Mechanistic Links Between the Sedimentary Redox Cycle and Marine Acid-Base Chemistry

The redox state of Earth's surface is controlled on geological timescales by the flow of electrons through the sedimentary rock cycle, mediated largely by the weathering and burial of C‐S‐Fe phases. These processes buffer atmospheric pO₂. At the same time, CO₂ influxes and carbonate burial control seawater acid‐base chemistry and climate over long timescales via the carbonate‐silicate cycle. However, these two systems are mechanistically linked and impact each other via charge balance in the hydrosphere. Here, we use a low‐order Earth system model to interrogate a subset of these connections, with a focus on changes that occur during perturbations to electron flow through the sedimentary rock cycle. We show that the net oxidation or reduction of the Earth's surface can play an important role in controlling acid‐base processes in the oceans and thus climate, and suggest that these links should be more fully integrated into interpretive frameworks aimed at understanding Earth system evolution throughout Precambrian and Phanerozoic time

Geochemical support for a climbing habit within the Paleozoic seed fern genus Medullosa

A long-standing problem in paleobotany is the accurate identification of the growth habits and statures of fossil plants. Tissue-specific analysis of stable carbon isotope ratios in plant fossils can provide an independent perspective on this issue. Lignin, a fundamental biopolymer providing structural support in plant tissues and the second most abundant organic material in plants, is ^(13)C depleted by several parts per thousand, averaging 4.1‰, relative to other plant constructional materials (e.g. cellulose). With this isotopic difference, the biochemical structural composition of ancient plants (and inferred stature) can be interrogated using microscale in situ isotope analysis between different tissues in fossils. We applied this technique to a well-preserved specimen of the Late Paleozoic seed plant Medullosa, an extinct genus with a variety of growth habits that includes several enigmatic yet abundant small-stemmed species widely found in calcium carbonate concretions (“coal balls”) in the Pennsylvanian coal beds of Iowa, USA. It remains unclear which of the medullosans were freestanding, and recent analysis of the medullosan vascular system has shown that this system provided little structural support to the whole plant. The leading hypothesis for small-stemmed medullosan specimens predicts that cortical tissues could have provided additional structural support, but only if they were lignified. The expected isotopic difference between lignified tissue and unlignified tissue is smaller than that expected from pure extracts, for the simple reason that even woody tissues maximally contain 40% lignin (by mass). This reduces the expected maximum difference between weakly and heavily lignified tissues by 60%, down to ~0.5‰–2‰. Analysis of the medullosan stem reveals a consistent difference in isotope ratios of 0.7‰–1.0‰ between lignified xylem and cortical tissues. This implies low abundances of lignin (between 0% and 11%) within the cortex. This inferred structural biochemistry supports hypotheses that the peripheral portions of these medullosan stems were not biomechanically reinforced to permit the plants to grow as freestanding, arborescent trees. A number of climbing or scandent medullosans have been identified in the fossil record, and this mode of growth has been suggested to be common within the group on the basis of observations from comparative biomechanics, hydraulics, and development. Finally, this mode of growth is common in several clades of stem group seed plants, including Lyginopteris and Callistophyton, along with Medullosa. This study provides further support for ideas that place a great portion of early seed plant diversity under the canopy, rather than forming it

An orbital window into the ancient Sun's mass

Models of the Sun's long-term evolution suggest that its luminosity was substantially reduced 2-4 billion years ago, which is inconsistent with substantial evidence for warm and wet conditions in the geological records of both ancient Earth and Mars. Typical solutions to this so-called "faint young Sun paradox" consider changes in the atmospheric composition of Earth and Mars, and while attractive, geological verification of these ideas is generally lacking-particularly for Mars. One possible underexplored solution to the faint young Sun paradox is that the Sun has simply lost a few percent of its mass during its lifetime. If correct, this would slow, or potentially even offset the increase in luminosity expected from a constant-mass model. However, this hypothesis is challenging to test. Here, we propose a novel observational proxy of the Sun's ancient mass that may be readily measured from accumulation patterns in sedimentary rocks on Earth and Mars. We show that the orbital parameters of the Solar system planets undergo quasi-cyclic oscillations at a frequency, given by secular mode g_2-g_5, that scales approximately linearly with the Sun's mass. Thus by examining the cadence of sediment accumulation in ancient basins, it is possible distinguish between the cases of a constant mass Sun and a more massive ancient Sun to a precision of greater than about 1 per cent. This approach provides an avenue toward verification, or of falsification, of the massive early Sun hypothesis.Comment: 7 pages, 4 Figures. Accepted to The Astrophysical Journal Letter

