TJ Practical metallurgy and materials of industry 2002 6th Upper Saddle River, NJ, Prentice Hall 464
  45. Cooley WE Parker SP Nickel McGraw-Hill encyclopedia of chemistry 1993 New York, McGraw-Hill, Inc.
  46. Epron F Gauthard F Pineda C Barbier J Catalytic reduction of nitrate and nitrite on Pt-Cu/Al2O3 catalysts in aqueous solution: Role of the interaction between copper and platinum in the reaction J Catal 2001 198 309 318 10.1006/jcat.2000.3138 · DOI
  47. Gauthard F Epron F Barbier J Palladium and platinum-based catalysts in the catalytic reduction of nitrate in water: effect of copper, silver, or gold addition J Catal 2003 220 182 191 10.1016/S0021-9517(03)00252-5 · DOI
  48. Hoashi M Brooks RR Reeves RD Palladium, platinum and rhutenium in iron meteorites and their taxonomic significance Chem Geol 1993 106 207 218 10.1016/0009-2541(93)90027-G · DOI
  49. Tolstykh N Krivenko A Sidorov E Laajoki K Podlipsky M Ore mineralogy of PGM placers in Siberia and the Russian Far East Ore Geol Rev 2002 20 1 25 10.1016/S0169-1368(02)00036-7 · DOI
  50. Cawthorn RG Lee CA Schouwstra RP Mellowship P Relationship between PGE and PGM in the Bushveld Complex Can Miner 2002 40 311 328 10.2113/gscanmin.40.2.311 · DOI
  51. Schoonen MAA Smirnov A Cohn C A perspective on the role of minerals in prebiotic synthesis Ambio 2004 33 539 551 15666687 10.1639/0044-7447(2004)033[0539:APOTRO]2.0.CO;2 · DOI
  52. Blesa MA Matijevič E Phase transformations of iron oxides, oxohydroxides, and hydrous oxides in aqueous media Adv Colloid Interfac Sci 1989 29 173 221 10.1016/0001-8686(89)80009-0 · DOI
  53. Refait P Memet JB Bon C Sabot R Genin JMR Formation of the Fe(II)-Fe(III) hydroxysulphate green rust during marine corrosion of steel Corros Sci 2003 45 833 845 10.1016/S0010-938X(02)00184-1 · DOI
  54. Cornell RM Schwertmann U The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses 2003 2nd Weinheim, Wiley 703
  55. Hansen HCB Koch CB NanckeKrogh H Borggaard OK Sorensen J Abiotic nitrate reduction to ammonium: Key role of green rust Environ Sci Technol 1996 30 2053 2056 10.1021/es950844w · DOI
  56. Hansen HCB Koch CB Reduction of nitrate to ammonium by sulphate green rust: activation energy and reaction mechanism Clay Miner 1998 33 87 101 10.1180/000985598545453 · DOI
  57. Rakshit S Matocha CJ Haszler GR Nitrate reduction in the presence of wustite J Environ Qual 2005 34 1286 1292 15998850 10.2134/jeq2004.0459 · DOI
  58. Ottley CJ Davison W Edmunds WM Chemical catalysis of nitrate reduction by iron (II) Geochim Cosmochim Ac 1997 61 1819 1828 10.1016/S0016-7037(97)00058-6 · DOI
  59. Abbott DH Hoffman SE Archaean plate tectonics revisited. 1. Heat flow, spreading rate, and the age of subducting oceanic lithosphere and their effects on the origin and evolution of continents Tectonics 1984 3 429 448 10.1029/TC003i004p00429 · DOI
  60. Turcotte DL On the thermal evolution of the Earth Earth Planet Sc Lett 1980 48 53 58 10.1016/0012-821X(80)90169-7 · DOI
  61. Elderfield H Schultz A Mid-ocean ridge hydrothermal fluxes and the chemical composition of the ocean Annu Rev Earth Pl Sc 1996 24 191 224 10.1146/annurev.earth.24.1.191 · DOI
  62. Kasting JF Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere Origins Life Evol B 1990 20 199 231 10.1007/BF01808105 11537523 · DOI
  63. Charlou JL Fouquet Y Bougault H Donval JP Etoubleau J Jean-Baptiste P Dapoigny A Appriou P Rona PA Intense CH4 plumes generated by serpentinization of ultramafic rocks at the intersection of the 15 degrees 20 ' N fracture zone and the Mid-Atlantic Ridge Geochim Cosmochim Ac 1998 62 2323 2333 10.1016/S0016-7037(98)00138-0 · DOI
  64. Von Damm KL Seafloor hydrothermal activity - Black smoker chemistry and chimneys Annu Rev Earth Pl Sc 1990 18 173 204 10.1146/annurev.ea.18.050190.001133 · DOI
  65. Macleod G McKeown C Hall AJ Russell MJ Hydrothermal and oceanic pH conditions of possible relevance to the origin of life Orig Life Evol Biosph 1994 24 19 41 11536657 10.1007/BF01582037 · DOI · Paper page
  66. Gaventman LH Lide DR Solubility of selected gases in water CRC Handbook of Chemistry and Physics 1994 75th Boca Raton, CRC Press 6 3
  67. Agrawal A Tratnyek PG Reduction of nitroaromatic compounds by zero-valent iron metal Environ Sci Technol 1996 30 153 150 10.1021/es950211h · DOI
  68. Matheson LJ Tratnyek PG Reductive dehalogenation of chlorinated methanes by iron metal Environ Sci Technol 1994 28 2045 2053 10.1021/es00061a012 22191743 · DOI · Paper page
  69. Warren KD Arnold RG Bishop TL Lindholm LC Batterton EA Kinetics and mechanism of reductive dehalogenation of carbon tetrachloride using zero-valent metals J Hazard Mater 1995 41 217 227 10.1016/0304-3894(94)00117-Y · DOI
  70. Gillham RW O'Hannesin F Enhanced degradation of halogenated aliphatics by zero-valent iron Ground Water 1994 32 958 967 10.1111/j.1745-6584.1994.tb00935.x · DOI
  71. Nagata T Carleton BJ Tetrataenite in carbonaceous chondrites P Jpn Acad B-Phys 1990 66 183 188 10.2183/pjab.66.183 · DOI
  72. Nagata T Carleton BJ Tetrataenite in chondritic meteorites P Jpn Acad B-Phys 1989 65 121 124 10.2183/pjab.65.121 · DOI
  73. Gattacceca J Rochette P Bourot-Denise M Magnetic properties of a freshly fallen LL ordinary chondrite: the Bensour meteorite Phys Earth Planet In 2003 140 343 358 10.1016/j.pepi.2003.10.001 · DOI
  74. Unik JP Henderson DJ Huizenga JR Radioactive species produced by cosmic rays in the Bogou iron meteorite Geochim Cosmochim Ac 1964 28 593 594 10.1016/0016-7037(64)90079-1 · DOI
  75. Franchi IA Wright IP Pillinger CT Constraints on the formation conditions of iron meteorites based on concentrations and isotopic compositions of iron meteorites Geochim Cosmochim Ac 1993 57 3105 3121 10.1016/0016-7037(93)90297-A · DOI
  76. Prombo CA Calyton RN Nitrogen isotopic compositions of iron meteorites Geochim Cosmochim Ac 1993 57 3749 3761 10.1016/0016-7037(93)90153-N · DOI
  77. Peretti A Dubessy J Mullis J Frost BR Trommsdorff V Highly reducing conditions during Alpine metamorphism of the Malenco peridotite (Sondrio, Northern Italy) indicated by mineral paragenesis and H2 in fluid inclusions Contrib Mineral Petr 1992 112 329 340 10.1007/BF00310464 · DOI
  78. Ahmed Z Comparison of the geochemistry of ophiolitic pyroxenites with a strongly fractionated dyke of pyroxenite from the Sakhakot-Qila Ophiolite, Pakistan Chem Geol 1991 91 335 355 10.1016/0009-2541(91)90094-8 · DOI

