Ar diffusion in K-feldspar: present and absent

The mechanisms of Ar release from K-feldspar samples in laboratory experiments and during their geological history are assessed here. Modern petrology clearly established that the chemical and isotopic record of minerals is normally dominated by aqueous recrystallization. The laboratory critique is trickier, which explains why so many conflicting approaches have been able to survive long past their expiration date. Current models are evaluated for self-consistency; especially Arrhenian non-linearity leads to paradoxes. The models’ testable geological predictions suggest that temperature-based downslope extrapolations often overestimate observed geological Ar mobility substantially. An updated interpretation is based on the unrelatedness of geological behaviour to laboratory experiments. The isotopic record of K-feldspar in geological samples is not a unique function of temperature, as recrystallisation promoted by aqueous fluids is the predominant mechanism controlling isotope transport. K-feldspar should therefore be viewed as a hygrochronometer. Laboratory degassing proceeds from structural rearrangements and phase transitions such as are observed in situ at high temperature in Na and Pb feldspars. These effects violate the mathematics of an inert Fick’s Law matrix and preclude downslope extrapolation. The similar upward-concave, non-linear shapes of Arrhenius trajectories of many silicates, hydrous and anhydrous, are likely common manifestations of structural rearrangements in silicate structures.

CO(2) Diffusion in Polar Ice: Observations from Naturally Formed CO(2) Spikes in the Siple Dome (Antarctica) Ice Core

One common assumption in interpreting ice-core CO(2) records is that diffusion in the ice does not affect the concentration profile. However, this assumption remains untested because the extremely small CO(2) diffusion coefficient in ice has not been accurately determined in the laboratory. In this study we take advantage of high levels of CO(2) associated with refrozen layers in an ice core from Siple Dome, Antarctica, to study CO(2) diffusion rates. We use noble gases (Xe/Ar and Kr/Ar), electrical conductivity and Ca(2+) ion concentrations to show that substantial CO(2) diffusion may occur in ice on timescales of thousands of years. We estimate the permeation coefficient for CO(2) in ice is similar to 4 x 10(-21) mol m(-1) s(-1) Pa(-1) at -23 degrees C in the top 287 m (corresponding to 2.74 kyr). Smoothing of the CO(2) record by diffusion at this depth/age is one or two orders of magnitude smaller than the smoothing in the firn. However, simulations for depths of similar to 930-950m (similar to 60-70 kyr) indicate that smoothing of the CO(2) record by diffusion in deep ice is comparable to smoothing in the firn. Other types of diffusion (e.g. via liquid in ice grain boundaries or veins) may also be important but their influence has not been quantified.

Thermal Convection in Ice Sheets: We Look But Do Not See

Thermal convection in the Antarctic and Greenland ice sheets has been dismissed on the grounds that radio-echo stratigraphy is undisturbed for long distances. However, the undisturbed stratigraphy lies, for the most part, above the density inversion in polar ice sheets and therefore does not disprove convection. An echo-free zone is widespread below the density inversion, yet nobody has cited this as a strong indication that convection is indeed present at d�pth. A generalized Rayleigh criterion for thermal convection in e1astic-viscoplastic polycrystalline solids heated from below is developed and applied to ice-sheet convection. An infinite Rayleigh number at the onset of primary creep decreases with time and becomes constant when secondary creep dominates, suggesting that any thermal buoyancy stress can initiate convection but convection cannot be sustained below a buoyancy stress of about 3 kPa. An analysis of the temperature profile down the Byrd Station core hole suggests that about 1000 m of ice below the density inversion will sustain convection. Creep along the Byrd Station strain network, radar sounding in East Antarctica, and seismic sounding in West Antarctica are examined for evidence of convective creep superimposed on advective creep. It is concluded that the evidence for convection is there, if we look for it with the intention offinding it.

Daily and seasonal thermal stresses in tilings: a field survey combined with numeric modeling

This study investigates thermally induced tensile stresses in ceramic tilings. Daily and seasonal thermal cycles, as well as, rare but extreme events, such as a hail-storm striking a heated terrace tiling, were studied in the field and by numerical modeling investigations. The field surveys delivered temperature– time diagrams and temperature profiles across tiling systems. These data were taken as input parameters for modeling the stress distribution in the tiling system in order to detect potential sites for material failure. Dependent on the thermal scenario (e.g., slow heating of the entire structure during morning and afternoon, or a rapid cooling of the tiles by a rain storm) the modeling indicates specific locations with high tensile stresses. Typically regions along the rim of the tiling field showed stresses, which can become critical with respect to the adhesion strength. Over the years, ongoing cycles of thermal expansion–contraction result in material fatigue promoting the propagation of cracks. However, the installation of flexible waterproofing membranes (applied between substrate and tile adhesive) represents an efficient technical innovation to reduce such crack propagation as confirmed by both numerical modeling results and microstructural studies on real systems.

