Phosphate minerals such as those in the apatite group tend to be the dominant forms of phosphorus in minerals on the Earth’s surface. Phosphate can be reduced to phosphides during high-energy events, such as lightning and impacts. Here we show that, in addition to formation of metal phosphides, a new compound was formed by lightning in a fulgurite from New Port Richey, Florida, USA. A calcium phosphite material, ideally CaHPO₃, was found in spherules mainly consisting of iron silicides that formed by lightning-induced fusion of sand around a tree root. This phosphite material bears a phosphorus oxidation state intermediate of that of phosphides and phosphates in a geologic sample and implicates phosphites as being potentially relevant to other high-energy events where phosphorus may partially change its redox state, and material similar to this phosphite may also be the source of phosphite that makes up part of the phosphorus biogeochemical cycle.

The availability of nucleotides on the early Earth is of great significance for the origin of a self-replicating system capable of undergoing evolution. We hereby report the successful phosphorylation reactions of the nucleoside uridine under heating in the “drying pool” prebiotic model at temperatures ranging from 60–75 °C, and by using pyrophosphate as a phosphorylation agent. Uridine monophosphates (UMP) such as uridine-5′-monophosphate (5′-UMP), 2′-UMP, and 3′-UMP, as well as cyclic 2′-3′-UMP, were identified by ³¹P-NMR. In addition to the above-mentioned products, a dimer of uridine-phosphate-uridine (U-P-U) was also observed. The reactions were promoted by white quartz sand, Mg²⁺, and by using urea as a condensation agent. The reactions also proceeded without this mixture; however, the yields increased remarkably with the presence of the above-mentioned materials. The results suggest that a hot/evaporating-drying pool of water containing organics, salts, and reactive phosphorus could be sufficient to form significant phosphate esters.

The in-fall of meteorites and interstellar dust particles during the Hadean–Archean heavy bombardment may have provided the early Earth with various reduced oxidation state phosphorus compounds and minerals, including phosphite (HPO₃²⁻)([Pi(III)]). The ion phosphite ([Pi(III)])has been postulated to be ubiquitous on the early Earth and consequently could have played a role in the emergence of organophosphorus compounds and other prebiotically relevant P species such as condensed P compounds, e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)]). In the present study, we show that phosphite ([Pi(III)]) oxidizes under mild heating conditions (e.g., wet–dry cycles and a prebiotic scenario mimicking a mildly hot-evaporating/drying pool on the early Earth at 78–83 °C) in the presence of urea and other additives, resulting in changes to orthophosphate ([Pi(V)]) alongside the formation of reactive condensed P compounds (e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)])) through a one-pot mechanism. Additionally, we also show that phosphite ([Pi(III)]) and the condensed P compounds readily react with organics (nucleosides and organic alcohol) to form organophosphorus compounds.

The formose reaction is a plausible prebiotic chemistry, famed for its production of sugars. In this work, we demonstrate that the Cannizzaro process is the dominant process in the formose reaction under many different conditions, thus necessitating a catalyst for the formose reaction under various environmental circumstances. The investigated formose reactions produce primarily organic acids associated with metabolism, a protometabolic system, and yield very little sugar left over. This is due to many of the acids forming from the degradation and Cannizaro reactions of many of the sugars produced during the formose reaction. We also show the heterogeneous Lewis-acid-based catalysis of the formose reaction by mineral systems associated with serpentinization. The minerals that showed catalytic activity include olivine, serpentinite, and calcium, and magnesium minerals including dolomite, calcite, and our Ca/Mg-chemical gardens. In addition, computational studies were performed for the first step of the formose reaction to investigate the reaction of formaldehyde, to either form methanol and formic acid under a Cannizzaro reaction or to react to form glycolaldehyde. Here, we postulate that serpentinization is therefore the startup process necessary to kick off a simple proto metabolic system—the formose protometabolic system.

Life is a complex, open chemical system that must be supported with energy inputs. If one fathoms how simple early life must have been, the complexity of modern-day life is staggering by comparison. A minimally complex system that could plausibly provide pyrophosphates for early life could be the oxidation of reduced phosphorus sources such as hypophosphite and phosphite. Like all plausible prebiotic chemistries, this system would have been altered by minerals and rocks in close contact with the evolving solutions. This study addresses the different types of perturbations that minerals might have on this chemical system. This study finds that minerals may inhibit the total production of oxidized phosphorus from reduced phosphorus species, they may facilitate the production of phosphate, or they may facilitate the production of pyrophosphate. This study concludes with the idea that mineral perturbations from the environment increase the chemical complexity of this system.

Iron silicide minerals (Fe-Si group) are found in terrestrial and solar system samples. These minerals tend to be more common in extraterrestrial rocks such as meteorites, and their existence in terrestrial rocks is limited due to a requirement of extremely reducing conditions to promote their formation. Such extremely reducing conditions can be found in fulgurites, which are glasses formed as cloud-to-ground lightning heats and fuses sand, soil, or rock. The objective of this paper is to review reports of iron silicides in fulgurites, note any similarities between separate fulgurite observations, and to explain the core connection between geological environments wherein these minerals are found. In addition, we also compare iron silicides in fulgurites to those in extraterrestrial samples.