Abundant geologic evidence shows that atmospheric oxygen levels were negligible until the Great Oxidation Event (GOE) at 2.4–2.1 Ga. The burial of organic matter is balanced by the release of oxygen, and if the release rate exceeds efficient oxygen sinks, atmospheric oxygen can accumulate until limited by oxidative weathering. The organic burial rate relative to the total carbon burial rate can be inferred from the carbon isotope record in sedimentary carbonates and organic matter, which provides a proxy for the oxygen source flux through time. Because there are no large secular trends in the carbon isotope record over time, it is commonly assumed that the oxygen source flux changed only modestly. Therefore, declines in oxygen sinks have been used to explain the GOE. However, the average isotopic value of carbon fluxes into the atmosphere–ocean system can evolve due to changing proportions of weathering and outgassing inputs. If so, large secular changes in organic burial would be possible despite unchanging carbon isotope values in sedimentary rocks. Here, we present an inverse analysis using a self‐consistent carbon cycle model to determine the maximum change in organic burial since ~4 Ga allowed by the carbon isotope record and other geological proxies. We find that fractional organic burial may have increased by 2–5 times since the Archean. This happens because O2‐dependent continental weathering of13C‐depleted organics changes carbon isotope inputs to the atmosphere–ocean system. This increase in relative organic burial is consistent with an anoxic‐to‐oxic atmospheric transition around 2.4 Ga without declining oxygen sinks, although these likely contributed. Moreover, our inverse analysis suggests that the Archean absolute organic burial flux was comparable to modern, implying high organic burial efficiency and ruling out very low Archean primary productivity.
The role that iron played in the oxygenation of Earth’s surface is equivocal. Iron could have consumed molecular oxygen when Fe3+-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. Using an isotopic fractionation model informed by these data, we constrain the relative sizes of sedimentary Fe3+-oxyhydroxide and pyrite sinks for Neoarchean marine iron. We show that pyrite burial could have resulted in molecular oxygen export exceeding local Fe2+oxidation sinks, thereby contributing to early episodes of transient oxygenation of Archean surface environments.
more » « less- NSF-PAR ID:
- 10198884
- Publisher / Repository:
- American Association for the Advancement of Science (AAAS)
- Date Published:
- Journal Name:
- Science
- Volume:
- 370
- Issue:
- 6515
- ISSN:
- 0036-8075
- Page Range / eLocation ID:
- p. 446-449
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Changes in the geological sulfur cycle are inferred from the sulfur isotopic composition of marine barite. The structure of the34S/32S record from the Mesozoic to present, which includes ∼50- and 100-Ma stepwise increases, has been interpreted as the result of microbial isotope effects or abrupt changes to tectonics and associated pyrite burial. Untangling the physical processes that govern the marine sulfur cycle and associated isotopic change is critical to understanding how climate, atmospheric oxygenation, and marine ecology have coevolved over geologic time. Here we demonstrate that the sulfur outgassing associated with emplacement of large igneous provinces can produce the apparent stepwise jumps in the isotopic record when coupled to long-term changes in burial efficiency. The record of large igneous provinces map onto the required outgassing events in our model, with the two largest steps in the sulfur isotope record coinciding with the emplacement of large igneous provinces into volatile-rich sedimentary basins. This solution provides a quantitative picture of the last 120 My of change in the ocean’s largest oxidant reservoir.
