Rapid sea level rise in the aftermath of a Neoproterozoic snowball Earth.

Earth's most severe climate changes occurred during global-scale "snowball Earth" glaciations, which profoundly altered the planet's atmosphere, oceans, and biosphere. Extreme rates of glacioeustatic sea level rise are predicted by the snowball Earth hypothesis, but supporting geologic evidence has been lacking. We use paleohydraulic analysis of wave ripples and tidal laminae in the Elatina Formation, Australia-deposited after the Marinoan glaciation ~635 million years ago-to show that water depths of 9 to 16 meters remained nearly constant for ~100 years throughout 27 meters of sediment accumulation. This accumulation rate was too great to have been accommodated by subsidence and instead indicates an extraordinarily rapid rate of sea level rise (0.2 to 0.27 meters per year). Our results substantiate a fundamental prediction of snowball Earth models of rapid deglaciation during the early transition to a supergreenhouse climate.

Sedimentary processes of the Bagnold Dunes: Implications for the eolian rock record of Mars.

The Mars Science Laboratory rover Curiosity visited two active wind-blown sand dunes within Gale crater, Mars, which provided the first ground-based opportunity to compare Martian and terrestrial eolian dune sedimentary processes and study a modern analog for the Martian eolian rock record. Orbital and rover images of these dunes reveal terrestrial-like and uniquely Martian processes. The presence of grainfall, grainflow, and impact ripples resembled terrestrial dunes. Impact ripples were present on all dune slopes and had a size and shape similar to their terrestrial counterpart. Grainfall and grainflow occurred on dune and large-ripple lee slopes. Lee slopes were ~29° where grainflows were present and ~33° where grainfall was present. These slopes are interpreted as the dynamic and static angles of repose, respectively. Grain size measured on an undisturbed impact ripple ranges between 50 µm and 350 µm with an intermediate axis mean size of 113 µm (median: 103 µm). Dissimilar to dune eolian processes on Earth, large, meter-scale ripples were present on all dune slopes. Large ripples had nearly symmetric to strongly asymmetric topographic profiles and heights ranging between 12 cm and 28 cm. The composite observations of the modern sedimentary processes highlight that the Martian eolian rock record is likely different from its terrestrial counterpart because of the large ripples, which are expected to engender a unique scale of cross stratification. More broadly, however, in the Bagnold Dune Field as on Earth, dune-field pattern dynamics and basin-scale boundary conditions will dictate the style and distribution of sedimentary processes.

Large wind ripples on Mars: A record of atmospheric evolution.

Wind blowing over sand on Earth produces decimeter-wavelength ripples and hundred-meter- to kilometer-wavelength dunes: bedforms of two distinct size modes. Observations from the Mars Science Laboratory Curiosity rover and the Mars Reconnaissance Orbiter reveal that Mars hosts a third stable wind-driven bedform, with meter-scale wavelengths. These bedforms are spatially uniform in size and typically have asymmetric profiles with angle-of-repose lee slopes and sinuous crest lines, making them unlike terrestrial wind ripples. Rather, these structures resemble fluid-drag ripples, which on Earth include water-worked current ripples, but on Mars instead form by wind because of the higher kinematic viscosity of the low-density atmosphere. A reevaluation of the wind-deposited strata in the Burns formation (about 3.7 billion years old or younger) identifies potential wind-drag ripple stratification formed under a thin atmosphere.

Deposition, exhumation, and paleoclimate of an ancient lake deposit, Gale crater, Mars.

The landforms of northern Gale crater on Mars expose thick sequences of sedimentary rocks. Based on images obtained by the Curiosity rover, we interpret these outcrops as evidence for past fluvial, deltaic, and lacustrine environments. Degradation of the crater wall and rim probably supplied these sediments, which advanced inward from the wall, infilling both the crater and an internal lake basin to a thickness of at least 75 meters. This intracrater lake system probably existed intermittently for thousands to millions of years, implying a relatively wet climate that supplied moisture to the crater rim and transported sediment via streams into the lake basin. The deposits in Gale crater were then exhumed, probably by wind-driven erosion, creating Aeolis Mons (Mount Sharp).

Electronic structure and thermodynamic stability of uranium-doped yttrium iron garnet.

The electronic and thermodynamic properties of yttrium iron garnet (Y3Fe5O12, YIG), as a possible uranium-bearing phase, have been investigated using first-principles and semi-empirical methods. The electronic structures of pure and U-doped YIG were calculated and compared in order to obtain a fundamental understanding of the incorporation mechanism and stability of U in a YIG matrix. Uranium at the A-site is in 4 +  oxidation state, acting as a single donor and introducing a localized defect state in the band gap. The ionic relaxations show U at the A-site is an off-center impurity. At the B-site, uranium is in 5 +  oxidation state giving rise to two localized defect states in the middle of the band gap. At thermodynamic equilibrium the incorporation of U is limited by (i) the relatively narrow stability domain of the host YIG and (ii) the precipitation of uranium oxides as secondary phases. Under Y-rich growth conditions, YIG is unstable with respect to competing phases such as the iron oxides, Y2O3 and YFeO3. Under O-rich conditions, the incorporation U is obstructed by the formation of uranium-oxide precipitates. Under Fe-rich growth conditions, the formation energies of UY (U at the A-site) and UFe (U at the B-site) become negative for 0 ≤ EF ≤ 0.62 eV and 0 ≤ EF ≤ 0.77 eV, respectively, indicating that U might be incorporated in p-type YIG.

