Francis A. Macdonald

Calibrating the Cryogenian

Aging Snowball Earth Earths glacial cycles have varied dramatically over time; at one point glaciers may have covered nearly the entire planet. Correlating various paleoclimate proxies such as fossil and isotope records from that time hinges on the ability to acquire precise age estimates of rocks deposited around the time of this so-called “Snowball Earth.” Macdonald et al. (p. 1241) report new high-precision U-Pb dates of Neoproterozoic strata in the Yukon and Northwest Territories, Canada, to calibrate the timing of carbon isotope variation in rocks from other locations around the globe. Based on the estimated past positions of where these rocks were deposited, glaciers probably extended to equatorial latitudes. The overlap with the survival and, indeed, diversification of some eukaryotes in the fossil record suggests that life survived in localized ecological niches during this global glaciation. A volcanic tuff dated to 716.5 million years ago calibrates the timing of a global glaciation event and eukaryotic survival. The Neoproterozoic was an era of great environmental and biological change, but a paucity of direct and precise age constraints on strata from this time has prevented the complete integration of these records. We present four high-precision U-Pb ages for Neoproterozoic rocks in northwestern Canada that constrain large perturbations in the carbon cycle, a major diversification and depletion in the microfossil record, and the onset of the Sturtian glaciation. A volcanic tuff interbedded with Sturtian glacial deposits, dated at 716.5 million years ago, is synchronous with the age of the Franklin large igneous province and paleomagnetic poles that pin Laurentia to an equatorial position. Ice was therefore grounded below sea level at very low paleolatitudes, which implies that the Sturtian glaciation was global in extent.

Authigenic Carbonate and the History of the Global Carbon Cycle

The Third Way Because organic carbon contains a larger fraction of the light isotope 12C than inorganic carbonate, variations in the carbon isotopic record of sedimentary rocks are thought to represent changes in the amount of organic carbon buried as sediments (and thus removed from the rest of the carbon cycle). Schrag et al. (p. 540; see the Perspective by Canfield and Kump) suggest that historically a third component was important: authigenic carbonate. Authigenic carbonate is not produced in any appreciable quantity today, but was much more abundant when the level of atmospheric oxygen was low. Carbonate produced in sediment pore fluids played a major role in the carbon cycle in the geological past. [Also see Perspective by Canfield and Kump] We present a framework for interpreting the carbon isotopic composition of sedimentary rocks, which in turn requires a fundamental reinterpretation of the carbon cycle and redox budgets over Earths history. We propose that authigenic carbonate, produced in sediment pore fluids during early diagenesis, has played a major role in the carbon cycle in the past. This sink constitutes a minor component of the carbon isotope mass balance under the modern, high levels of atmospheric oxygen but was much larger in times of low atmospheric O2 or widespread marine anoxia. Waxing and waning of a global authigenic carbonate sink helps to explain extreme carbon isotope variations in the Proterozoic, Paleozoic, and Triassic.

Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation.

Sedimentary rocks deposited across the Proterozoic–Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.

A Cryogenian chronology: Two long-lasting synchronous Neoproterozoic glaciations

The snowball Earth hypothesis predicts globally synchronous glaciations that persisted on a multimillion year time scale. Geochronological tests of this hypothesis have been limited by a dearth of reliable age constraints bracketing these events on multiple cratons. Here we present four new Re-Os geochronology age constraints on Sturtian (717–660 Ma) and Marinoan (635 Ma termination) glacial deposits from three different paleocontinents. A 752.7 ± 5.5 Ma age from the base of the Callison Lake Formation in Yukon, Canada, confirms nonglacial sedimentation on the western margin of Laurentia between ca. 753 and 717 Ma. Coupled with a new 727.3 ± 4.9 Ma age directly below the glacigenic deposits of the Grand Conglomerate on the Congo craton (Africa), these data refute the notion of a global ca. 740 Ma Kaigas glaciation. A 659.0 ± 4.5 Ma age directly above the Maikhan-Uul diamictite in Mongolia confirms previous constraints on a long duration for the 717–660 Ma Sturtian glacial epoch and a relatively short nonglacial interlude. In addition, we provide the first direct radiometric age constraint for the termination of the Marinoan glaciation in Laurentia with an age of 632.3 ± 5.9 Ma from the basal Sheepbed Formation of northwest Canada, which is identical, within uncertainty, to U-Pb zircon ages from China, Australia, and Namibia. Together, these data unite Re-Os and U-Pb geochronological constraints and provide a refined temporal framework for Cryogenian Earth history.

