Daniel J. Condon

U-Pb zircon date from the Neoproterozoic Ghaub Formation, Namibia: Constraints on Marinoan glaciation

Dropstone-bearing glaciomarine sedimentary rocks of the Ghaub Formation within metamorphosed Neoproterozoic basinal strata (Swakop Group) in central Namibia contain interbedded mafic lava flows and thin felsic ash beds. U-Pb zircon geochronology of an ash layer constrains the deposition of the glaciomarine sediments to 635.5 ± 1.2 Ma, providing an age for what has been described as a “Marinoan-type” glaciation. In addition, this age provides a maximum limit for the proposed lower boundary of the terminal Proterozoic (Ediacaran) system and period. Combined with reliable age constraints from other Neoproterozoic glacial units—the ca. 713 Ma Gubrah Member (Oman) and the 580 Ma Gaskiers Formation (Newfoundland)—these data provide unequivocal evidence for at least three, temporally discrete, glacial episodes during Neoproterozoic time with interglacial periods, characterized by prolonged positive δ 13 C excursions, lasting at most ∼50– 80 m.y.

Fossil steroids record the appearance of Demospongiae during the Cryogenian period

The Neoproterozoic era (1,000–542 Myr ago) was an era of climatic extremes and biological evolutionary developments culminating in the emergence of animals (Metazoa) and new ecosystems. Here we show that abundant sedimentary 24-isopropylcholestanes, the hydrocarbon remains of C30 sterols produced by marine demosponges, record the presence of Metazoa in the geological record before the end of the Marinoan glaciation (∼635 Myr ago). These sterane biomarkers are abundant in all formations of the Huqf Supergroup, South Oman Salt Basin, and, based on a new high-precision geochronology, constitute a continuous 100-Myr-long chemical fossil record of demosponges through the terminal Neoproterozoic and into the Early Cambrian epoch. The demosponge steranes occur in strata that underlie the Marinoan cap carbonate (>635 Myr ago). They currently represent the oldest evidence for animals in the fossil record, and are evidence for animals pre-dating the termination of the Marinoan glaciation. This suggests that shallow shelf waters in some late Cryogenian ocean basins (>635 Myr ago) contained dissolved oxygen in concentrations sufficient to support basal metazoan life at least 100 Myr before the rapid diversification of bilaterians during the Cambrian explosion. Biomarker analysis has yet to reveal any convincing evidence for ancient sponges pre-dating the first globally extensive Neoproterozoic glacial episode (the Sturtian, ∼713 Myr ago in Oman).

238U/235U Systematics in Terrestrial Uranium-Bearing Minerals

A Better Date Uranium-lead (U-Pb) dating, which is one of the most commonly used methods of radiometric dating for old terrestrial materials, operates by comparing the ratio of trace levels of U with its nuclear decay product Pb. This dating method, and the similar Pb-Pb method, assumes that the ratio between the two most common U isotopes (238U and 235U) is constant. By accurately measuring the 238U/235U ratio in a suite of minerals representing a range of tectonic environments, Hiess et al. (p. 1610; see the Perspective by Stirling) demonstrate that this ratio is more variable than was previously thought. The variability does not reflect any systematic bias with time, location, or temperature—suggesting that ideally 238U/235U should be determined for every sample to calculate ages. In the absence of such data, a revised 238U/235U ratio for zircon minerals could significantly modify previous age estimates using U-Pb and Pb-Pb dating techniques. Highly variable uranium isotope ratios highlight the need for a revised approach to radiometric dating. The present-day 238U/235U ratio has fundamental implications for uranium-lead geochronology and cosmochronology. A value of 137.88 has previously been considered invariant and has been used without uncertainty to calculate terrestrial mineral ages. We report high-precision 238U/235U measurements for a suite of uranium-bearing minerals from 58 samples representing a diverse range of lithologies. This data set exhibits a range in 238U/235U values of >5 per mil, with no clear relation to any petrogenetic, secular, or regional trends. Variation between comagmatic minerals suggests that 238U/235U fractionation processes operate at magmatic temperatures. A mean 238U/235U value of 137.818 ± 0.045 (2σ) in zircon samples reflects the average uranium isotopic composition and variability of terrestrial zircon. This distribution is broadly representative of the average crustal and “bulk Earth” 238U/235U composition.

Geochronologic constraints on the chronostratigraphic framework of the Neoproterozoic Huqf Supergroup, Sultanate of Oman

