[1] Oceanic anoxic events (OAEs) record profound changes in the climatic and paleoceanographic state of the planet and represent major disturbances in the global carbon cycle. OAEs that manifestly caused major chemical change in the Mesozoic Ocean include those of the early Toarcian (Posidonienschiefer event, T-OAE, ∼183 Ma), early Aptian (Selli event, OAE 1a, ∼120 Ma), early Albian (Paquier event, OAE 1b, ∼111 Ma), and Cenomanian–Turonian (Bonarelli event, C/T OAE, OAE 2, ∼93 Ma). Currently available data suggest that the major forcing function behind OAEs was an abrupt rise in temperature, induced by rapid influx of CO2 into the atmosphere from volcanogenic and/or methanogenic sources. Global warming was accompanied by an accelerated hydrological cycle, increased continental weathering, enhanced nutrient discharge to oceans and lakes, intensified upwelling, and an increase in organic productivity. An increase in continental weathering is typically recorded by transient increases in the seawater values of 87Sr/86Sr and 187Os/188Os ratios acting against, in the case of the Cenomanian-Turonian and early Aptian OAEs, a longer-term trend to less radiogenic values. This latter trend indicates that hydrothermally and volcanically sourced nutrients may also have stimulated local increases in organic productivity. Increased flux of organic matter favored intense oxygen demand in the water column, as well as increased rates of marine and lacustrine carbon burial. Particularly in those restricted oceans and seaways where density stratification was favored by paleogeography and significant fluvial input, conditions could readily evolve from poorly oxygenated to anoxic and ultimately euxinic (i.e., sulfidic), this latter state being geochemically the most significant. The progressive evolution in redox conditions through phases of denitrification/anammox, through to sulfate reduction accompanied by water column precipitation of pyrite framboids, resulted in fractionation of many isotope systems (e.g., N, S, Fe, Mo, and U) and mobilization and incorporation of certain trace elements into carbonates (Mn), sulfides, and organic matter. Sequestration of CO2 in organic-rich black shales and by reaction with silicate rocks exposed on continents would ultimately restore climatic equilibrium but at the expense of massive chemical change in the oceans and over time scales of tens to hundreds of thousands of years.

https://agupubs.onlinelibrary.wiley.com/doi/epdf/10.1029/2009GC002788

Geochemistry of oceanic anoxic events

Ocean acidification may have severe consequences for marine ecosystems; however, assessing its future impact is difficult because laboratory experiments and field observations are limited by their reduced ecologic complexity and sample period, respectively. In contrast, the geological record contains long-term evidence for a variety of global environmental perturbations, including ocean acidification plus their associated biotic responses. We review events exhibiting evidence for elevated atmospheric CO2, global warming, and ocean acidification over the past ~300 million years of Earth’s history, some with contemporaneous extinction or evolutionary turnover among marine calcifiers. Although similarities exist, no past event perfectly parallels future projections in terms of disrupting the balance of ocean carbonate chemistry—a consequence of the unprecedented rapidity of CO2 release currently taking place.

/pdf/the-geological-record-of-ocean-acidification-2rys4hl08r.pdf

The Geological Record of Ocean Acidification

Iron formations are economically important sedimentary rocks that are most common in Precambrian sedimentary successions. Although many aspects of their origin remain unresolved, it is widely accepted that secular changes in the style of their deposition are linked to environmental and geochemical evolution of Earth. Two types of Precambrian iron formations have been recognized with respect to their depositional setting. Algoma-type iron formations are interlayered with or stratigraphically linked to submarine-emplaced volcanic rocks in greenstone belts and, in some cases, with volcanogenic massive sulfide (VMS) deposits. In contrast, larger Superior-type iron formations are developed in passive-margin sedimentary rock successions and generally lack direct relationships with volcanic rocks. The early distinction made between these two iron-formation types, although mimimized by later studies, remains a valid first approximation. Texturally, iron formations were also divided into two groups. Banded iron formation (BIF) is dominant in Archean to earliest Paleoproterozoic successions, whereas granular iron formation (GIF) is much more common in Paleoproterozoic successions. Secular changes in the style of iron-formation deposition, identified more than 20 years ago, have been linked to diverse environmental changes. Geochronologic studies emphasize the episodic nature of the deposition of giant iron formations, as they are coeval with, and genetically linked to, time periods when large igneous provinces (LIPs) were emplaced. Superior-type iron formation first appeared at ca. 2.6 Ga, when construction of large continents changed the heat flux at the core-mantle boundary. From ca. 2.6 to ca. 2.4 Ga, global mafic magmatism culminated in the deposition of giant Superior-type BIF in South Africa, Australia, Brazil, Russia, and Ukraine. The younger BIFs in this age range were deposited during the early stage of a shift from reducing to oxidizing conditions in the ocean-atmosphere system. Counterintuitively, enhanced magmatism at 2.50 to 2.45 Ga may have triggered atmospheric oxidation. After the rise of atmospheric oxygen during the GOE at ca. 2.4 Ga, GIF became abundant in the rock record, compared to the predominance of BIF prior to the Great Oxidation Event (GOE). Iron formations generally disappeared at ca. 1.85 Ga, reappearing at the end of the Neoproterozoic, again tied to periods of intense magmatic activity and also, in this case, to global glaciations, the so-called Snowball Earth events. By the Phanerozoic, marine iron deposition was restricted to local areas of closed to semiclosed basins, where volcanic and hydrothermal activity was extensive (e.g., back-arc basins), with ironstones additionally being linked to periods of intense magmatic activity and ocean anoxia.