Cited by

Sorted by citations

Authors
Smirnov, A., Hausner, D., Laffers, R., Strongin, D. R., & Schoonen, M. A.
Affiliations
  • Stony Brook University (US)
  • Temple University (US)
Corresponding author
Smirnov, Alexander
ORCID
Venue
Geochemical Transactions
Publisher
Springer Science and Business Media LLC
Published
2008-05-19
Volume
9
Issue
1
Pages
5-5
ISSN
1467-4866 (ISSN-L)
DOI
10.1186/1467-4866-9-5
PMC
PMC2430951
OpenAlex
W2147833251
Cited by
115
References
9
Citations by year
2026: 3 · 2025: 9 · 2024: 5 · 2023: 9 · 2022: 6 · 2021: 7 · 2020: 5 · 2019: 5 · 2018: 5 · 2017: 5 · 2016: 11 · 2015: 7 · 2014: 8 · 2013: 12 · 2012: 7
FWCI
2.14
Type
journal article
Language
en
Open access
Licence
cc-by
Locations
  • Geochemical Transactions (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • TUScholarShare (Temple University) (submittedVersion, cc-by)
Funders
National Aeronautics and Space Administration (NAG513438)
Topics
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Astro and Planetary Science
Keywords
nitrogen reduction, Fe-Ni alloys, awaruite, tetrataenite, submarine hydrothermal systems, meteorites, anatase, nitrogen nitrides, prebiotic synthesis, nitrogen molecule, nitrite, nitrate, temperature dependence

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review