The Huqf Supergroup, Sultanate of Oman, contains an important record of Neoproterozoic history, including evidence for two glaciations, a massive reorganization of the global carbon cycle, and the Ediacaran-Cambrian transition. New U-Pb geochronologic data provide precise constraints on the age of several key stratigraphic levels in the Neoproterozoic Huqf Supergroup and its subjacent crystalline basement rocks. The basement ages constrain an interval of felsic magmatism to have occurred from at least 840 Ma to approximately 810 Ma. Detrital zircons from several stratigraphic levels within the Huqf Supergroup yield ages in excess of 2.5 Ga, suggesting proximity of Archean crust during the Neoproterozoic evolution of the eastern Arabian Peninsula. Volcanic ash beds intercalated within the Huqf Supergroup were dated in the Oman Mountains, and in several subsurface wells (South Oman Salt Basin). Glacial deposits of the Abu Mahara Group in the Oman Mountains (Ghubrah Formation) contain volcaniclastic rocks that are approximately 713 Ma; overlying syn-glacial turbiditic sandstones of the Fiq Formation yield a suite of detrital zircon dates ranging from 920 to 664 Ma so that deposition of at least the upper Fiq must have post-dated 664 Ma. In the South Oman Salt Basin, volcaniclastic deposits intercalated within glaciogenic strata of the Fiq Formation yielded zircons, the youngest of which is about 645 Ma. These data indicate two distinct episodes of glaciation at approximately 713 and <645 Ma. The uppermost Ara Group of the Huqf Supergoup contains multiple ash beds within its carbonate strata, where an age of roughly 547 Ma is reported for rocks that occur above strata marked by a pronounced negative (-12‰) to positive (+4‰) excursion in carbon isotope composition. Higher in the Ara sequence, three distinct ash beds dated at about 543 Ma, 542 Ma, and 541 Ma closely approximate the Ediacaran-Cambrian boundary in Oman. The dramatic carbon isotope excursion of ∼16 permil in the Shuram Formation (middle Nafun Group) has a firm maximum age of approximately 620 Ma as provided by detrital zircon ages from the base of the formation. Interpolation and downward extrapolation from the Ara Group ages, coupled with correlation to other global strata, suggests the base of the Shuram C-isotope excursion to be on the order of 560 Ma, with an estimated duration of approximately 5 to 11 m.y. This excursion is inferred to post-date the last well-documented Neoproterozoic glaciation (about 582 Ma) and is broadly coincident with the appearance of complex organisms in the fossil record.

Intercalibration of radioisotopic and astrochronologic time scales for the Cenomanian-Turonian boundary interval, Western Interior Basin, USA

We develop an intercalibrated astrochronologic and radioisotopic time scale for the Cenomanian-Turonian boundary (CTB) interval near the Global Stratotype Section and Point in Colorado, USA, where orbitally influenced rhythmic strata host bentonites that contain sanidine and zircon suitable for 40Ar/39Ar and U-Pb dating. Paired 40Ar/39Ar and U-Pb ages are determined from four bentonites that span the Vascoceras diartianum to Pseudaspidoceras flexuosum ammonite biozones, utilizing both newly collected material and legacy sanidine samples of J. Obradovich. Comparison of the 40Ar/39Ar and U-Pb results underscores the strengths and limitations of each system, and supports an astronomically calibrated Fish Canyon sanidine standard age of 28.201 Ma. The radioisotopic data and published astrochronology are employed to develop a new CTB time scale, using two statistical approaches: (1) a simple integration that yields a CTB age of 93.89 ± 0.14 Ma (2σ; total radioisotopic uncertainty), and (2) a Bayesian intercalibration that explicitly accounts for orbital time scale uncertainty, and yields a CTB age of 93.90 ± 0.15 Ma (95% credible interval; total radioisotopic and orbital time scale uncertainty). Both approaches firmly anchor the floating orbital time scale, and the Bayesian technique yields astronomically recalibrated radioisotopic ages for individual bentonites, with analytical uncertainties at the permil level of resolution, and total uncertainties below 2‰. Using our new results, the duration between the Cenomanian-Turonian and the Cretaceous-Paleogene boundaries is 27.94 ± 0.16 Ma, with an uncertainty of less than one-half of a long eccentricity cycle.

Temporal constraints on the Paleoproterozoic Lomagundi-Jatuli carbon isotopic event

The Paleoproterozoic Lomagundi-Jatuli positive 13C excursion in sedimentary carbonates represents an event whose magnitude and duration is unique in Earth history, although precise absolute chronology of this event remains poorly constrained. In northeastern Fennoscandia, an 1300-m-thick sedimentary-volcanic succession of the Pechenga Greenstone Belt records decline of this isotopic excursion. Zircons from sedimentary rocks that occur within the decline have yielded 207Pb/206Pb dates at 2058 ± 2 Ma (±6 Ma including U decay constant uncertainties) and provide the first maximum age constraint on the termination of the Lomagundi-Jatuli event. Combined with existing constraints, these data indicate an 140 m.y. interval characterized by 13C-rich carbonate accumulation.

Constraints on the numerical age of the Paleocene‐Eocene boundary

Here we present combined radio-isotopic dating (U-Pb zircon) and cyclostratigraphic analysis of the carbon isotope excursion at the Paleocene/Eocene (P/E) boundary in Spitsbergen, to determine the numerical age of the boundary. Incorporating the total uncertainty from both radio-isotopic and cyclostratigraphic datasets gives an age ranging from 55.728-55.964 Ma, within error of a recently proposed astronomical age of ~55.93 Ma. Combined with the assumption that the Paleocene Epoch spans twenty-five 405 kyr cycles, our new age for the boundary suggests an age of ~66 Ma for the Cretaceous/Paleogene (K/Pg) boundary. Furthermore, our P/E boundary age is consistent with the hypothesis that the onset of the Paleocene-Eocene thermal maximum (PETM) at the boundary occurred on the falling limb of a 405 kyr cycle, suggesting the event was initiated by a different mechanism to that which triggered the other early Eocene hyperthermals.

