Carbonate Platform Growth and Cyclicity at a Terminal Proterozoic Passive Margin, Infra Krol Formation and Krol Group, Lesser Himalaya, India

The Infra Krol Formation and overlying Krol Group constitute a thick (less than 2 km), carbonate-rich succession of terminal Proterozoic age that crops out in a series of doubly plunging synclines in the Lesser Himalaya of northern India. The rocks include 18 carbonate and siliciclastic facies, which are grouped into eight facies associations: (1) deep subtidal; (2) shallow subtidal; (3) sand shoal; (4) peritidal carbonate complex; (5) lagoonal; (6) peritidal siliciclastic–carbonate; (7) incised valley fill; and (8) karstic fill. The stromatolite-rich, peritidal complex appears to have occupied a location seaward of a broad lagoon, an arrangement reminiscent of many Phanerozoic and Proterozoic platforms. Growth of this complex was accretionary to progradational, in response to changes in siliciclastic influx from the south-eastern side of the lagoon. Metre-scale cycles tend to be laterally discontinuous, and are interpreted as mainly autogenic. Variations in the number of both sets of cycles and component metre-scale cycles across the platform may result from differential subsidence of the interpreted passive margin. Apparently non-cyclic intervals with shallow-water features may indicate facies migration that was limited compared with the dimensions of facies belts. Correlation of these facies associations in a sequence stratigraphic framework suggests that the Infra Krol Formation and Krol Group represent a north- to north-west-facing platform with a morphology that evolved from a siliciclastic ramp, to carbonate ramp, to peritidal rimmed shelf and, finally, to open shelf. This interpretation differs significantly from the published scheme of a basin centred on the Lesser Himalaya, with virtually the entire Infra Krol–Krol succession representing sedimentation in a persistent tidal-flat environment. This study provides a detailed Neoproterozoic depositional history of northern India from rift basin to passive margin, and predicts that genetically related Neoproterozoic deposits, if they are present in the High Himalaya, are composed mainly of slope/basinal facies characterized by fine-grained siliciclastic and detrital carbonate rocks, lithologically different from those of the Lesser Himalaya

Chemostratigraphic Correlations Across the First Major Trilobite Extinction and Faunal Turnovers Between Laurentia and South China

During Cambrian Stage 4 (~514 Ma) the oceans were widely populated with endemic trilobites and three major faunas can be distinguished: olenellids, redlichiids, and paradoxidids. The lower–middle Cambrian boundary in Laurentia was based on the first major trilobite extinction event that is known as the Olenellid Biomere boundary. However, international correlation across this boundary (the Cambrian Series 2–Series 3 boundary) has been a challenge since the formal proposal of a four-series subdivision of the Cambrian System in 2005. Recently, the base of the international Cambrian Series 3 and of Stage 5 has been named as the base of the Miaolingian Series and Wuliuan Stage. This study provides detailed chemostratigraphy coupled with biostratigraphy and sequence stratigraphy across this critical boundary interval based on eight sections in North America and South China. Our results show robust isotopic evidence associated with major faunal turnovers across the Cambrian Series 2–Series 3 boundary in both Laurentia and South China. While the olenellid extinction event in Laurentia and the gradual extinction of redlichiids in South China are linked by an abrupt negative carbonate carbon excursion, the first appearance datum of Oryctocephalus indicus is currently the best horizon to achieve correlation between the two regions

Perspectives on Proterozoic surface ocean redox from iodine contents in ancient and recent carbonate

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 463 (2017): 159-170, doi:10.1016/j.epsl.2017.01.032.The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today’s, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.TL, ZL, and DH thank NSF EAR-1349252. ZL further thanks OCE-1232620. DH, ZL, and TL acknowledge further funding from a NASA Early Career Collaboration Award. TL, AB, NP, DH, and AK thank the NASA Astrobiology Institute. TL and NP received support from the Earth-Life Transitions Program of the NSF. AB acknowledges support from NSF grant EAR-05-45484 and an NSERC Discovery and Accelerator Grants. CW acknowledges support from NSFC grant 40972021

Subglacial Meltwater Supported Aerobic Marine Habitats During Snowball Earth

The Earth’s most severe ice ages interrupted a crucial interval in eukaryotic evolution with widespread ice coverage during the Cryogenian Period (720 to 635 Ma). Aerobic eukaryotes must have survived the “Snowball Earth” glaciations, requiring the persistence of oxygenated marine habitats, yet evidence for these environments is lacking. We examine iron formations within globally distributed Cryogenian glacial successions to reconstruct the redox state of the synglacial oceans. Iron isotope ratios and cerium anomalies from a range of glaciomarine environments reveal pervasive anoxia in the ice-covered oceans but increasing oxidation with proximity to the ice shelf grounding line. We propose that the outwash of subglacial meltwater supplied oxygen to the synglacial oceans, creating glaciomarine oxygen oases. The confluence of oxygen-rich meltwater and iron-rich seawater may have provided sufficient energy to sustain chemosynthetic communities. These processes could have supplied the requisite oxygen and organic carbon source for the survival of early animals and other eukaryotic heterotrophs through these extreme glaciations

