Matthew A. Pasek

Rethinking early Earth phosphorus geochemistry

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO32−), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.

Evidence for reactive reduced phosphorus species in the early Archean ocean

It has been hypothesized that before the emergence of modern DNA–RNA–protein life, biology evolved from an “RNA world.” However, synthesizing RNA and other organophosphates under plausible early Earth conditions has proved difficult, with the incorporation of phosphorus (P) causing a particular problem because phosphate, where most environmental P resides, is relatively insoluble and unreactive. Recently, it has been proposed that during the Hadean–Archean heavy bombardment by extraterrestrial impactors, meteorites would have provided reactive P in the form of the iron–nickel phosphide mineral schreibersite. This reacts in water, releasing soluble and reactive reduced P species, such as phosphite, that could then be readily incorporated into prebiotic molecules. Here, we report the occurrence of phosphite in early Archean marine carbonates at levels indicating that this was an abundant dissolved species in the ocean before 3.5 Ga. Additionally, we show that schreibersite readily reacts with an aqueous solution of glycerol to generate phosphite and the membrane biomolecule glycerol–phosphate under mild thermal conditions, with this synthesis using a mineral source of P. Phosphite derived from schreibersite was, hence, a plausible reagent in the prebiotic synthesis of phosphorylated biomolecules and was also present on the early Earth in quantities large enough to have affected the redox state of P in the ocean. Phosphorylated biomolecules like RNA may, thus, have first formed from the reaction of reduced P species with the prebiotic organic milieu on the early Earth.

Extraterrestrial Flux of Potentially Prebiotic C, N, and P to the Early Earth

With growing evidence for a heavy bombardment period ending 4–3.8 billion years ago, meteorites and comets may have been an important source of prebiotic carbon, nitrogen, and phosphorus on the early Earth. Life may have originated shortly after the late-heavy bombardment, when concentrations of organic compounds and reactive phosphorus were enough to “kick life into gear”. This work quantifies the sources of potentially prebiotic, extraterrestrial C, N, and P and correlates these fluxes with a comparison to total Ir fluxes, and estimates the effect of atmosphere on the survival of material. We find (1) that carbonaceous chondrites were not a good source of organic compounds, but interplanetary dust particles provided a constant, steady flux of organic compounds to the surface of the Earth, (2) extraterrestrial metallic material was much more abundant on the early Earth, and delivered reactive P in the form of phosphide minerals to the Earth’s surface, and (3) large impacts provided substantial local enrichments of potentially prebiotic reagents. These results help elucidate the potential role of extraterrestrial matter in the origin of life.

CLATHRATION OF VOLATILES IN THE SOLAR NEBULA AND IMPLICATIONS FOR THE ORIGIN OF TITAN'S ATMOSPHERE

We describe a scenario of Titans formation matching the constraints imposed by its current atmospheric composition. Assuming that the abundances of all elements, including oxygen, are solar in the outer nebula, we show that the icy planetesimals were agglomerated in the feeding zone of Saturn from a mixture of clathrates with multiple guest species, so-called stochiometric hydrates such as ammonia hydrate, and pure condensates. We also use a statistical thermodynamic approach to constrain the composition of multiple guest clathrates formed in the solar nebula. We then infer that krypton and xenon, that are expected to condense in the 20-30 K temperature range in the solar nebula, are trapped in clathrates at higher temperatures than 50 K. Once formed, these ices either were accreted by Saturn or remained embedded in its surrounding subnebula until they found their way into the regular satellites growing around Saturn. In order to explain the carbon monoxide and primordial argon deficiencies of Titans atmosphere, we suggest that the satellite was formed from icy planetesimals initially produced in the solar nebula and that were partially devolatilized at a temperature not exceeding ~50 K during their migration within Saturns subnebula. The observed deficiencies of Titans atmosphere in krypton and xenon could result from other processes that may have occurred both prior to or after the completion of Titan. Thus, krypton and xenon may have been sequestrated in the form of XH+ 3 complexes in the solar nebula gas phase, causing the formation of noble gas-poor planetesimals ultimately accreted by Titan. Alternatively, krypton and xenon may have also been trapped efficiently in clathrates located on the satellites surface or in its atmospheric haze. We finally discuss the subsequent observations that would allow us to determine which of these processes is the most likely.

