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Framboidal pyrite shroud confirms the ‘death mask' model for moldic preservation of ediacaran soft-bodied organisms—a reply
No full textThin, laterally extensive veneers of framboidal pyrite on fossiliferous bedding planes in eastern Newfoundland, Canada, provide evidence for post-burial microbially mediated pyritization of the seafloor in the late Ediacaran Period (Liu 2016). Pyrite is inferred to have formed on the external surfaces of soft-bodied organisms and microbial matgrounds as a result of bacterial sulfate reduction, consistent with the ‘death mask' taphonomic model for Ediacaran moldic preservation (Gehling 1999). Retallack (2017) accepts the evidence presented by Liu (2016) for early diagenetic pyritization of bedding planes in Newfoundland, and seems to offer at least tacit acceptance of evidence for modern oxidation of that pyrite, its widespread occurrence in global Ediacaran localities, and the potential influence of sedimentary pyrite burial on global Ediacaran oxygen concentrations. However, Retallack questions whether the presence of such pyrite veneers can be taken to demonstrate the ‘death mask' taphonomic model, and specifically queries the source of the observed pyrite
Diversity and abundance of microbial eukaryotes in stream sediments from Svalbard
No full textMicrobial eukaryotes are increasingly being recognised for their role in global biogeochemical cycles, yet very few studies have focussed on their distribution in high-latitude stream sediments, an important habitat which influences stream water nutrient chemistry. In this study, we present the first comparison of microbial eukaryotes from two different polar habitats by determining the abundance and taxonomic affiliation of 18S rRNA gene fragments recovered from four sediment samples in Svalbard: two from a glaciated catchment and two from an unglaciated permafrost-dominated catchment. Whilst there was no difference between the two catchments in terms of Rao’s phylogenetic diversity (0.18±0.04, 1SD), the glaciated catchment samples had slightly higher richness (138–139) than the unglaciated catchment samples (67–106). At the phylum level, Ciliophora had the highest relative abundance in the samples from the glaciated catchment (32–63%), but only comprised 0–17% of the unglaciated catchment samples. Bacillariophyta was the most abundant phylum in one of the samples from the unglaciated catchment (43%) but phototrophic microbial eukaryotes only formed a minor component of the glaciated catchment samples (<2%), suggesting that in these environments the microbial eukaryotes are predominantly heterotrophic (chemotrophic). This is in contrast to previously published data from Robertson Glacier, Canada where the relative abundance of chlorophyta (phototrophs) in three samples was 48–57%. The contrast may be due to differences in glacial hydrology and/or geology, highlighting the variation in microbial eukaryote communities between nominally similar environments
Investigating the effects of growth rate and temperature on the B/Ca ratio and δ11B during inorganic calcite formation
No full textTo deconvolve the effect of growth rate and temperature on the boron partitioning into calcite and its isotope fractionation, seeded calcite precipitation experiments were performed at a constant temperature and various growth rates and at a constant growth rate and various temperatures. We show that boron partitioning increases with increasing growth rate and decreases with increasing temperature. The B isotope fractionation between calcite and B(OH)4− increases with increasing growth rate favoring the lighter B isotope for incorporation into calcite whereas no effect of temperature was observed within the temperature range investigated (12 °C to 32 °C). At the lowest temperature and growth rate δ11B of the calcite almost equals that of B(OH)4− in solution. Applying the surface entrapment model (SEMO) of Watson and Liang (1995) to our data, we demonstrate that the observed effects of temperature and growth rate on B concentration can be explained by processes in the near surface layer of the calcite crystal
Microbial sulfur metabolism evidenced from pore fluid isotope geochemistry at Site U1385
No full textAt Site U1385, drilled during IODP Expedition 339 off the coast of Portugal on the continental slope, high-resolution sulfate concentration measurements in the pore fluids display non-steady-state behavior. At this site there is a zone of sulfate reduction in the uppermost seven meters of sediment, followed by a 38-meter interval where sulfate concentrations do not change, and finally sulfate concentrations are depleted to zero between 45 and 55 meters below seafloor. Below the sulfate minimum zone, there is abundant methane, suggesting that the lower sulfate consumption zone is coupled to anaerobic methane oxidation. We analyze pore water samples from IODP Site U1385 for sulfur and oxygen isotope ratios of dissolved sulfate, as well as the sulfur isotope composition of sedimentary pyrite. The sulfur isotopes in pore fluid sulfate display similar non-steady-state behavior similar to that of the sulfate concentrations, increasing over the uppermost zone of sulfate reduction and again over the lower zone of sulfate-driven anaerobic methane oxidation. The oxygen isotopes in sulfate increase to the 'apparent equilibrium' value in the uppermost zone of sulfate reduction and do not change further. Our calculations support the idea that sulfite to sulfide reduction is the limiting step in microbial sulfate reduction, and that the isotope fractionation expressed in the residual pore water sulfate pool is inversely proportional to the net sulfate reduction rate. The sulfur isotope composition of pyrite acquires one value in the uppermost sediments, which may be overprinted by a second value in the deeper sediments, possibly due to iron release during anaerobic methane oxidation or iron diffusion from a higher zone of bacterial iron reduction. Our results have implications for modeling the sulfur isotope composition of the pyrite burial flux in the global biogeochemical sulfur cycle
