Lateral redox variability in ca. 1.9 Ga marine environments indicated by organic carbon and nitrogen isotope compositions.

The stepwise oxygenation of Earth's surficial environment is thought to have shaped the evolutionary history of life. Microfossil records and molecular clocks suggest eukaryotes appeared during the Paleoproterozoic, perhaps shortly after the Great Oxidation Episode at ca. 2.

Onset of coupled atmosphere-ocean oxygenation 2.3 billion years ago.

The initial rise of molecular oxygen (O) shortly after the Archaean-Proterozoic transition 2.5 billion years ago was more complex than the single step-change once envisioned. Sulfur mass-independent fractionation records suggest that the rise of atmospheric O was oscillatory, with multiple returns to an anoxic state until perhaps 2.

Preservation and Distributions of Covalently Bound Polyaromatic Hydrocarbons in Ancient Biogenic Kerogens and Insoluble Organic Macromolecules.

The likelihood of finding pristine molecular biosignatures preserved in Earth's oldest rocks or on other planetary bodies is low, and new approaches are needed to assess the origins of highly altered and recalcitrant organic matter. In this study, we aim to understand the distributions and systematics of preservation of ancient polycyclic aromatic hydrocarbons (PAHs), as both free hydrocarbons and bound within insoluble macromolecules. We report the distributions of bound PAHs generated by catalytic hydropyrolysis from ancient biogenic kerogens and from insoluble organic matter (IOM) in high-temperature carbonaceous residues from pyrobitumens and synthetic coke.

A 200-million-year delay in permanent atmospheric oxygenation.

The rise of atmospheric oxygen fundamentally changed the chemistry of surficial environments and the nature of Earth's habitability. Early atmospheric oxygenation occurred over a protracted period of extreme climatic instability marked by multiple global glaciations, with the initial rise of oxygen concentration to above 10 of the present atmospheric level constrained to about 2.43 billion years ago.

A late Paleoproterozoic (1.74 Ga) deep-sea, low-temperature, iron-oxidizing microbial hydrothermal vent community from Arizona, USA.

Modern marine hydrothermal vents occur in a wide variety of tectonic settings and are characterized by seafloor emission of fluids rich in dissolved chemicals and rapid mineral precipitation. Some hydrothermal systems vent only low-temperature Fe-rich fluids, which precipitate deposits dominated by iron oxyhydroxides, in places together with Mn-oxyhydroxides and amorphous silica. While a proportion of this mineralization is abiogenic, most is the result of the metabolic activities of benthic, Fe-oxidizing bacteria (FeOB), principally belonging to the Zetaproteobacteria.

A persistently low level of atmospheric oxygen in Earth's middle age.

Resolving how Earth surface redox conditions evolved through the Proterozoic Eon is fundamental to understanding how biogeochemical cycles have changed through time. The redox sensitivity of cerium relative to other rare earth elements and its uptake in carbonate minerals make the Ce anomaly (Ce/Ce*) a particularly useful proxy for capturing redox conditions in the local marine environment. Here, we report Ce/Ce* data in marine carbonate rocks through 3.

Triple iron isotope constraints on the role of ocean iron sinks in early atmospheric oxygenation.

The role that iron played in the oxygenation of Earth's surface is equivocal. Iron could have consumed molecular oxygen when Fe-oxyhydroxides formed in the oceans, or it could have promoted atmospheric oxidation by means of pyrite burial. Through high-precision iron isotopic measurements of Archean-Paleoproterozoic sediments and laboratory grown pyrites, we show that the triple iron isotopic composition of Neoarchean-Paleoproterozoic pyrites requires both extensive marine iron oxidation and sulfide-limited pyritization.

The geologic history of seawater oxygen isotopes from marine iron oxides.

The oxygen isotope composition (δO) of marine sedimentary rocks has increased by 10 to 15 per mil since Archean time. Interpretation of this trend is hindered by the dual control of temperature and fluid δO on the rocks' isotopic composition. A new δO record in marine iron oxides covering the past ~2000 million years shows a similar secular rise.

Author Correction: Microbially induced potassium enrichment in Paleoproterozoic shales and implications for reverse weathering on early Earth.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Microbially induced potassium enrichment in Paleoproterozoic shales and implications for reverse weathering on early Earth.

Illitisation requires potassium incorporation into a smectite precursor, a process akin to reverse weathering. However, it remains unclear whether microbes facilitate K uptake to the sediments and whether illitisation was important in the geological past. The 2.