Stable Isotopic Evidence for Methane Seeps in Neoproterozoic Postglacial Cap Carbonates

The Earth's most severe glaciations are thought to have occurred about 600 million years ago, in the late Neoproterozoic era. A puzzling feature of glacial deposits from this interval is that they are overlain by 1–5-m-thick 'cap carbonates' (particulate deep-water marine carbonate rocks) associated with a prominent negative carbon isotope excursion. Cap carbonates have been controversially ascribed to the aftermath of almost complete shutdown of the ocean ecosystems for millions of years during such ice ages—the 'snowball Earth' hypothesis. Conversely, it has also been suggested that these carbonate rocks were the result of destabilization of methane hydrates during deglaciation and concomitant flooding of continental shelves and interior basins. The most compelling criticism of the latter 'methane hydrate' hypothesis has been the apparent lack of extreme isotopic variation in cap carbonates inferred locally to be associated with methane seeps. Here we report carbon isotopic and petrographic data from a Neoproterozoic postglacial cap carbonate in south China that provide direct evidence for methane-influenced processes during deglaciation. This evidence lends strong support to the hypothesis that methane hydrate destabilization contributed to the enigmatic cap carbonate deposition and strongly negative carbon isotopic anomalies following Neoproterozoic ice ages. This explanation requires less extreme environmental disturbance than that implied by the snowball Earth hypothesis

Uranium and molybdenum isotope evidence for an episode of widespread ocean oxygenation during the late Ediacaran Period

The final publication is available at Elsevier via https://doi.org/10.1016/j.gca.2015.02.025 © 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/To improve estimates of the extent of ocean oxygenation during the late Ediacaran Period, we measured the U and Mo isotope compositions of euxinic (anoxic and sulfidic) organic-rich mudrocks (ORM) of Member IV, upper Doushantuo Formation, South China. The average d238U of most samples is 0.24 ± 0.16& (2SD; relative to standard CRM145), which is slightly higher than the average d238U of 0.02 ± 0.12& for restricted Black Sea (deep-water Unit I) euxinic sediments and is similar to a modeled d238U value of 0.2& for open ocean euxinic sediments in the modern well-oxygenated oceans. Because 238U is preferentially removed to euxinic sediments compared to 235U, expanded ocean anoxia will deplete seawater of 238U relative to 235U, ultimately leading to deposition of ORM with low d238U. Hence, the high d238U of Member IV ORM points to a common occurrence of extensive ocean oxygenation ca. 560 to 551 Myr ago. The Mo isotope composition of sediments deposited from strongly euxinic bottom waters ([H2S]aq >11 lM) either directly records the global seawater Mo isotope composition (if Mo removal from deep waters is quantitative) or represents a minimum value for seawater (if Mo removal is not quantitative). Near the top of Member IV, d98Mo approaches the modern seawater value of 2.34 ± 0.10&. High d98Mo points to widespread ocean oxygenation because the preferential removal of isotopically light Mo to sediments occurs to a greater extent in O2-rich compared to O2-deficient marine environments. However, the d98Mo value for most Member IV ORM is near 0&(relative to standard NIST SRM 3134 = 0.25&), suggesting extensive anoxia. The low d98Mo is at odds with the high Mo concentrations of Member IV ORM, which suggest a large seawater Mo inventory in well-oxygenated oceans, and the high d238U. Hence, we propose that the low d98Mo of most Member IV ORM was fractionated from contemporaneous seawater. Possible mechanisms driving this isotope fractionation include: (1) inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater-like d98Mo signature in sediments or (2) delivery of isotopically light Mo to sediments via a particulate Fe–Mn oxyhydroxide shuttle. A compilation of Mo isotope data from euxinic ORM suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late Neoproterozoic and early Paleozoic time. Hence, Member IV does not capture irreversible deep ocean oxygenation. Instead, complex ocean redox variations likely marked the transition from O2-deficient Proterozoic oceans to widely oxygenated later Phanerozoic oceans.National Science Foundation NASA Astrobiology Institute Agouron Institute Natural Sciences and Engineering Research Council of Canada Discovery Gran

Paired carbonate-organic carbon and nitrogen isotope variations in Lower Mississippian strata of the southern Great Basin, western United States