Re-Os geochronology and coupled Os-Sr isotope constraints on the Sturtian snowball Earth

Significance The causal mechanisms of global glaciations are poorly understood. The transition to a Neoproterozoic Snowball Earth after more than 1 Gy without glaciation represents the most dramatic episode of climate change in the geological record. Here we present new Re-Os geochronology, which, together with existing U-Pb ages, reveal that the glacial period in northwest Canada lasted ∼55 My. Additionally, we present an original method to track tectonic influences on these climatic perturbations with a high-resolution coupled Os-Sr isotope curve across the transition from an ice-free world to a Neoproterozoic Snowball Earth. The data indicate that increases in mantle-derived, juvenile material emplaced onto continents and subsequently weathered into the oceans led to enhanced consumption and sequestration of CO2 into sediments. After nearly a billion years with no evidence for glaciation, ice advanced to equatorial latitudes at least twice between 717 and 635 Mya. Although the initiation mechanism of these Neoproterozoic Snowball Earth events has remained a mystery, the broad synchronicity of rifting of the supercontinent Rodinia, the emplacement of large igneous provinces at low latitude, and the onset of the Sturtian glaciation has suggested a tectonic forcing. We present unique Re-Os geochronology and high-resolution Os and Sr isotope profiles bracketing Sturtian-age glacial deposits of the Rapitan Group in northwest Canada. Coupled with existing U-Pb dates, the postglacial Re-Os date of 662.4 ± 3.9 Mya represents direct geochronological constraints for both the onset and demise of a Cryogenian glaciation from the same continental margin and suggests a 55-My duration of the Sturtian glacial epoch. The Os and Sr isotope data allow us to assess the relative weathering input of old radiogenic crust and more juvenile, mantle-derived substrate. The preglacial isotopic signals are consistent with an enhanced contribution of juvenile material to the oceans and glacial initiation through enhanced global weatherability. In contrast, postglacial strata feature radiogenic Os and Sr isotope compositions indicative of extensive glacial scouring of the continents and intense silicate weathering in a post–Snowball Earth hothouse.

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10–100 million years) characterized by δ13C in carbonate (δ13Ccarb) enriched to more than +5 per mil. Classically, δ13Ccarb is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ13Ccarb and δ13C in organic carbon (δ13Corg) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ13Ccarb excursions that are decoupled from δ13Corg, however, indicates that other mechanisms may account for these excursions. Here we present δ13C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ13Ccarb excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ13Ccarb anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.

Stratigraphic and tectonic implications of a newly discovered glacial diamictite–cap carbonate couplet in southwestern Mongolia

We report here the discovery of a new end-Cryogenian glacial diamictite and an overlying basal Ediacaran cap carbonate within the Tsagaan Oloom Formation of southwestern Mongolia. The identifi cation of the Cryogenian-Ediacaran boundary, coupled with new δ 13 C chemostratigraphic profi les, facilitates the integration of the Neoproterozoic stratigraphy of Mongolia with records elsewhere. These correlations indicate that a previously unrecognized, ‐16‰ Cryogenian δ 13 C anomaly is present in the newly defi ned Tayshir member (informal) of the Tsagaan Oloom Formation. Furthermore, chemostratigraphic and lithostratigraphic relationships suggest an ~35 m.y. depositional hiatus below the phosphorite-bearing Zunne Arts member (informal) of the upper Tsagaan Oloom Formation and that subsidence renewed in the latest Ediacaran‐Early Cambrian. We propose that the lower ~1500 m of the Tsagaan Oloom Formation was deposited on a thermally subsiding passive margin after Rodiniaage rifting, whereas the Zunne Arts member and the overlying ~1600 m of Early Cambrian strata were deposited in a foredeep basin that formed as the southern margin of the Dzabkhan terrane was subducted beneath the Khantayshir-Dariv arc.

Phosphate biomineralization in mid-Neoproterozoic protists

The origin and expansion of biomineralization in eukaryotes played a critical role in Earth history, linking biological and geochemical processes. However, the onset of this phenomenon is poorly constrained due to a limited early fossil record of biomineralization. Although macroscopic evidence for biomineralization is not known until the late Ediacaran, we here report biologically controlled phosphatic biomineralization of scale microfossils from mid-Neoproterozoic (pre-Sturtian) strata of northwest Canada. Primary biological control on mineralization is supported by the identification of apatite in both chert-hosted and limestone-hosted specimens, the conspicuously rigid original morphology of the scale microfossils relative to co-occurring organic-walled cyanobacteria and acritarchs, and the microstructure of the constituent phosphate. Cell-enveloping mineralized scales occur in a wide range of extant protists, but the apparent restriction of phosphate scales to one modern taxon of green algae suggests a possible affiliation for these fossils. Documentation of primary phosphate biomineralization in Fifteenmile Group (Yukon Territory, Canada) microfossils greatly extends the known record of biologically controlled mineralization and provides a unique window into the diversity of early eukaryotes.