Limited oxygen production in the Mesoarchean ocean.

The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to "oxygen oases" well documented for the Neoarchean [2.8 to 2.

Organism motility in an oxygenated shallow-marine environment 2.1 billion years ago.

Evidence for macroscopic life in the Paleoproterozoic Era comes from 1.8 billion-year-old (Ga) compression fossils [Han TM, Runnegar B (1992) 257:232-235; Knoll et al. (2006) 361:1023-1038], Stirling biota [Bengtson S et al.

Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.

Ediacara biota flourished in oligotrophic and bacterially dominated marine environments across Baltica.

Middle-to-late Ediacaran (575-541 Ma) marine sedimentary rocks record the first appearance of macroscopic, multicellular body fossils, yet little is known about the environments and food sources that sustained this enigmatic fauna. Here, we perform a lipid biomarker and stable isotope (δN and δC) investigation of exceptionally immature late Ediacaran strata (<560 Ma) from multiple locations across Baltica. Our results show that the biomarker assemblages encompass an exceptionally wide range of hopane/sterane ratios (1.

Titanium isotopic evidence for felsic crust and plate tectonics 3.5 billion years ago.

Earth exhibits a dichotomy in elevation and chemical composition between the continents and ocean floor. Reconstructing when this dichotomy arose is important for understanding when plate tectonics started and how the supply of nutrients to the oceans changed through time. We measured the titanium isotopic composition of shales to constrain the chemical composition of the continental crust exposed to weathering and found that shales of all ages have a uniform isotopic composition.

Fungus-like mycelial fossils in 2.4-billion-year-old vesicular basalt.

Fungi have recently been found to comprise a significant part of the deep biosphere in oceanic sediments and crustal rocks. Fossils occupying fractures and pores in Phanerozoic volcanics indicate that this habitat is at least 400 million years old, but its origin may be considerably older. A 2.

Timing and tempo of the Great Oxidation Event.

The first significant buildup in atmospheric oxygen, the Great Oxidation Event (GOE), began in the early Paleoproterozoic in association with global glaciations and continued until the end of the Lomagundi carbon isotope excursion ca. 2,060 Ma. The exact timing of and relationships among these events are debated because of poor age constraints and contradictory stratigraphic correlations.

Selenium isotopes record extensive marine suboxia during the Great Oxidation Event.

It has been proposed that an "oxygen overshoot" occurred during the early Paleoproterozoic Great Oxidation Event (GOE) in association with the extreme positive carbon isotopic excursion known as the Lomagundi Event. Moreover, it has also been suggested that environmental oxygen levels then crashed to very low levels during the subsequent extremely negative Shunga-Francevillian carbon isotopic anomaly. These redox fluctuations could have profoundly influenced the course of eukaryotic evolution, as eukaryotes have several metabolic processes that are obligately aerobic.

The 2.1 Ga old Francevillian biota: biogenicity, taphonomy and biodiversity.

The Paleoproterozoic Era witnessed crucial steps in the evolution of Earth's surface environments following the first appreciable rise of free atmospheric oxygen concentrations ∼2.3 to 2.1 Ga ago, and concomitant shallow ocean oxygenation.

Biological carbon precursor to diagenetic siderite with spherical structures in iron formations.

During deposition of Precambrian iron formation, the combined sedimentation of ferrihydrite and phytoplankton biomass should have facilitated Fe(III) reduction during diagenesis. However, the only evidence for this reaction in iron formations is the iron and carbon isotope values preserved in the authigenic ferrous iron-containing minerals. Here we show experimentally that spheroidal siderite, which is preserved in many iron formation and could have been precursor to rhombohedral or massive siderite, forms by reacting ferrihydrite with glucose (a proxy for microbial biomass) at pressure and temperature conditions typical of diagenesis (170 °C and 1.

Proterozoic ocean redox and biogeochemical stasis.

The partial pressure of oxygen in Earth's atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5-0.543 Ga).

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event.

Carbonates from approximately 2.3-2.1 billion years ago show markedly positive δ(13)C values commonly reaching and sometimes exceeding +10‰.

Deposition of 1.88-billion-year-old iron formations as a consequence of rapid crustal growth.

Iron formations are chemical sedimentary rocks comprising layers of iron-rich and silica-rich minerals whose deposition requires anoxic and iron-rich (ferruginous) sea water. Their demise after the rise in atmospheric oxygen by 2.32 billion years (Gyr) ago has been attributed to the removal of dissolved iron through progressive oxidation or sulphidation of the deep ocean.