© 2017 Elsevier B.V. The Early Mississippian K-O (Kinderhookian-Osagean) carbon isotope (δ13C) excursion or TICE (mid-Tournaisian carbon isotope excursion) is one of the most prominent positive δ13C excursions of the Phanerozoic. Recent studies raise uncertainties about the representative shape (single vs. double spikes) and magnitude of this δ13C excursion (3‰ to ≥ 6‰ in South China; ≥ 5.5‰ in Europe; and ≥ 7‰ in North America) and the 3‰ unidirectional increase in nitrogen isotopes across the δ13C excursion, which is unanticipated considering the amount of organic carbon burial required to form the δ13C excursion and the resultant oxygen increase and global cooling. To test if stratigraphic completeness and spatial isotope variations caused such uncertainties, we have conducted paired carbonate carbon (δ13Ccarb), organic carbon (δ13Corg) and nitrogen (δ15N) isotope analyses across the K-O interval in two well-exposed sections of the southern Great Basin, western United States. The two sections represent proximal shallow-water and distal deep-water depositional settings of a west-dipping carbonate ramp. In the distal ramp section where no exposure surface is present, both δ13Ccarb and δ13Corg show double spikes with peak δ13Ccarb values up to 7‰ and a negative shift down to 4‰ between the peaks. In the proximal shallower-water section where two karstic disconformities are observed, δ13Corg shows similar double spikes but δ13Ccarb displays only a single peak with the highest value of 5.5‰. The missing δ13Ccarb spike is likely caused by diagenetic alteration below a karstic disconformity that lowered δ13Ccarb but not δ13Corg values, resulting in smaller magnitude of the δ13Ccarb excursion. These features suggest that the 7‰ magnitude and double spikes are more representative of the K-O δ13C excursion in the southern Great Basin. The smaller magnitude of the K-O δ13Ccarb excursion in some sections of the Great Basin and the TICE in other sections globally may have overprinted with local environmental/diagenetic signal or resulted from stratigraphic hiatus/truncation, which needs to be clarified in future research. The δ15N across the K-O δ13C excursion in the distal ramp section is decoupled from δ13C, with the majority of δ15N values around 4 ± 1‰ that do not show any obvious temporal trend. In contrast, δ15N values in the shallow-water section is coupled with the K-O δ13C excursion, with a 3‰ positive shift from 4‰ to 7‰ at the rising limb of the δ13C excursion and a negative shift from 7‰ to 1–2‰ at the falling limb of the δ13C excursion. The δ15N trend from the distal ramp section is, in some extent, comparable with that documented from a section in South China, while the coupled δ13C–δ15N pattern in the proximal section seems better explain the potential redox change across a prominent δ13C excursion. Considering the sensitivity of δ15N to redox conditions of depositional environments, a more comprehensive δ15N study in a broader paleogeographic context is required to better understand the interactions between carbon and nitrogen cycles across the K-O interval—a critical transition from the mid-Paleozoic greenhouse clime to Late Paleozoic Ice Age (LPIA)

Sulfur isotope change across the Early Mississippian K–O (Kinderhookian–Osagean) δ\u3csup\u3e13\u3c/sup\u3eC excursion

© 2018 Paired carbonate associate sulfate (CAS) sulfur isotopes (δ34SCAS), pyrite sulfur isotopes (δ34SPY) and CAS oxygen isotopes (δ18OCAS) across the Early Mississippian K–O δ13C excursion are documented from two sections of a west-dipping carbonate ramp in the southern Great Basin, western U.S.A. A 4–6‰ positive δ34SCAS anomaly, accompanied by negative shifts in δ34SPY and δ18OCAS is found within the K–O δ13C excursion. In the section with a broader δ13C excursion, Δ34S (Δ34S=δ34SCAS–δ34SPY) increases from 15‰ to 45‰ and δ13Ccarb drops from 7‰ to 4‰ at the same stratigraphic interval. If this δ34SCAS anomaly represents a global phenomenon, the large magnitude (4–6‰) and short duration (shorter than that of δ13C) suggest an unusual pyrite burial event that expanded from sediments to the ocean water column. In this scenario, the areal and volumetric expansion of sulfate reduction and pyrite burial was likely triggered by abundantly available organic matter near the peak of the K–O δ13C excursion, during which organic carbon production and burial may have reached a maximum, thus substantially expanding the oxygen minimum zone (OMZ). Numerical simulations suggest that pyrite burial rates 2.5–5 times higher than that of the modern ocean followed by sulfide oxidation are required to produce the observed δ34SCAS anomaly in a sulfate-rich ([SO4] ≥28 mM) Early Mississippian ocean. Alternatively, the sulfur and CAS oxygen isotope anomalies may record local sulfur cycling in a foreland basin where changes in weathering input and bottom-water redox conditions in response to sea-level fall and cooling resulted in isotope changes. In both scenarios (either local or global), the integrated carbon, sulfur, and CAS-oxygen isotope data suggest a much more dynamic sulfur cycle across the K–O δ13C excursion than has been previously suggested