Timothy D. Raub

An Appalachian Amazon? Magnetofossil evidence for the development of a tropical river‐like system in the mid‐Atlantic United States during the Paleocene‐Eocene thermal maximum

On the mid-Atlantic Coastal Plain of the United States, Paleocene sands and silts are replaced during the Paleocene-Eocene Thermal Maximum (PETM) by the kaolinite-rich Marlboro Clay. The clay preserves abundant magnetite produced by magnetotactic bacteria and novel, presumptively eukaryotic, iron-biomineralizing microorganisms. Using ferromagnetic resonance spectroscopy and electron microscopy, we map the magnetofossil distribution in the context of stratigraphy and carbon isotope data and identify three magnetic facies in the clay: one characterized by a mix of detrital particles and magnetofossils, a second with a higher magnetofossil-to-detrital ratio, and a third with only transient magnetofossils. The distribution of these facies suggests that suboxic conditions promoting magnetofossil production and preservation occurred throughout inner middle neritic sediments of the Salisbury Embayment but extended only transiently to outer neritic sediments and the flanks of the embayment. Such a distribution is consistent with the development of a system resembling a modern tropical river-dominated shelf.

Gigantism in unique biogenic magnetite at the Paleocene–Eocene Thermal Maximum

We report the discovery of exceptionally large biogenic magnetite crystals in clay-rich sediments spanning the Paleocene–Eocene Thermal Maximum (PETM) in a borehole at Ancora, NJ. Aside from previously described abundant bacterial magnetofossils, electron microscopy reveals novel spearhead-like and spindle-like magnetite up to 4 μm long and hexaoctahedral prisms up to 1.4 μm long. Similar to magnetite produced by magnetotactic bacteria, these single-crystal particles exhibit chemical composition, lattice perfection, and oxygen isotopes consistent with an aquatic origin. Electron holography indicates single-domain magnetization despite their large crystal size. We suggest that the development of a thick suboxic zone with high iron bioavailability—a product of dramatic changes in weathering and sedimentation patterns driven by severe global warming—drove diversification of magnetite-forming organisms, likely including eukaryotes.

Globally synchronous marinoan deglaciation indicated by U-Pb geochronology of the cottons Breccia, Tasmania, Australia

U-Pb zircon data from the uppermost Cottons Breccia, representing the Marinoan glacial-postglacial transition on King Island, Tasmania, provide the first direct age constraint on the Cryogenian-Ediacaran boundary in Australia. Zircons in four samples from the topmost meter of the Cottons Breccia, dated by sensitive high-resolution ion microprobe, exhibit two modes ca. 660 Ma and ca. 635 Ma. The younger component predominates in the uppermost sample, a possibly volcanolithic dolomitic sandstone, apparently lacking glacially transported debris, in the transition to cap carbonate. Chemical abrasion–thermal ionization mass spectrometry (CA-TIMS) U-Pb dating of euhedral zircons from that sample yields a weighted-mean age of 636.41 ± 0.45 Ma. Equivalence to published TIMS ash bed dates from Cryogenian-Ediacaran transitional strata in Namibia (635.51 ± 0.82 Ma, within glacial deposit) and China (635.23 ± 0.84 Ma, 2 m above glacial deposit) supports correlation of those strata to the Australian type sections and globally synchronous deglaciation at the end of the Cryogenian Period.

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.

Proterozoic onset of crustal reworking and collisional tectonics: Reappraisal of the zircon oxygen isotope record

A global U-Pb and δ18O zircon database shows temporal changes in the magmatic record related to changes in the degree of crustal reworking. The δ18O composition of bulk sediment remains relatively constant through geologic time, with a mean value of 14.9‰. In contrast, the δ18O values in magmatic zircons vary from relatively low values averaging ∼6‰ in the Archean to increasingly higher and scattered values defining a series of peaks and troughs in post-Archean data. The degree of crustal reworking increases at times of supercontinent assembly. Therefore we attribute the pattern of post-Archean δ18O values recorded by magmatic zircons to a significant increase in the incorporation of high δ18O sediment in response to enhanced crustal thickening and reworking associated with the onset of collisional tectonics, especially during formation of supercontinents.

Zn isotope evidence for immediate resumption of primary productivity after snowball Earth

The Ediacaran period began with the deglaciation of the ca. 635 Ma Marinoan snowball Earth and the deposition of cap dolostones on continental shelves worldwide during post-glacial sea-level rise. These carbonates sharply overlie glacial sediments deposited at low paleolatitudes and preserve negative carbon isotope excursions. The snowball Earth hypothesis invokes an almost complete cessation of primary productivity in the surface ocean. Because assimilatory uptake of Zn appears to fractionate its isotopes, Zn isotope ratios measured in carbonate precipitated in the surface ocean should track fluctuations in primary productivity. Here we report the first Zn isotopic data, together with carbon and oxygen isotopic profiles from a Neoproterozoic cap dolostone, the Nuccaleena Formation in the Flinders Ranges, South Australia. We interpret the Zn isotopic data in terms of a two-stage evolution of the deglacial ocean. Slightly ^(66)Zn-enriched values at the base of the cap dolostone indicate immediate resumption of the biological pump upon melting of the surface ocean, but this signal was diluted by intense surface runoff that drove δ^(66)Zn (^(66)Zn/^(64)Zn, versus the JMC Lyon reference) values down to the composition of continentally derived Zn. A subsequent rise in δ^(66)Zn records a vigorous increase in primary production and export from a nutrient-laden surface ocean.