Integrating 40Ar/39Ar, U-Pb, and astronomical clocks in the Cretaceous Niobrara Formation, Western Interior Basin, USA

This study revises and improves the chronostratigraphic framework for late Turonian through early Campanian time based on work in the Western Interior U.S. and introduces new methods to better quantify uncertainties associated with the development of such time scales. Building on the unique attributes of the Western Interior Basin, which contains abundant volcanic ash beds and rhythmic strata interpreted to record orbital cycles, we integrate new radioisotopic data of improved accuracy with a recently published astrochronologic framework for the Niobrara Formation. New 40Ar/39Ar laser fusion ages corresponding to eight different ammonite biozones are determined by analysis of legacy samples, as well as newly collected material. These results are complemented by new U-Pb (zircon) chemical abrasion–isotope dilution–thermal ionization mass spectrometry ages from four biozones in the study interval. When combined with published radioisotopic data from the Cenomanian-Turonian boundary, paired 206Pb/238U and 40Ar/39Ar ages spanning Cenomanian to Campanian time support an astronomically calibrated Fish Canyon sanidine standard age of 28.201 Ma. Stage boundary ages are estimated via integration of new radioisotopic data with the floating astrochronology for the Niobrara Formation. The ages are determined by anchoring the long eccentricity bandpass from spectral analysis of the Niobrara Formation to radioisotopic ages with the lowest uncertainty proximal to the boundary, and adding or subtracting time by parsing the 405 k.y. cycles. The new stage boundary age determinations are: 89.75 ± 0.38 Ma for the Turonian-Coniacian, 86.49 ± 0.44 Ma for the Coniacian-Santonian, and 84.19 ± 0.38 Ma for the Santonian-Campanian boundary. The 2σ uncertainties for these estimates include systematic contributions from the radioisotopic measurements, astrochronologic methods, and geologic uncertainties (related to stratigraphic correlation and the presence of hiatuses). The latter geologic uncertainties have not been directly addressed in prior time scale studies and their determination was made possible by critical biostratigraphic observations. Each methodological approach employed in this study—new radioisotopic analysis, stratigraphic correlation, astrochronology, and ammonite and inoceramid biostratigraphy—was critical for achieving the final result.

Nature and timing of Late Mississippian to Mid-Pennsylvanian glacio-eustatic sea-level changes of the Pennine Basin, UK

The Pennine Basin of northern England contains a comparatively complete Serpukhovian– Moscovian succession characterized by high-resolution ammonoid zonation and cyclic paralic sedimentation. Two new isotope dilution thermal ionization mass spectrometry zircon ages from a bentonite deposited during the Arnsbergian (mid-Serpukhovian) regional substage and tonstein of earliest Bolsovian (early Moscovian) regional substage have been determined. The weighted mean 206Pb/238U ages of 328.34 ± 0.55 and 314.37 ± 0.53 Ma (total uncertainty), respectively, require modification of the time scale for the Western Europe regional chronostratigraphy. The areal extent of acme ammonoid facies is used as a proxy for the magnitude of 47 discrete flooding events. Incised valleys (major sequence boundaries) are used as a proxy for the magnitude of sea-level falls. The frequency of these events, in the light of the new radiometric dating, indicates the following: (1) there is temporal coincidence between major glaciations in Gondwana and phases of increased frequency of sequence boundaries in the Pennine Basin; (2) high-amplitude flooding surfaces have an average frequency of c. 400 ka; (3) average cycle durations during the Pendleian–early Arnsbergian and Chokierian–Bolsovian, of c. 111 and c. 150 ka, respectively, reflect short-duration eccentricities; (4) multiple flooding surfaces with the same ammonoid assemblages may equate with sub-100 ka precession or obliquity frequencies. Supplementary material: U–Pb method description and data, procedure for the calculation of the areal extent of marine bands, and tables showing a full listing of biostratigraphical data used in the study are available at www.geolsoc.org.uk/SUP18505.

Duration and nature of the end-Cryogenian (Marinoan) glaciation

The end-Cryogenian glaciation (Marinoan) is portrayed commonly as the archetype of snowball Earth, yet its duration and character remain uncertain. Here we report U-Pb zircon ages for two ash beds from widely separated localities of the Marinoan-equivalent Ghaub Formation in Namibia: 639.29 ± 0.26 Ma and 635.21 ± 0.59 Ma. These findings verify, for the first time, the key prediction of the snowball Earth hypothesis for the Marinoan glaciation, i.e., longevity, with a duration of ≥4 m.y. They also show that the nonglacial interlude of Cryogenian time spanned 20 m.y. or less and that glacigenic erosion and sedimentation, and at least intermittent open-water conditions, occurred 4 m.y. prior to termination of the Marinoan glaciation.