Sulfate Burial Constraints on the Phanerozoic Sulfur Cycle

The sulfur cycle influences the respiration of sedimentary organic matter, the oxidation state of the atmosphere and oceans, and the composition of seawater. However, the factors governing the major sulfur fluxes between seawater and sedimentary reservoirs remain incompletely understood. Using macrostratigraphic data, we quantified sulfate evaporite burial fluxes through Phanerozoic time. Approximately half of the modern riverine sulfate flux comes from weathering of recently deposited evaporites. Rates of sulfate burial are unsteady and linked to changes in the area of marine environments suitable for evaporite formation and preservation. By contrast, rates of pyrite burial and weathering are higher, less variable, and largely balanced, highlighting a greater role of the sulfur cycle in regulating atmospheric oxygen

Breathing room for early animals

If life has been present on our planet for much of its history—more than three and a half billion years—why did it take so long for animals to appear? This question emerged long ago from the incipient fabric of the fossil record, which embodies the sudden appearance of metazoans in sedimentary strata deposited near the end of Precambrian time—and scientists have wrestled with this issue now for well over a hundred years (1). For the past 50 or so years, the most popular and pertinacious hypotheses have concerned atmospheric dioxygen (2–5). Because of their aerobic physiology, the idea was that O_2 levels were perhaps too low to have supported animals until sometime near the end of Precambrian time, and that rising O2 levels thereafter provided a quantum evolutionary leap of sorts for aerobic biology culminating in the “late” evolution of animals (3). A recent study of middle Proterozoic sedimentary rocks in China, however, favors a different view—suggesting that O_2 levels capable of supporting animal physiology were present more than 500 million years before the appearance of animals (6)

Climate change and the selective signature of the Late Ordovician mass extinction

Selectivity patterns provide insights into the causes of ancient extinction events. The Late Ordovician mass extinction was related to Gondwanan glaciation; however, it is still unclear whether elevated extinction rates were attributable to record failure, habitat loss, or climatic cooling. We examined Middle Ordovician-Early Silurian North American fossil occurrences within a spatiotemporally explicit stratigraphic framework that allowed us to quantify rock record effects on a per-taxon basis and assay the interplay of macrostratigraphic and macroecological variables in determining extinction risk. Genera that had large proportions of their observed geographic ranges affected by stratigraphic truncation or environmental shifts at the end of the Katian stage were particularly hard hit. The duration of the subsequent sampling gaps had little effect on extinction risk, suggesting that this extinction pulse cannot be entirely attributed to rock record failure; rather, it was caused, in part, by habitat loss. Extinction risk at this time was also strongly influenced by the maximum paleolatitude at which a genus had previously been sampled, a macroecological trait linked to thermal tolerance. A model trained on the relationship between 16 explanatory variables and extinction patterns during the early Katian interval substantially underestimates the extinction of exclusively tropical taxa during the late Katian interval. These results indicate that glacioeustatic sea-level fall and tropical ocean cooling played important roles in the first pulse of the Late Ordovician mass extinction in Laurentia

