Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate.
The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.
McCollom
T M
TM
Petroleum and Environmental Geochemistry Group, College of Oceanic and Atmospheric Sciences, Oregon State University, Corvallis 97331, USA. tmccollom@whoi.edu
Simoneit
B R
BR
D052203:Ferrosoferric Oxide; D008401:Gas Chromatography-Mass Spectrometry; D006358:Hot Temperature; D006838:Hydrocarbons / Q000138:chemical synthesis* / Q000737:chemistry; D007501:Iron; D010070:Oxalates / Q000737:chemistry*; D010087:Oxides; D010100:Oxygen
D006838:Hydrocarbons; D010070:Oxalates; D010087:Oxides; D007501:Iron; D010100:Oxygen; D052203:Ferrosoferric Oxide