SQUID-SIMS is a useful approach to uncover primary signals in the Archean sulfur cycle

Significance A challenge to understanding ancient sulfur-cycle processes on early Earth is the persistent observation that postdepositional processes have affected all Archean-age rocks, impacting geochemical signals, and the quality of paleoenvironmental interpretations. To solve this problem we developed a combination of texture-specific microscale techniques—scanning high-resolution low-temperature superconducting quantum interference device microscopy and secondary ion mass spectrometry. We applied these techniques in a well-studied Archean-age sedimentary succession in South Africa to unravel the mineralization and isotopic history and reveal primary sulfur-cycle processes. We observed systematic patterns of isotope ratios at microscopic scales that inform the nature of enigmatic sulfur-isotope mass anomalies unique to this time interval and further support hypotheses for the early evolution of sulfate-reduction metabolisms. Many aspects of Earth’s early sulfur cycle, from the origin of mass-anomalous fractionations to the degree of biological participation, remain poorly understood—in part due to complications from postdepositional diagenetic and metamorphic processes. Using a combination of scanning high-resolution magnetic superconducting quantum interference device (SQUID) microscopy and secondary ion mass spectrometry (SIMS) of sulfur isotopes (32S, 33S, and 34S), we examined drill core samples from slope and basinal environments adjacent to a major Late Archean (∼2.6–2.5 Ga) marine carbonate platform from South Africa. Coupled with petrography, these techniques can untangle the complex history of mineralization in samples containing diverse sulfur-bearing phases. We focused on pyrite nodules, precipitated in shallow sediments. These textures record systematic spatial differences in both mass-dependent and mass-anomalous sulfur-isotopic composition over length scales of even a few hundred microns. Petrography and magnetic imaging demonstrate that mass-anomalous fractionations were acquired before burial and compaction, but also show evidence of postdepositional alteration 500 million y after deposition. Using magnetic imaging to screen for primary phases, we observed large spatial gradients in Δ33S (>4‰) in nodules, pointing to substantial environmental heterogeneity and dynamic mixing of sulfur pools on geologically rapid timescales. In other nodules, large systematic radial δ34S gradients (>20‰) were observed, from low values near their centers increasing to high values near their rims. These fractionations support hypotheses that microbial sulfate reduction was an important metabolism in organic-rich Archean environments—even in an Archean ocean basin dominated by iron chemistry.

Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

SUTTON HOTSPOT: RESOLVING EDIACARAN-CAMBRIAN TECTONICS AND TRUE POLAR WANDER FOR LAURENTIA

Hotspot tracks represent plate motions relative to mantle sources, and paleomagnetic data from magmatic units along those tracks can quantify motions of those mantle anomalies relative to the Earths magnetic field and rotational axis. The Ediacaran Period is notable for rapid and large paleomagnetic apparent polar wander (APW) for many continents. Whereas magmatic units attributed to the “Sutton” mantle plume suggest a practically stationary hotspot track, paleolatitudes of Laurentia for that interval vary dramatically; geologic and paleomagnetic data are at odds unless true polar wander (TPW) is invoked to explain a majority of APW. Here we test the plume-TPW hypothesis by generating the predicted Sutton hotspot track for a stationary plume under a moving plate along the Laurentian margin during the interval from 615 to 530 Ma. Our model is the first to provide a kinematic framework for the extensive large igneous province associated with opening the Iapetus Ocean.

Origin of giant wave ripples in snowball Earth cap carbonate

The most extreme climate transitions in Earth history are recorded by the juxtaposition of Neoproterozoic glacial deposits with overlying cap carbonate beds. Some of the most remarkable sedimentary structures within these beds are sharp-crested (trochoidal) bedforms with regular spacing of as much as several meters that are often interpreted as giant wave ripples formed under extreme wave conditions in a nonuniform postglacial climate. Here we evaluate this hypothesis using a new bedform stability diagram for symmetric oscillatory fl ows that indicates that the fi rst-order control on the formation of trochoidal rather than hummocky bedforms is sediment size, not wave climate. New measurements of bedform wavelengths and particle sizes from the ca. 635 Ma Nuccaleena Formation, Australia, indicate that the giant ripples are generally composed of coarse to very coarse sand; most are within the trochoidal bedform stability phase space for normal wave climates. Moreover, numerical simulations of flover fi xed bedforms show that symmetric trochoidal ripples with a nearly vertical angle of climb may be produced over long time periods with variable wave climates in conjunction with rapid seabed cementation. These data reveal that, rather than extreme wave conditions, the giant wave ripples are a consequence of the unusual mode of carbonate precipitation during a global carbon cycle perturbation unprecedented in Earth history.