-
The evolution of oxygen cycles on Earth’s surface has been regulated by the balance between molecular oxygen production and consumption. The Neoproterozoic–Paleozoic transition likely marks the second rise in atmospheric and oceanic oxygen levels, widely attributed to enhanced burial of organic carbon. However, it remains disputed how marine organic carbon production and burial respond to global environmental changes and whether these feedbacks trigger global oxygenation during this interval. Here, we report a large lithium isotopic and elemental dataset from marine mudstones spanning the upper Neoproterozoic to middle Cambrian [~660 million years ago (Ma) to 500 Ma]. These data indicate a dramatic increase in continental clay formation after ~525 Ma, likely linked to secular changes in global climate and compositions of the continental crust. Using a global biogeochemical model, we suggest that intensified continental weathering and clay delivery to the oceans could have notably increased the burial efficiency of organic carbon and facilitated greater oxygen accumulation in the earliest Paleozoic oceans.more » « less
-
The disappearance of mass-independent sulfur isotope fractionation (S-MIF) within the c. 2.3-billion-year-old (Ga) Rooihoogte Formation has been heralded as a chemostratigraphic marker of permanent atmospheric oxygenation. Reports of younger S-MIF, however, question this narrative, leaving significant uncertainties surrounding the timing, tempo, and trajectory of Earth’s oxygenation. Leveraging a new bulk quadruple S-isotope record, we return to the South African Transvaal Basin in search of support for supposed oscillations in atmospheric oxygen beyond 2.3 Ga. Here, as expected, within the Rooihoogte Formation, our data capture a collapse in Δ 3× S values and a shift from Archean-like Δ 36 S/Δ 33 S slopes to their mass-dependent counterparts. Importantly, the interrogation of a Δ 33 S-exotic grain reveals extreme spatial variability, whereby atypically large Δ 33 S values are separated from more typical Paleoproterozoic values by a subtle grain-housed siderophile-enriched band. This isotopic juxtaposition signals the coexistence of two sulfur pools that were able to escape diagenetic homogenization. These large Δ 33 S values require an active photochemical sulfur source, fingerprinting atmospheric S-MIF production after its documented cessation elsewhere at ∼2.4 Ga. By contrast, the Δ 33 S monotony observed in overlying Timeball Hill Formation, with muted Δ 33 S values (<0.3‰) and predominantly mass-dependent Δ 36 S/Δ 33 S systematics, remains in stark contrast to recent reports of pronounced S-MIF within proximal formational equivalents. If reflective of atmospheric processes, these observed kilometer-scale discrepancies disclose heterogenous S-MIF delivery to the Transvaal Basin and/or poorly resolved fleeting returns to S-MIF production. Rigorous bulk and grain-scale analytical campaigns remain paramount to refine our understanding of Earth’s oxygenation and substantiate claims of post-2.3 Ga oscillations in atmospheric oxygen.more » « less
-
more » « less
Abstract Careful evaluation of the local geochemical conditions in past marine settings can provide a window to the average redox state of the global ocean during episodes of extensive organic carbon deposition. These comparisons aid in identifying the interplay between climate and biotic feedbacks contributing to and resulting from these events. Well‐documented examples are known from the Mesozoic Era, which is characterized by episodes of widespread organic carbon deposition known as Oceanic Anoxic Events. This organic carbon burial typically leads to coeval positive carbon‐isotope excursions. Geochemical data are presented here for several palaeoredox proxies (Cr/Ti, V, Mo, Zn, Mn, Fe speciation, I/Ca and sulphur isotopes) from a section exposed at Furlo in the Marche–Umbrian Apennines of Italy that spans the Cenomanian–Turonian boundary. Here, Oceanic Anoxic Event 2 is represented by a
ca 1 m thick radiolarian‐rich millimetre‐laminated organic‐rich shale known locally as the Bonarelli Level. Iron speciation data for thin organic‐rich intervals observed below the Bonarelli Level imply a local redox shift going into the Oceanic Anoxic Event, with ferruginous conditions (i.e. anoxic with dissolved ferrous iron) transiently developed prior to the event and euxinia (i.e. anoxic and sulphidic bottom waters) throughout the event itself. Pre‐Oceanic Anoxic Event enrichments of elements sensitive to anoxic water columns were due to initial development of locally ferruginous bottom waters as a precursor to the event. However, the greater global expanse of dysoxic to euxinic conditions during the Oceanic Anoxic Event greatly reduced redox‐sensitive trace‐metal concentrations in seawater. Pyrite sulphur isotopes document a positive excursion during the Oceanic Anoxic Event. Carbonate I/Ca ratios were generally low, suggesting locally reduced bottom‐water oxygen conditions preceding the event and relatively increased oxygen concentrations post‐event. Combined, the Furlo geochemical data suggest a redox‐stratified water column with oxic surface waters and a shallow chemocline overlying locally ferruginous bottom waters preceding the event, globally widespread euxinic bottom waters during the Oceanic Anoxic Event, followed by chemocline shallowing but sustained local redox stratification following the event.
