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Keywords = organic compounds Fenton chemistry

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14 pages, 2597 KB  
Article
Chemical and Isotopic Investigation of Abiotic Oxidation of Lactate Substrate in the Presence of Varied Electron Acceptors and Under Circumneutral Anaerobic Conditions
by Tsigabu A. Gebrehiwet and R. V. Krishnamurthy
Water 2025, 17(15), 2308; https://doi.org/10.3390/w17152308 - 3 Aug 2025
Viewed by 360
Abstract
Abiotic processes have ramifications in wastewater treatment, in situ degradation of organic matter, and cycling of nutrients in wetland ecosystems. Experiments were conducted to investigate abiotic oxidation of organic compounds (lactate) as a function of electron acceptors (ferric citrate and hydrous ferric oxide [...] Read more.
Abiotic processes have ramifications in wastewater treatment, in situ degradation of organic matter, and cycling of nutrients in wetland ecosystems. Experiments were conducted to investigate abiotic oxidation of organic compounds (lactate) as a function of electron acceptors (ferric citrate and hydrous ferric oxide (HFO), media composition, and pH under anaerobic conditions, using sodium bicarbonate as the buffering agent. Dissolved inorganic carbon (DIC) was used as a proxy for the oxidation of substrates. HFO media generated more DIC compared to ferric citrate containing media. Light and pH had major roles in the oxidation of lactate in the presence of ferric iron. Under dark conditions in the presence or absence of Fe(III), the DIC produced was low in all pH conditions. Inhibition of DIC production was also observed upon photo exposure when Fe (III) was absent. Isotopically, the system showed initial mixing between the bicarbonate and the carbon dioxide produced from oxidation later being dominated by carbon isotope value of lactate used. These redox conditions align with previous studies suggesting cleavage of organic compounds by hydroxyl radicals. The slower redox processes observed here, compared to previous studies, could be due to the scavenging effect of chloride ion on the hydroxyl radical. Full article
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23 pages, 2745 KB  
Article
Prebiotic Syntheses of Organophosphorus Compounds from Reduced Source of Phosphorus in Non-Aqueous Solvents
by Maheen Gull, Tian Feng, Benjamin Smith, Laurent Calcul and Matthew A. Pasek
Life 2023, 13(11), 2134; https://doi.org/10.3390/life13112134 - 29 Oct 2023
Cited by 3 | Viewed by 2248
Abstract
Reduced-oxidation-state phosphorus (reduced P, hereafter) compounds were likely available on the early Earth via meteorites or through various geologic processes. Due to their reactivity and high solubility, these compounds could have played a significant role in the origin of various organophosphorus compounds of [...] Read more.
Reduced-oxidation-state phosphorus (reduced P, hereafter) compounds were likely available on the early Earth via meteorites or through various geologic processes. Due to their reactivity and high solubility, these compounds could have played a significant role in the origin of various organophosphorus compounds of biochemical significance. In the present work, we study the reactions between reduced P compounds and their oxidation products, with the three nucleosides (uridine, adenosine, and cytidine), with organic alcohols (glycerol and ethanolamine), and with the tertiary ammonium organic compound, choline chloride. These reactions were studied in the non-aqueous solvent formamide and in a semi-aqueous solvent comprised of urea: ammonium formate: water (UAFW, hereafter) at temperatures of 55–68 °C. The inorganic P compounds generated through Fenton chemistry readily dissolve in the non-aqueous and semi-aqueous solvents and react with organics to form organophosphites and organophosphates, including those which are identified as phosphate diesters. This dual approach (1) use of non-aqueous and semi-aqueous solvents and (2) use of a reactive inorganic P source to promote phosphorylation and phosphonylation reactions of organics readily promoted anhydrous chemistry and condensation reactions, without requiring any additive, catalyst, or other promoting agent under mild heating conditions. We also present a comparative study of the release of P from various prebiotically relevant phosphate minerals and phosphite salts (e.g., vivianite, apatite, and phosphites of iron and calcium) into formamide and UAFW. These results have direct implications for the origin of biological P compounds from non-aqueous solvents of prebiotic provenance. Full article
(This article belongs to the Special Issue Origin of Life in Chemically Complex Messy Environments: 2nd Edition)
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