On the use of sensitivity tests in seismic tomography
No full textSensitivity analysis with synthetic models is widely used in seismic tomography as a means for assessing the spatial resolution of solutions produced by, in most cases, linear or iterative nonlinear inversion schemes. The most common type of synthetic reconstruction test is the so-called checkerboard resolution test in which the synthetic model comprises an alternating pattern of higher and lower wave speed (or some other seismic property such as attenuation) in 2-D or 3-D. Although originally introduced for application to large inverse problems for which formal resolution and covariance could not be computed, these tests have achieved popularity, even when resolution and covariance can be computed, by virtue of being simple to implement and providing rapid and intuitive insight into the reliability of the recovered model. However, checkerboard tests have a number of potential drawbacks, including (1) only providing indirect evidence of quantitative measures of reliability such as resolution and uncertainty, (2) giving a potentially misleading impression of the range of scale-lengths that can be resolved, and (3) not giving a true picture of the structural distortion or smearing that can be caused by the data coverage. The widespread use of synthetic reconstruction tests in seismic tomography is likely to continue for some time yet, so it is important to implement best practice where possible. The goal of this paper is to develop the underlying theory and carry out a series of numerical experiments in order to establish best practice and identify some common pitfalls. Based on our findings, we recommend (1) the use of a discrete spike test involving a sparse distribution of spikes, rather than the use of the conventional tightly spaced checkerboard; (2) using data coverage (e.g. ray-path geometry) inherited from the model constrained by the observations (i.e. the same forward operator or matrix), rather than the data coverage obtained by solving the forward problem through the synthetic model; (3) carrying out multiple tests using structures of different scale length; (4) taking special care with regard to what can be inferred when using synthetic structures that closely mimic what has been recovered in the observation-based model; (5) investigating the range of structural wavelengths that can be recovered using realistic levels of imposed data noise; and (6) where feasible, assessing the influence of model parametrization error, which arises from making a choice as to how structure is to be represented. © The Authors 2016. Published by Oxford University Press on behalf of The Royal Astronomical Society
First-principles reinvestigation of bulk WO3
No full textUsing first-principles calculations, we analyze the structural properties of tungsten trioxide WO3. Our calculations rely on density functional theory and the use of the B1-WC hybrid functional, which provides very good agreement with experimental data. We show that the hypothetical high-symmetry cubic reference structure combines several ferroelectric and antiferrodistortive (antipolar cation motions, rotations, and tilts of oxygen octahedra) structural instabilities. Although the ferroelectric instability is the largest, the instability related to antipolar W motions combines with those associated to oxygen rotations and tilts to produce the biggest energy reduction, yielding a P21/c ground state. This nonpolar P21/c phase is only different from the experimentally reported Pc ground state by the absence of a very tiny additional ferroelectric distortion. The calculations performed on a stoichiometric compound so suggest that the low-temperature phase of WO3 is not intrinsically ferroelectric and that the experimentally observed ferroelectric character might arise from extrinsic defects such as oxygen vacancies. Independently, we also identify never observed R3m and R3c ferroelectric metastable phases with large polarizations and low energies close to the P21/c ground state, which makes WO3 a potential antiferroelectric material. The relative stability of various phases is discussed in terms of the anharmonic couplings between different structural distortions, highlighting a very complex interplay
Record of paleofluid circulation in faults revealed by hematite (U-Th)/He and apatite fission-track dating: An example from Gower Peninsula fault fissures, Wales
No full textFault rock low-temperature thermochronometry can inform the timing, temperature, and significance of hydrothermal fluid circulation in fault systems. We demonstrate this with combined hematite (U-Th)/He (He) dating, and sandstone apatite fission-track (AFT) and apatite and zircon (U-Th)/He (He) thermochronometry from fault-related fissures on the Gower Peninsula, Wales. Hematite He dates from 141 ± 5.1 Ma to 120 ± 5.0 Ma overlap with a 131 ± 20 Ma sandstone infill AFT date. Individual zircon He dates are 402–260 Ma, reflecting source material erosion, and imply a maximum Late Permian infill depositional age. Burial history reconstruction reveals modern exposures were not buried sufficiently in the Triassic–Early Cretaceous to have caused reheating to temperatures necessary to reset the AFT or hematite He systems, and thus these dates cannot reflect cooling due to erosion alone. Hot fluids circulating through fissures in the Early Cretaceous reset the AFT system. Hematite was either also reset by fluids or precipitated from these fluids. Similar hematite He dates from fault-related mineralization in south Glamorgan (Wales) and Cumbria (England) imply concomitant regional hot groundwater flow along faults. In this example, hydrothermal fluid circulation, coeval with North Atlantic rifting, occurred in higher-permeability fissures and fault veins long after they initially formed, directly influencing local and regional geothermal gradients
The origin of animals: Can molecular clocks and the fossil record be reconciled?