Effects of ionizing radiation and temperature on uranyl silicates: soddyite (UO2)2(SiO4)(H2O)2 and Uranophane Ca(UO2)2(SiO3OH)2·5H2O.

The stability of soddyite under electron irradiation has been studied over the temperature range of 25-300 °C. At room temperature, soddyite undergoes a crystalline-to-amorphous transformation (amorphization) at a total dose of 6.38 × 10(8) Gy. The electron beam irradiation results suggest that the soddyite structure is susceptible to radiation-induced nanocrystallization of UO(2). The temperature dependence of amorphization dose increases linearly up to 300 °C. A thermogravimetric and calorimetric analysis (TGA-DSC) combined with X-ray diffraction (XRD) indicates that soddyite retains its water groups up to 400 °C, followed by the collapse of the structure. Based on thermal analysis of uranophane, the removal of some water groups at relatively low temperatures provokes the collapse of the uranophane structure. This structural change appears to be the reason for the increase of amorphization dose at 140 °C. According to the results obtained, radiation field of a nuclear waste repository, rather than temperature effects, may cause changes in the crystallinity of soddyite and affect its stability during long-term storage.

Pressure-induced disordering and anomalous lattice expansion in La2Zr2O7 pyrochlore.

Pressure-induced cation and anion disordering in La2Zr2O7 pyrochlore is quantitatively analyzed by Rietveld refinement of in situ x-ray diffraction patterns, Raman, and infrared measurements. An anomalous lattice expansion and obvious change of the pressure dependence of the vibrational modes occur at ∼10 GPa. The pressure-induced water incorporation in the La2Zr2O7 pyrochlore structure may be related to a previously noted photoelectrochemical effect.

Phase stability and pressure dependence of defect formation in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores.

We report dramatically different behaviors between isostructural Gd2Ti2O7 and Gd2Zr2O7 pyrochlore at pressures up to 44 GPa, in which the substitution of Ti for Zr significantly increases structural stability. Upon release of pressure, the Gd2Ti2O7 becomes amorphous. In contrast, the high-pressure phase of Gd2Zr2O7 transforms to a disordered defect-fluorite structure. First-principle calculations for both compositions revealed that the response of pyrochlore to high pressure is controlled by the intrinsic energetics of defect formation.

Structural stability and phase transitions in WO3 thin films.

Tungsten oxide (WO3) thin films have been produced by KrF excimer laser (lambda = 248 nm) ablation of bulk ceramic WO3 targets. The crystal structure, surface morphology, chemical composition, and structural stability of the WO3 thin films have been studied in detail. Characterization of freshly grown WO3 thin films has been performed using X-ray diffraction (XRD), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy (RS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) measurements. The results indicate that the freshly grown WO3 thin films are nearly stoichiometric and well crystallized as monoclinic WO3. The surface morphology of the resulting WO3 thin film has grains of approximately 60 nm in size with a root-mean-square (rms) surface roughness of 10 nm. The phase transformations in the WO3 thin films were investigated by annealing in the TEM column at 30-500 degrees C. The phase transitions in the WO3 thin films occur in sequence as the temperature is increased: monoclinic --> orthorhombic --> hexagonal. Distortion and tilting of the WO6 octahedra occurs with the phase transitions and significantly affects the electronic properties and, hence, the electrochemical device applications of WO3.

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

X-ray photoelectron spectroscopy study of disordering in Gd2(Ti1-xZrx)2O7 pyrochlores.

The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25 < x < or =0.75), the corresponding O 1s XPS spectrum merges into a single symmetric peak. This confirms that the cation antisite disorder occurs simultaneously with anion disorder. Furthermore, the O 1s XPS spectrum of Gd2Zr2O7 experimentally suggests the formation of a split vacancy.

Nanocrystalline zirconia can be amorphized by ion irradiation.

Nanocrystalline composites are finding applications in high-radiation environments due to their excellent mechanical and electronic properties. We show, however, that at the smallest particle sizes, radiation damage effects can be so strongly enhanced that under the right conditions, materials that have never been made amorphous can become highly susceptible to irradiation-induced amorphization. Because light-weight, high-strength nanocomposites are potential materials for spacecraft shielding and sensor systems, these fundamental results have significant implications for the design and selection of materials to be used in environments where a large ion flux will be encountered.

Nanoscale manipulation of pyrochlore: new nanocomposite ionic conductors.

The ionic conductivity of isometric pyrochlore, ideally A2B2O (7), is extremely sensitive to disordering of A- and B-site cations and oxygen anion vacancies. We report the first use of ion beam irradiation-induced disordering in Gd 2Ti 2O (7) to produce a strain-free, buried, disordered defect-fluorite layer approximately 12 nm thick within an ordered pyrochlore matrix. This approach provides a new means of creating nanoscale, mixed ionic-electronic conductors in pyrochlore ceramics, such as those required for solid-state electrochemical cells.