Redox chemistry in the phosphorus biogeochemical cycle

Significance Phosphorus is an important nutrient for living organisms. Phosphorus is generally considered to bear a 5+ oxidation state, but several lower redox states have been reported, including the toxic gas phosphine. We show here that the lower redox states of phosphorus are common in Florida water samples, and that based on the global concentration of phosphine, we might expect to see 5−15% of all dissolved phosphorus in a lower redox state. The element phosphorus (P) controls growth in many ecosystems as the limiting nutrient, where it is broadly considered to reside as pentavalent P in phosphate minerals and organic esters. Exceptions to pentavalent P include phosphine—PH3—a trace atmospheric gas, and phosphite and hypophosphite, P anions that have been detected recently in lightning strikes, eutrophic lakes, geothermal springs, and termite hindguts. Reduced oxidation state P compounds include the phosphonates, characterized by C−P bonds, which bear up to 25% of total organic dissolved phosphorus. Reduced P compounds have been considered to be rare; however, the microbial ability to use reduced P compounds as sole P sources is ubiquitous. Here we show that between 10% and 20% of dissolved P bears a redox state of less than +5 in water samples from central Florida, on average, with some samples bearing almost as much reduced P as phosphate. If the quantity of reduced P observed in the water samples from Florida studied here is broadly characteristic of similar environments on the global scale, it accounts well for the concentration of atmospheric phosphine and provides a rationale for the ubiquity of phosphite utilization genes in nature. Phosphine is generated at a quantity consistent with thermodynamic equilibrium established by the disproportionation reaction of reduced P species. Comprising 10–20% of the total dissolved P inventory in Florida environments, reduced P compounds could hence be a critical part of the phosphorus biogeochemical cycle, and in turn may impact global carbon cycling and methanogenesis.

Acidification of Europa's subsurface ocean as a consequence of oxidant delivery

Oxidants are formed at the surface of Europa and may be delivered to the subsurface ocean, possibly in great quantities. Whether these substances would be available for biological metabolism is uncertain, because they may react with sulfides and other compounds to generate sulfuric and other acids. If this process has been active on Europa for much of its age, then not only would it rob the ocean of life-supporting oxidants but the subsurface ocean could have a pH of ~2.6, which is so acidic as to present an environmental challenge for life, unless organisms consume or sequester the oxidants fast enough to ameliorate the acidification.

Darwin's Warm Little Pond: A One‐Pot Reaction for Prebiotic Phosphorylation and the Mobilization of Phosphate from Minerals in a Urea‐Based Solvent

The poor reactivity of insoluble phosphates, such as apatite-group minerals, has been a long-appreciated obstacle for proposed models of prebiotic organophosphate formation. This obstacle presents a significant challenge to the nascent development of an RNA world and other models for the origins of life on Earth. Herein, we demonstrate that a scenario based on the formation of a urea/ammonium formate/water (UAFW) eutectic solution leads to an increase in phosphorylation when compared to urea alone for phosphate sources of varying solubility. In addition, under evaporative conditions and in the presence of MgSO4 , the UAFW eutectic mobilizes the phosphate sequestered in water-insoluble hydroxyapatite, giving rise to a marked increase in phosphorylation. These results suggest that the prebiotic concentrations of urea in a geologically plausible evaporitic environment could solve the problem of organic phosphorylation on a prebiotic Earth.

Nucleoside phosphorylation by the mineral schreibersite

Phosphorylation of the nucleosides adenosine and uridine by the simple mixing and mild heating of aqueous solutions of the organic compounds with synthetic analogs of the meteoritic mineral schreibersite, (Fe,Ni)3P under slightly basic conditions (pH ~9) is reported. These results suggest a potential role for meteoritic phosphorus in the origin and development of early life.

A primordial origin for the atmospheric methane of Saturn’s moon Titan

The origin of Titan’s atmospheric methane is a key issue for understanding the origin of the saturnian satellite system. It has been proposed that serpentinization reactions in Titan’s interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan’s planetesimals before its formation. Here, we point out that serpentinization reactions in Titan’s interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/ H ratio in Titan’s water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan’s interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite’s planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan’s interior can be up to � 1300 times the current mass of atmospheric methane.

Is struvite a prebiotic mineral

The prebiotic relevance of mineral struvite, MgNH4PO4·6H2O, was studied experimentally as a phosphorylating reagent and, theoretically, to understand the geochemical requirements for its formation. The effectiveness of phosphorylation by the phosphate mineral, monetite, CaHPO4, was also studied to compare to the efficiency of struvite. The experiments focused on the phosphorylation reactions of the minerals with organic compounds, such as nucleosides, glycerol and choline chloride, and heat at 75 °C for about 7–8 days and showed up to 28% phosphorylation of glycerol. In contrast, the compositional requirements for the precipitation of struvite are high ammonium and phosphate concentrations, as well as a little Ca2+ dissolved in the water. Combined, these requirements suggest that it is not likely that struvite was present in excess on the early Earth to carry out phosphorylation reactions. The present study focuses on the thermodynamic aspects of struvite formation, complementing the results given by Orgel and Handschuh (1973), which were based on the kinetic effects.