No full textThe evolutionary emergence of animals is one of the most significant episodes in the history of life, but its timing remains poorly constrained. Molecular clocks estimate that animals originated and began diversifying over 100 million years before the first definitive metazoan fossil evidence in the Cambrian. However, closer inspection reveals that clock estimates and the fossil record are less divergent than is often claimed. Modern clock analyses do not predict the presence of the crown-representatives of most animal phyla in the Neoproterozoic. Furthermore, despite challenges provided by incomplete preservation, a paucity of phylogenetically informative characters, and uncertain expectations of the anatomy of early animals, a number of Neoproterozoic fossils can reasonably be interpreted as metazoans. A considerable discrepancy remains, but much of this can be explained by the limited preservation potential of early metazoans and the difficulties associated with their identification in the fossil record. Critical assessment of both records may permit better resolution of the tempo and mode of early animal evolution
Deep mixing of mantle melts beneath continental flood basalt provinces: Constraints from olivine-hosted melt inclusions in primitive magmas
No full textWe present major and trace element compositions of 154 re-homogenised olivine-hosted melt inclusions found in primitive rocks (picrites and ferropicrites) from the Mesozoic Paraná–Etendeka and Karoo Continental Flood Basalt (CFB) provinces. The major element compositions of the melt inclusions, especially their Fe/Mg ratios, are variable and erratic, and attributed to the re-homogenisation process during sample preparation. In contrast, the trace element compositions of both the picrite and ferropicrite olivine-hosted melt inclusions are remarkably uniform and closely reflect those of the host whole-rocks, except in a small subset affected by hydrothermal alteration. The Paraná–Etendeka picrites and ferropicrites are petrogenetically related to the more evolved and voluminous flood basalts, and so we propose that compositional homogeneity at the melt inclusion scale implies that the CFB parental mantle melts were well mixed prior to extensive crystallisation. The incompatible trace element homogeneity of olivine-hosted melt inclusions in Paraná–Etendeka and Karoo primitive magmatic rocks has also been identified in other CFB provinces and contrasts with findings from studies of basalts from mid-ocean ridges (e.g. Iceland and FAMOUS on the Mid Atlantic Ridge), where heterogeneity of incompatible trace elements in olivine-hosted melt inclusions is more pronounced. We suggest that the low variability in incompatible trace element contents of olivine-hosted melt inclusions in near-primitive CFB rocks, and also ocean island basalts associated with moderately thick lithosphere (e.g. Hawaii, Galápagos, Samoa), may reflect mixing along their longer transport pathways during ascent and/or a temperature contrast between the liquidus and the liquid when it arrives in the crust. These thermal paths promote mixing of mantle melts prior to their entrapment by growing olivine crystals in crustal magma chambers. Olivine-hosted melt inclusions of ferropicrites from the Paraná–Etendeka and Karoo CFB have the least variable compositions of all global melt inclusion suites, which may be a function of their unusually deep origin and low viscosity
The Composition of Melts from a Heterogeneous Mantle and the Origin of Ferropicrite: Application of a Thermodynamic Model
No full textEvidence for chemical and lithological heterogeneity in the Earth’s convecting mantle is widely acknowledged, yet the major element signature imparted on mantle melts by this heterogeneity is still poorly resolved. In this study, a recent thermodynamic melting model is tested on a range of compositions that correspond to potential mantle lithologies (harzburgitic to pyroxenitic), to demonstrate its applicability over this compositional range, in particular for pyroxenite melting. Our results show that, despite the model’s calibration in peridotitic systems, it effectively reproduces experimental partial melt compositions for both Si-deficient and Si-excess pyroxenites. Importantly, the model accurately predicts the presence of a free silica phase at high pressures in Si-excess pyroxenites, indicating the activation of the pyroxene–garnet thermal divide. This thermal divide has a dominant control on solidus temperature, melt productivity and partial melt composition. The model is used to make new inferences on the link between mantle composition and melting behaviour. In silica-deficient and low-pressure (olivine-bearing) lithologies, melt composition is not very sensitive to source composition. Linearly varying the source composition between peridotite and basaltic pyroxenite, we find that the concentration of oxides in the melt tends to be buffered by the increased stability of more fusible phases, causing partial melts of even highly fertile lithologies to be similar to those of peridotite. An exception to this behaviour is FeO, which is elevated in partial melts of silica-deficient pyroxenite even if the bulk composition does not have a high FeO content relative to peridotite. Melt Al2O3 and MgO vary predominantly as a function of melting depth rather than bulk composition. We have applied the thermodynamic model to test the hypothesis that Fe-rich mantle melts such as ferropicrites are derived by partial melting of Si-deficient pyroxenite at elevated mantle potential temperatures. We show that the conspicuously high FeO in ferropicrites at a given MgO content does not require a high-Fe mantle source and is indeed best matched by model results involving around 0–20% melting of silica-deficient pyroxenite. A pyroxenite source lithology also accounts for the low CaO content of ferropicrites, whereas their characteristic low Al2O3 is a function of their high pressure of formation. Phanerozoic ferropicrites are exclusively located in continental flood basalt (CFB) provinces and this model of formation confirms that lithological heterogeneity (perhaps recycled oceanic crust) is present in CFB mantle sources