Late Paleoproterozoic iron formations and Paleozoic ironstones were deposited at the redoxcline where biological and nonbiological oxidation occurred. In contrast, older iron formations were deposited in anoxic oceans, where ferrous iron oxidation by anoxygenic photosynthetic bacteria was likely an important process. Endogenic and exogenic factors contributed to produce the conditions necessary for deposition of iron formation. Mantle plume events that led to the formation of LIPs also enhanced spreading rates of midocean ridges and produced higher growth rates of oceanic plateaus, both processes thus having contributed to a higher hydrothermal flux to the ocean. Oceanic and atmospheric redox states determined the fate of this flux. When the hydrothermal flux overwhelmed the oceanic oxidation state, iron was transported and deposited distally from hydrothermal vents. Where the hydrothermal flux was insufficient to overwhelm the oceanic redox state, iron was deposited only proximally, generally as oxides or sulfides. Manganese, in contrast, was more mobile. We conclude that occurrences of BIF, GIF, Phanerozoic ironstones, and exhalites surrounding VMS systems record a complex interplay involving mantle heat, tectonics, and surface redox conditions throughout Earth history, in which mantle heat unidirectionally declined and the surface oxidation state mainly unidirectionally increased, accompanied by superimposed shorter term fluctuations.

/pdf/iron-formation-the-sedimentary-product-of-a-complex-r6geq57jzt.pdf

Iron Formation: The Sedimentary Product of a Complex Interplay among Mantle, Tectonic, Oceanic, and Biospheric Processes

The reconstruction of oceanic paleoredox conditions on Earth is essential for investigating links between biospheric oxygenation and major periods of biological innovation and extinction, and for unravelling feedback mechanisms associated with paleoenvironmental change. The occurrence of anoxic, iron-rich (ferruginous) oceanic conditions often goes unrecognized, but refined techniques are currently providing evidence to suggest that ferruginous deep-ocean conditions were likely dominant throughout much of Earth's history. The prevalence of this redox state suggests that a detailed appraisal of the influence of ferruginous conditions on the evolution of biogeochemical cycles, climate, and the biosphere is increasingly required.

Ferruginous Conditions: A Dominant Feature of the Ocean through Earth's History

Calcareous nannofossils and Mesozoic oceanic anoxic events

[1] Mid-Cretaceous (Barremian-Turonian) plankton preserved in deep-sea marl, organic-rich shale, and pelagic carbonate hold an important record of how the marine biosphere responded to short- and long-term changes in the ocean-climate system. Oceanic anoxic events (OAEs) were short-lived episodes of organic carbon burial that are distinguished by their widespread distribution as discrete beds of black shale and/or pronounced carbon isotopic excursions. OAE1a in the early Aptian (∼120.5 Ma) and OAE2 at the Cenomanian/Turonian boundary (∼93.5 Ma) were global in their distribution and associated with heightened marine productivity. OAE1b spans the Aptian/Albian boundary (∼113–109 Ma) and represents a protracted interval of dysoxia with multiple discrete black shales across parts of Tethys (including Mexico), while OAE1d developed across eastern and western Tethys and in other locales during the latest Albian (∼99.5 Ma). Mineralized plankton experienced accelerated rates of speciation and extinction at or near the major Cretaceous OAEs, and strontium isotopic evidence suggests a possible link to times of rapid oceanic plateau formation and/or increased rates of ridge crest volcanism. Elevated levels of trace metals in OAE1a and OAE2 strata suggest that marine productivity may have been facilitated by increased availability of dissolved iron. The association of plankton turnover and carbon isotopic excursions with each of the major OAEs, despite the variable geographic distribution of black shale accumulation, points to widespread changes in the ocean-climate system. Ocean crust production and hydrothermal activity increased in the late Aptian. Faster spreading rates [and/or increased ridge length] drove a long-term (Albian–early Turonian) rise in sea level and CO2-induced global warming. Changes in ocean circulation, water column stratification, and nutrient partitioning lead to a reorganization of plankton community structure and widespread carbonate (chalk) deposition during the Late Cretaceous. We conclude that there were important linkages between submarine volcanism, plankton evolution, and the cycling of carbon through the marine biosphere.

Richard Cashman

Papers

Oceanic anoxic events and plankton evolution: Biotic response to tectonic forcing during the mid-Cretaceous