Dodging snowballs: Geochronology of the Gaskiers glaciation and the first appearance of the Ediacaran biota

The snowball Earth hypothesis predicts that low-latitude glaciation lasted millions of years while CO2 built up to critical levels to culminate in catastrophic deglaciation in a supergreenhouse climate. The Gaskiers Formation of eastern Newfoundland (Canada) has been attributed to a snowball glaciation event, but the lack of robust paleomagnetic data and precise geochronological constraints has precluded tests of the hypothesis. Here we present high-precision U-Pb zircon geochronology (chemical abrasion–isotope dilution–thermal ionization mass spectrometry) from eight tuffs from multiple distant stratigraphic sections that bracket glacial diamictites and the first appearance of large Ediacaran fossils. Including internal error, deposition of the Gaskiers diamictite on the Avalon Peninsula is constrained to have been between 580.90 ± 0.40 and 579.88 ± 0.44 Ma, and the Trinity diamictite on Bonavista Peninsula was deposited between 579.63 ± 0.15 and 579.24 ± 0.17 Ma. Assuming approximately synchronous deglaciation, these results imply a maximum duration for deposition of the Trinity diamictite of ≤340 k.y.; this is inconsistent with the multimillion year duration predicted by the snowball Earth hypothesis. Our geochronologic data also constrain the first appearance datum of Ediacaran fossils to <9.5 m.y. after the Gaskiers glaciation. Thus, despite existing paleomagnetic constraints that indicate that marine ice sheets extended to low to middle latitudes, it appears that Earth narrowly escaped a third Neoproterozoic snowball glaciation just prior to the late Ediacaran expansion of metazoan ecosystems.

Neoproterozoic glaciation on a carbonate platform margin in Arctic Alaska and the origin of the North Slope subterrane

The rotation model for the opening of the Canada Basin of the Arctic Ocean predicts stratigraphic links between the Alaskan North Slope and the Canadian Arctic islands. The Katakturuk Dolomite is a 2080-m-thick Neo protero zoic carbonate succession exposed in the northeastern Brooks Range of Arctic Alaska. These strata have previously been correlated with the pre– 723 Ma Shaler Supergroup of the Amundson Basin. Herein we report new composite δ 13 C profi les and detrital zircon ages that test this connection. We go further and use stratigraphic markers and a compilation of δ 13 C chemostratigraphy from around the world, tied to U-Pb ages, to derive an age model for deposition of the Katakturuk Dolomite. In particular, we report the identifi cation of ca. 760 Ma detrital zircons in strata underlying the Katakturuk Dolomite. Moreover, a diamictite present at the base of the Katakturuk Dolomite is capped by a dark-colored limestone with peculiar roll-up structures. Chemostratigraphy and lithostratigraphy suggest this is an earlyCryogenian glacial diamictite-cap carbonate couplet and that deposition of the Katakturuk Dolomite spanned much of the late Neoproterozoic. Approximately 500 m above the diamictite, a micropeloidal dolomite, with idiosyncratic textures that are characteristic of basal Ediacaran cap carbonates, such as tubestone stromatolites, giant wave ripples, and decameters of pseudo morphosed former aragonite crystal fans, rests on a silicifi ed surface. Chemostratigraphic correlations also indicate a large increase in sedimentation rate in the upper ~1 km of the Katakturuk Dolomite and in the overlying lower Nanook Limestone. We suggest that the accompanying increase in accommodation space, along with the presence of two low-angle unconformities within these strata, are the product of late Ediacaran rifting along the southern margin of the North Slope subterrane. There are no strata present in the Amundson Basin that are potentially correlative with the late Neoproterozoic Katakturuk Dolomite, as the Cambrian Saline River Formation rests on the ca. 723 Ma Natkusiak Formation. Detrital zircon geochronology, chemostratigraphic correlations, and the style of sedimentation are inconsistent with both a Canadian Arctic origin of the North Slope subterrane and a simple rotation model for the origin of the Arctic Ocean. If the rotation model is to be retained, the exotic North Slope subterrane must have accreted to northwest Laurentia in the Early to Middle Devonian.