Resolving diffusion in clay minerals at different time scales: Combination of experimental and modeling approaches

Since no single experimental or modeling technique provides data that allow a description of transport processes in clays and clay minerals at all relevant scales, several complementary approaches have to be combined to understand and explain the interplay between transport relevant phenomena. In this paper molecular dynamics simulations (MD) were used to investigate the mobility of water in the interlayer of montmorillonite (Mt), and to estimate the influence of mineral surfaces and interlayer ions on the water diffusion. Random Walk (RW) simulations based on a simplified representation of pore space in Mt were used to estimate and understand the effect of the arrangement of Mt particles on the meso- to macroscopic diffusivity of water. These theoretical calculations were complemented with quasielastic neutron scattering (QENS) measurements of aqueous diffusion in Mt with two pseudo-layers of water performed at four significantly different energy resolutions (i.e. observation times). The size of the interlayer and the size of Mt particles are two characteristic dimensions which determine the time dependent behavior of water diffusion in Mt. MD simulations show that at very short time scales water dynamics has the characteristic features of an oscillatory motion in the cage formed by neighbors in the first coordination shell. At longer time scales, the interaction of water with the surface determines the water dynamics, and the effect of confinement on the overall water mobility within the interlayer becomes evident. At time scales corresponding to an average water displacement equivalent to the average size of Mt particles, the effects of tortuosity are observed in the meso- to macroscopic pore scale simulations. Consistent with the picture obtained in the simulations, the QENS data can be described using a (local) 3D diffusion at short observation times, whereas at sufficiently long observation times a 2D diffusive motion is clearly observed. The effects of tortuosity measured in macroscopic tracer diffusion experiments are in qualitative agreement with RW simulations. By using experimental data to calibrate molecular and mesoscopic theoretical models, a consistent description of water mobility in clay minerals from the molecular to the macroscopic scale can be achieved. In turn, simulations help in choosing optimal conditions for the experimental measurements and the data interpretation. (C) 2014 Elsevier B.V. All rights reserved.

Atomistic Modeling of Effect of Mg on Oxygen Vacancy Diffusion in α-Alumina

Oxygen diffusion plays an important role in grain growth and densification during the sintering of alumina ceramics and governs high-temperature processes such as creep. The atomistic mechanism for oxygen diffusion in alumina is, however, still debated; atomistic calculations not being able to match experimentally determined activation energies for oxygen vacancy diffusion. These calculations are, however, usually performed for perfectly pure crystals, whereas virtually every experimental alumina sample contains a significant fraction of impurity/dopants ions. In this study, we use atomistic defect cluster and nudged elastic band (NEB) calculations to model the effect of Mg impurities/dopants on defect binding energies and migration barriers. We find that oxygen vacancies can form energetically favorable clusters with Mg, which reduces the number of mobile species and leads to an additional 1.5 eV energy barrier for the detachment of a single vacancy from Mg. The migration barriers of diffusive jumps change such that an enhanced concentration of oxygen vacancies is expected around Mg ions. Mg impurities were also found to cause destabilization of certain vacancy configurations as well as enhanced vacancy–vacancy interaction.

The Effects of Heat Acclimation Followed by Sleep Deprivation on Perceived Exertion, Thirst, and Thermal Sensations in Exercising Males

Subjects were tested while walking on a tradmill for 11 days in a row at sub-maximal levels for 90 minutes the heat. After the 10th day, subjects were kept awake for 24 hours before being tested in a state of sleep deprivation on the 11th day. Subjects rated their perceived exertion, thirst levels, and thermal sensations at regular intervals before, during, and after exercise each day. The changes in RPE, thirst, and thermal sensations were examined to determine the progression of heat acclimation and to observe changes in the subjects' perceived workloads. While subjects were significantly less thirsty on day 10 than when beginning the study on day 1, no significant changes occured in regards to thermal sensations or RPE values. On the 11th day, these variables were again observed in order to examine the effects of sleep deprivation on the adaptations of heat acclimation. After 28 hours of sleep loss, subjects rated themselves as feeling significantly more thristy after exercise than they had on day 10, yet again there was no significant change in thermal sensations or RPE values. Throughout the study, RPE and thermal sensation ratings seemed to be closely linked while sensations of thirst fluctuated independently.

