Relatively oxidized fluids fed Earth's earliest hydrothermal systems.

The properties of high-temperature lithospheric fluids within the early Earth are poorly known, yet many origin-of-life scenarios depend upon their characteristics. These fluids represent a key communication pathway between Earth's interior and hydrothermal pools. We use zircon chemistry, experiments, and modeling to infer the character of lithospheric fluids approaching 4 billion years. We constrain oxygen fugacity, chlorine content, and temperature, which allow us to model the solubility and transport of metals that are hypothesized to be crucial for the origin of life. We show that these fluids were more oxidized than the terrestrial mantle during this time and that they were interacting with near-surface aqueous systems, possibly subaerial hydrothermal pools, amplifying redox gradients in a location attractive for prebiotic molecular synthesis or sustained microbial activity.

Eoarchean and Hadean melts reveal arc-like trace element and isotopic signatures.

Constraining the lithological diversity and tectonics of the earliest Earth is critical to understanding our planet's evolution. Here we use detrital Jack Hills zircon (3.7 - 4.2 Ga) analyses coupled with new experimental partitioning data to model the silica content, Si+O isotopic composition, and trace element contents of their parent melts. Comparing our derived Jack Hills zircons' parent melt Si+O isotopic compositions (-1.92 ≤ δ30SiNBS28 ≤ 0.53 ‰; 5.23 ≤ δ18OVSMOW ≤ 9.00 ‰) to younger crustal lithologies, we conclude that the chemistry of the parent melts was influenced by the assimilation of terrigenous sediments, serpentinites, cherts, and silicified basalts, followed by igneous differentiation, leading to the formation of intermediate to felsic melts in the early Earth. Trace element measurements also show that the formational regime had an arc-like chemistry, implying the presence of mobile-lid tectonics in the Hadean. Finally, we propose that these continental-crust forming processes operated uniformly from 4.2 to at least 3.7 Ga.

Frontiers in Prebiotic Chemistry and Early Earth Environments.

The Prebiotic Chemistry and Early Earth Environments (PCE3) Consortium is a community of researchers seeking to understand the origins of life on Earth and in the universe. PCE3 is one of five Research Coordination Networks (RCNs) within NASA's Astrobiology Program. Here we report on the inaugural PCE3 workshop, intended to cross-pollinate, transfer information, promote cooperation, break down disciplinary barriers, identify new directions, and foster collaborations. This workshop, entitled, "Building a New Foundation", was designed to propagate current knowledge, identify possibilities for multidisciplinary collaboration, and ultimately define paths for future collaborations. Presentations addressed the likely conditions on early Earth in ways that could be incorporated into prebiotic chemistry experiments and conceptual models to improve their plausibility and accuracy. Additionally, the discussions that followed among workshop participants helped to identify within each subdiscipline particularly impactful new research directions. At its core, the foundational knowledge base presented in this workshop should underpin future workshops and enable collaborations that bridge the many disciplines that are part of PCE3.

Origin and significance of Si and O isotope heterogeneities in Phanerozoic, Archean, and Hadean zircon.

Hydrosphere interactions and alteration of the terrestrial crust likely played a critical role in shaping Earth's surface, and in promoting prebiotic reactions leading to life, before 4.03 Ga (the Hadean Eon). The identity of aqueously altered material strongly depends on lithospheric cycling of abundant and water-soluble elements such as Si and O. However, direct constraints that define the character of Hadean sedimentary material are absent because samples from this earliest eon are limited to detrital zircons (ZrSiO4). Here we show that concurrent measurements of Si and O isotope ratios in Phanerozoic and detrital pre-3.0 Ga zircon constrain the composition of aqueously altered precursors incorporated into their source melts. Phanerozoic zircon from (S)edimentary-type rocks contain heterogeneous δ18O and δ30Si values consistent with assimilation of metapelitic material, distinct from the isotopic character of zircon from (I)gneous- and (A)norogenic-type rocks. The δ18O values of detrital Archean zircons are heterogeneous, although yield Si isotope compositions like mantle-derived zircon. Hadean crystals yield elevated δ18O values (vs. mantle zircon) and δ30Si values span almost the entire range observed for Phanerozoic samples. Coupled Si and O isotope data represent a constraint on Hadean weathering and sedimentary input into felsic melts including remelting of amphibolites possibly of basaltic origin, and fractional addition of chemical sediments, such as cherts and/or banded iron formations (BIFs) into source melts. That such sedimentary deposits were extensive enough to change the chemical signature of intracrustal melts suggests they may have been a suitable niche for (pre)biotic chemistry as early as 4.1 Ga.