A shorter Archean day-length biases interpretations of the early Earth's climate

Earth's earliest sedimentary record contains evidence that surface temperatures were similar to, or perhaps even warmer than modern. In contrast, standard Solar models suggest the Sun was 25% less luminous at this ancient epoch, implying a cold, frozen planet—all else kept equal. This discrepancy, known as the Faint Young Sun Paradox, remains unresolved. Most proposed solutions invoke high concentrations of greenhouse gases in the early atmosphere to offset for the fainter Sun, though current geological constraints are insufficient to verify or falsify these scenarios. In this work, we examined several simple mechanisms that involve the role played by Earth's spin rate, which was significantly faster during Archean time. This faster spin rate enhances the equator-to-pole temperature gradient, facilitating a warm equator, while maintaining cold poles. Results show that such an enhanced meridional gradient augments the meridional gradient in carbonate deposition, which biases the surviving geological record away from the global mean, toward warmer waters. Moreover, using simple atmospheric models, we found that the faster-spinning Earth was less sensitive to ice-albedo feedbacks, facilitating larger meridional temperature gradients before succumbing to global glaciation. We show that within the faster-spinning regime, the greenhouse warming required to generate an ice-free Earth can differ from that required to generate an Earth with permanent ice caps by the equivalent of 1–2 orders of magnitude of pCO_2. Accordingly, the resolution of the Faint Young Sun problem depends significantly on whether the early Earth was ever, or even at times, ice-free

A shorter Archean day-length biases interpretations of the early Earth's climate

Earth's earliest sedimentary record contains evidence that surface temperatures were similar to, or perhaps even warmer than modern. In contrast, standard Solar models suggest the Sun was 25% less luminous at this ancient epoch, implying a cold, frozen planet-all else kept equal. This discrepancy, known as the Faint Young Sun Paradox, remains unresolved. Most proposed solutions invoke high concentrations of greenhouse gases in the early atmosphere to offset for the fainter Sun, though current geological constraints are insufficient to verify or falsify these scenarios. In this work, we examined several simple mechanisms that involve the role played by Earth's spin rate, which was significantly faster during Archean time. This faster spin rate enhances the equator-to-pole temperature gradient, facilitating a warm equator, while maintaining cold poles. Results show that such an enhanced meridional gradient augments the meridional gradient in carbonate deposition, which biases the surviving geological record away from the global mean, toward warmer waters. Moreover, using simple atmospheric models, we found that the faster-spinning Earth was less sensitive to ice-albedo feedbacks, facilitating larger meridional temperature gradients before succumbing to global glaciation. We show that within the faster-spinning regime, the greenhouse warming required to generate an ice-free Earth can differ from that required to generate an Earth with permanent ice caps by the equivalent of 1-2 orders of magnitude of pCO2. Accordingly, the resolution of the Faint Young Sun problem depends significantly on whether the early Earth was ever, or even at times, ice-free.Comment: 15 pages. 7 Figures. Accepted for publication in Earth and Planetary Science Letter

An iron shuttle for deepwater silica in Late Archean and early Paleoproterozoic iron formation

Iron formations are typically thinly bedded or laminated sedimentary rocks containing 15% or more of iron and a large proportion of silica (commonly > 40%). In the ca. 2590-2460 Ma Campbellrand-Kuruman Complex, Transvaal Supergroup, South Africa, iron formation occurs as a sediment-starved deepwater facies distal to carbonates and shales. Iron minerals, primarily siderite, define the lamination. The silica primarily occurs as thin beds and nodules of diagenetic chert (now microcrystalline quartz), filling pore space and replacing iron formation minerals and co-occurring deepwater lithologies. Mechanisms proposed to explain precipitation of the iron component of iron formation include photosynthetic oxygen production, anoxygenic photosynthesis, abiotic photochemistry, and chemoautotrophy using Fe(II) as an electron donor. The origin and mechanism of silica precipitation in these deposits have received less attention. Here we present a conceptual model of iron formation that offers insight into the deposition of silica. The model hinges on the proclivity of dissolved silica to adsorb onto the hydrous surfaces of ferric oxides. Soluble ferrous iron is oxidized in the surface ocean to form ferric hydroxides, which precipitate. Fe(OH)_3 binds silica and sinks from the surface ocean along with organic matter, shuttling silica to basinal waters and sediments. Fe(III) respiration in the sediments returns the majority of iron to the water column but also generates considerable alkalinity in pore waters, driving precipitation of siderite from Fe2+ and respiration-influenced CO2. Silica liberated during iron reduction becomes concentrated in pore fluids and is ultimately precipitated as diagenetic mineral phases. This model explains many of the mineralogical, textural, and environmental features of Late Archean and earliest Paleo-proterozoic iron formation