Calcareous nannofossil during the Paleocene Eocene Thermal Maximum in sediments of Walvish Ridge

Compositions and abundances of calcareous nannofossil taxa have been determined in a ca 170 kyrs long time interval across the Paleocene/Eocene boundary at 1-cm to 10-cm resolution from two ODP Sites (1262, 1263) drilled along the flank of the Walvis Ridge in the South Atlantic. The results are compared to published data from ODP Site 690 in the Weddell Sea. The assemblages underwent rapid evolution over a 74 kyrs period, indicating stressed, unstable and/or extreme photic zone environments during the PETM hyperthermal. This rapid evolution, which created 5 distinct stratigraphic horizons, is consistent with the restricted brief occurrences of malformed and/or weakly calcified morphotypes. The production of these aberrant morphotypes is possibly caused by major global scale changes in carbon cycling in the ocean-atmosphere system, affecting also photic zone environments. No marked paleoecologically induced changes are observed in abundances of the genera Discoaster, Fasciculithus and Sphenolithus at the Walvis Ridge sites. Surprisingly, there is no significant correlation in abundance between these three genera, presumed to have had a similar paleoecological preference for warm and oligotrophic conditions.

Nannofossil and stable isotope record across the Paleocene/Eocene Thermal Maximum in ODP Hole 183-1135A

The Paleocene/Eocene Thermal Maximum (PETM, ca. 55 Ma) is an abrupt, profound perturbation of climate and the carbon cycle associated with a massive injection of isotopically light carbon into the ocean-atmosphere system. As such, it provides an analogue for understanding the interplay between phytoplankton and climate under modern anthropogenic global-warming conditions. However, the accompanying enhanced dissolution poses uncertainty on the reconstruction of the affected ecology and productivity. We present a high-resolution record of bulk isotopes and nannofossil absolute abundance from Ocean Drilling Program (ODP) Site 1135 on the Kerguelen Plateau, Southern Indian Ocean to quantitatively constrain for the first time the influence of dissolution on paleoecological reconstruction. Our bulk-carbonate isotope record closely resembles that of the classic PETM site at ODP Site 690 on the opposite side of the Antarctic continent, and its correlation with those from ODP Sites 690, 1262 and 1263 records allows recognition of 14 precessional cycles upsection from the onset of the carbon isotopic excursion (CIE). This, together with a full range of common Discoasteraraneus and an abundance crossover between Fasciculithus and Zygrhablithusbijugatus, indicates the presence of the PETM at Site 1135, a poorly known record with calcareous fossils throughout the interval. The strong correlation between the absolute abundances of Chiasmolithus and coccolith assemblages reveals a dominant paleoecological signal in the poorly preserved fossil assemblages, while the influence of dissolution is only strong during the CIE. This suggests that r-selected taxa can preserve faithful ecological information even in the severely-altered assemblages studied here, and therefore provide a strong case for the application of nannofossils to paleoecological studies in better-preserved PETM sections. The inferred nannoplankton productivity drops abruptly at the CIE onset, but rapidly increases after the CIE peak, both of which may be driven by nutrient availability related to ocean stratification and vertical mixing due to changed sea-surface temperatures.

Stable carbon isotope record of benthic foraminifera across the Paleocene-Eocene thermal maximum in the New Jersey Coastal Plain

In the New Jersey Coastal Plain, a silty to clayey sedimentary unit (the Marlboro Formation) represents deposition during the Paleocene-Eocene thermal maximum (PETM). This interval is remarkably different from the glauconitic sands and silts of the underlying Paleocene Vincentown and overlying Eocene Manasquan Formation. We integrate new and published stable isotope, biostratigraphic, lithostratigraphic and ecostratigraphic records, constructing a detailed time frame for the PETM along a depth gradient at core sites Clayton, Wilson Lake, Ancora and Bass River (updip to downdip). The onset of the PETM, marked by the base of the carbon isotope excursion (CIE), is within the gradual transition from glauconitic silty sands to silty clay, and represented fully at the updip sites (Wilson Lake and Clayton). The CIE "core" interval is expanded at the updip sites, but truncated. The CIE "core" is complete at the Bass River and Ancora sites, where the early part of the recovery is present (most complete at Ancora). The extent to which the PETM is expressed in the sediments is highly variable between sites, with a significant unconformity at the base of the overlying lower Eocene sediments. Our regional correlation framework provides an improved age model, allowing better understanding of the progression of environmental changes during the PETM. High-resolution benthic foraminiferal data document the change from a sediment-starved shelf setting to a tropical, river-dominated mud-belt system during the PETM, probably due to intensification of the hydrologic cycle. The excellent preservation of foraminifera during the PETM and the lack of severe benthic extinction suggest there was no extreme ocean acidification in shelf settings.