Possible Biosphere-Lithosphere Interactions Preserved in Igneous Zircon and Implications for Hadean Earth.

Granitoids are silicic rocks that make up the majority of the continental crust, but different models arise for the origins of these rocks. One classification scheme defines different granitoid types on the basis of materials involved in the melting/crystallization process. In this end-member case, granitoids may be derived from melting of a preexisting igneous rock, while other granitoids, by contrast, are formed or influenced by melting of buried sedimentary material. In the latter case, assimilated sedimentary material altered by chemical processes occurring at the near surface of Earth-including biological activity-could influence magma chemical properties. Here, we apply a redox-sensitive calibration based on the incorporation of Ce into zircon crystals found in these two rock types, termed sedimentary-type (S-type) and igneous-type (I-type) granitoids. The ∼400 Ma Lachlan Fold Belt rocks of southeastern Australia were chosen for investigation here; these rocks have been a key target used to describe and explore granitoid genesis for close to 50 years. We observe that zircons found in S-type granitoids formed under more reducing conditions than those formed from I-type granitoids from the same terrain. This observation, while reflecting 9 granitoids and 289 analyses of zircons from a region where over 400 different plutons have been identified, is consistent with the incorporation of (reduced) organic matter in the former and highlights one possible manner in which life may modify the composition of igneous minerals. The chemical properties of rocks or igneous minerals may extend the search for ancient biological activity to the earliest period of known igneous activity, which dates back to ∼4.4 billion years ago. If organic matter was incorporated into Hadean sediments that were buried and melted, then these biological remnants could imprint a chemical signature within the subsequent melt and the resulting crystal assemblage, including zircon.

RNA Oligomerization in Laboratory Analogues of Alkaline Hydrothermal Vent Systems.

Discovering pathways leading to long-chain RNA formation under feasible prebiotic conditions is an essential step toward demonstrating the viability of the RNA World hypothesis. Intensive research efforts have provided evidence of RNA oligomerization by using circular ribonucleotides, imidazole-activated ribonucleotides with montmorillonite catalyst, and ribonucleotides in the presence of lipids. Additionally, mineral surfaces such as borates, apatite, and calcite have been shown to catalyze the formation of small organic compounds from inorganic precursors (Cleaves, 2008 ), pointing to possible geological sites for the origins of life. Indeed, the catalytic properties of these particular minerals provide compelling evidence for alkaline hydrothermal vents as a potential site for the origins of life since, at these vents, large metal-rich chimney structures can form that have been shown to be energetically favorable to diverse forms of life. Here, we test the ability of iron- and sulfur-rich chimneys to support RNA oligomerization reactions using imidazole-activated and non-activated ribonucleotides. The chimneys were synthesized in the laboratory in aqueous "ocean" solutions under conditions consistent with current understanding of early Earth. Effects of elemental composition, pH, inclusion of catalytic montmorillonite clay, doping of chimneys with small organic compounds, and in situ ribonucleotide activation on RNA polymerization were investigated. These experiments, under certain conditions, showed successful dimerization by using unmodified ribonucleotides, with the generation of RNA oligomers up to 4 units in length when imidazole-activated ribonucleotides were used instead. Elemental analysis of the chimney precipitates and the reaction solutions showed that most of the metal cations that were determined were preferentially partitioned into the chimneys.

The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.