Nuclear waste forms for actinides.

The disposition of actinides, most recently 239Pu from dismantled nuclear weapons, requires effective containment of waste generated by the nuclear fuel cycle. Because actinides (e.g., 239Pu and 237Np) are long-lived, they have a major impact on risk assessments of geologic repositories. Thus, demonstrable, long-term chemical and mechanical durability are essential properties of waste forms for the immobilization of actinides. Mineralogic and geologic studies provide excellent candidate phases for immobilization and a unique database that cannot be duplicated by a purely materials science approach. The "mineralogic approach" is illustrated by a discussion of zircon as a phase for the immobilization of excess weapons plutonium.

Performance assessments of nuclear waste repositories: a dialogue on their value and limitations.

Performance Assessment (PA) is the use of mathematical models to simulate the long-term behavior of engineered and geologic barriers in a nuclear waste repository; methods of uncertainty analysis are used to assess effects of parametric and conceptual uncertainties associated with the model system upon the uncertainty in outcomes of the simulation. PA is required by the U.S. Environmental Protection Agency as part of its certification process for geologic repositories for nuclear waste. This paper is a dialogue to explore the value and limitations of PA. Two "skeptics" acknowledge the utility of PA in organizing the scientific investigations that are necessary for confident siting and licensing of a repository; however, they maintain that the PA process, at least as it is currently implemented, is an essentially unscientific process with shortcomings that may provide results of limited use in evaluating actual effects on public health and safety. Conceptual uncertainties in a PA analysis can be so great that results can be confidently applied only over short time ranges, the antithesis of the purpose behind long-term, geologic disposal. Two "proponents" of PA agree that performance assessment is unscientific, but only in the sense that PA is an engineering analysis that uses existing scientific knowledge to support public policy decisions, rather than an investigation intended to increase fundamental knowledge of nature; PA has different goals and constraints than a typical scientific study. The "proponents" describe an ideal, six-step process for conducting generalized PA, here called probabilistic systems analysis (PSA); they note that virtually all scientific content of a PA is introduced during the model-building steps of a PSA; they contend that a PA based on simple but scientifically acceptable mathematical models can provide useful and objective input to regulatory decision makers. The value of the results of any PA must lie between these two views and will depend on the level of knowledge of the site, the degree to which models capture actual physical and chemical processes, the time over which extrapolations are made, and the proper evaluation of health risks attending implementation of the repository. The challenge is in evaluating whether the quality of the PA matches the needs of decision makers charged with protecting the health and safety of the public.

Inappropriate use of high-dose glyburide to treat uncontrolled type 2 diabetes mellitus.

OBJECTIVE: To report a case of chronic glyburide overdose. CASE SUMMARY: A patient with noninsulin-dependent diabetes mellitus (NIDDM) who had previously developed secondary failure while taking a maximal dosage of glipizide was switched to glyburide 5 mg/d. The patient initially experienced adequate glycemic control while taking glyburide, but subsequently experienced deterioration in glycemic control. This necessitated gradual increases in the dosage of glyburide until the maximum dosage of 20 mg/d was reached. Because the patient's diabetic control did not improve with this dosage of glyburide, she decided independently to increase the dosage further. She ingested an average daily dose of 37.7 mg of glyburide over the 18 days that preceded her clinic visit without experiencing any glyburide-related adverse effects. DISCUSSION: Progression of NIDDM may be responsible for the development of secondary sulfonylurea failure in NIDDM patients treated with oral sulfonylurea drugs. Consequently, these patients should be treated as patients dependent on insulin. CONCLUSIONS: NIDDM patients treated with oral sulfonylurea drugs require long-term blood glucose monitoring to detect the development of secondary sulfonylurea failure. Patients who experience secondary failure to a particular sulfonylurea drug do not appear to develop long-term blood glucose control when switched to a different oral sulfonylurea drug. These patients should be treated with insulin therapy.

Alpha-decay--induced fracturing in zircon: the transition from the crystalline to the metamict state.

A natural single crystal of zircon, ZrSiO(4,) from Sri Lanka exhibited zonation due to alpha-decay damage. The zones vary in thickness on a scale from one to hundreds of micrometers. The uranium and thorium concentrations vary from zone to zone such that the alpha-decay dose is between 0.2 x 10(16) and 0.8 x 10(16) alpha-events per milligram (0.15 to 0.60 displacement per atom). The transition from the crystalline to the aperiodic metamict state occurs over this dose range. Differential expansion of individual layers due to variations in their alpha-decay dose caused a systematic pattern of fractures that do not propagate across aperiodic layers. High-resolution transmission electron microscopy revealed a systematic change in the microstructure from a periodic atomic array to an aperiodic array with increasing alpha-decay dose. At doses greater than 0.8 x 10(16) alpha-events per milligram there is no evidence for long-range order. This type of damage will accumulate in actinide-bearing, ceramic nuclear waste forms. The systematic pattern of fractures would occur in crystalline phases that are zoned with respect to actinide radionuclides.