Sample records for temperature equilibration rate

  1. Molecular dynamics studies of electron-ion temperature equilibration in hydrogen plasmas within the coupled-mode regime

    DOE PAGES

    Benedict, Lorin X.; Surh, Michael P.; Stanton, Liam G.; ...

    2017-04-10

    Here, we use classical molecular dynamics (MD) to study electron-ion temperature equilibration in two-component plasmas in regimes for which the presence of coupled collective modes has been predicted to substantively reduce the equilibration rate. Guided by previous kinetic theory work, we examine hydrogen plasmas at a density of n = 10 26cm –3, T i = 10 5K, and 10 7 K < Te < 10 9K. The nonequilibrium classical MD simulations are performed with interparticle interactions modeled by quantum statistical potentials (QSPs). Our MD results indicate (i) a large effect from time-varying potential energy, which we quantify by appealingmore » to an adiabatic two-temperature equation of state, and (ii) a notable deviation in the energy equilibration rate when compared to calculations from classical Lenard-Balescu theory including the QSPs. In particular, it is shown that the energy equilibration rates from MD are more similar to those of the theory when coupled modes are neglected. We suggest possible reasons for this surprising result and propose directions of further research along these lines.« less

  2. Unshocked Equilibrated H Chondrites: A Common Low-Temperature Record from Fe-Mg Ordering in Orthopyroxene

    NASA Astrophysics Data System (ADS)

    Folco, L.; Mellini, M.; Pillinger, C. T.

    1995-09-01

    The study of the thermal metamorphism of ordinary chondrites through geothermometers can provide significant constraints on the parent body thermal models which remain controversial. We report here results from Fe-Mg ordering closure temperatures (Tc) of orthopyroxenes from eight unshocked equilibrated H-chondrites obtained by means of single crystal X-ray diffraction. The method is based on the fact that cation partitioning in orthopyroxene is sensitive to temperature [1], and makes use of the experimental calibration by Molin et al. [2]. The goal of the investigation is to check how petrographic types relate to cation ordering thermal records. Results: The orthopyroxenes show a very similar degree of Fe-Mg ordering (see Table 1.). The Tc's cluster within the 384+/-48 to 480+/-28 degrees C interval, and show no correlation with petrographic type. The lack of a correlation does not mean that the distribution is random, rather, it appears to be controlled in individual samples by the degree of equilibration. In fact, the higher the petrographic type, the more coherent the results of the grains from individual chondrites. The spread of Tc's in the least equilibrated chondrites could be either a memory of heterogeneous pre-metamorphic records related to individual chondrule histories, or an artefact due to crystal defects. Therefore (1) the thermal records, inferred from the Fe-Mg ordering, are nearly the same for all the equilibrated H-chondrites; (2) the most equilibrated chondrites record distinct Tc values within the larger common Tc range; (3) the spread of Tc in H4's maybe indicative of disequilibrium and merits further study. The closure temperature conveys information on the cooling rate close to its value, regardless of the temperature regimes when the ordering process started. Extrapolation to high temperatures can be made only if the cooling path is constrained. Since we have no data to establish the temperature when ordering began and to decide whether the cooling was linear, we have not attempted quantitative estimates of cooling rates. However we can say that as equilibrated H-chondrites carry similar Tc records, they cooled at similar rates through 380-480 degrees C. However, the k(sub)D's (i.e., the intracrystalline Fe-Mg distribution coefficient) range 0.029 to 0.054, suggesting that H-chondrites cooled in petrogenetic environments intermediate between those of volcanic [3] and granulitic rocks [3,4]. Conclusion: Our results provide the following constraints: (1) Equilibrated H-chondrites, regardless the petrographic type, were located in petrogenetic environments characterized by similar temperature-time conditions when cooling through 380-480 degrees C, and, in terms of terrestrial environments, intermediate between those of volcanic and granulitic facies. (2) Different petrographic types reflect distinct metamorphic thermal regimes. Thus, to account for constraint (1), petrographic type was determined at temperatures above the 380-480 degrees C interval. This implies that equilibrated H-chondrites were placed in different geological environments characterized by distinct temperature-time regimes when still above this temperature range. In the case of the least equilibrated chondrites, for which the two events could coincide. Acknowledgments: We thank EUROMET for providing us with the Frontier Mt. samples, and PNRA for supporting this study. References: [1] Saxena S. K. and Dal Negro A. (1983) Bull. Min ral., 106, 443-449. [2] Molin G. M. et al. (1991) EPSL, 105, 260-265. [3] Bertolo S. and Nimis P. (1993) EJM, 5, 707-719. [4] Tribaudino M. and Talarico F. (1992) EJM, 4, 453-463.

  3. Evolution of light hydrocarbon gases in subsurface processes: Constraints from chemical equilibrium

    NASA Astrophysics Data System (ADS)

    Sugisaki, Ryuichi; Nagamine, Koichiro

    1995-06-01

    The behaviour of CH 4, C 2H 6 and C 3H 8 in subsurface processes such as magma intrusion, volcanic gas discharge and natural gas generation have been examined from the viewpoint of chemical equilibrium. It seems that equilibrium among these three hydrocarbons is attainable at about 200°C. When a system at high temperatures is cooled, re-equilibration is continued until a low temperature is reached. The rate at which re-equilibration is achieved, however, steadily diminishes and, below 200°C, the reaction between the hydrocarbons stops and the gas composition at this time is frozen in, and it remains unchanged in a metastable state for a long period of geological time. Natural gas compositions from various fields have shown that, when a hydrocarbon system out of chemical equilibrium is heated, it gradually approaches equilibrium above 150°C. On the way towards equilibration, compositions of thermogenic gases apparently temporarily show a thermodynamic equilibrium constant at a temperature that is higher than the real equilibrium temperature expected from the ambient temperature of the samples; in contrast, biogenic gases indicate a lower temperature. In lower temperature regions, kinetic effects probably control the gas composition; the compositions are essentially subjected to genetic processes operating on the gases (such as pyrolysis of organic material and bacterial activity) and they fluctuate substantially. Examination of volcanic gases and pyrolysis experimental data, however, have suggested that the equilibration rate of these hydrocarbons is sluggish in comparison with that of reactive inorganic species such as H 2S and SO 2. The view presented in this study will be helpful in understanding the genetic processes that create oil and gas and the migration of these hydrocarbons and in interpreting the origins of magmatic gases.

  4. Effects of large-angle Coulomb collisions on inertial confinement fusion plasmas.

    PubMed

    Turrell, A E; Sherlock, M; Rose, S J

    2014-06-20

    Large-angle Coulomb collisions affect the rates of energy and momentum exchange in a plasma, and it is expected that their effects will be important in many plasmas of current research interest, including in inertial confinement fusion. Their inclusion is a long-standing problem, and the first fully self-consistent method for calculating their effects is presented. This method is applied to "burn" in the hot fuel in inertial confinement fusion capsules and finds that the yield increases due to an increase in the rate of temperature equilibration between electrons and ions which is not predicted by small-angle collision theories. The equilibration rate increases are 50%-100% for number densities of 10(30)  m(-3) and temperatures around 1 keV.

  5. Combinations of glycerol percent, glycerol equilibration time, and thawing rate upon freezability of bull spermatozoa in plastic straws.

    PubMed

    Wiggin, H B; Almquist, J O

    1975-03-01

    Twelve ejaculates were used in a central composite experiment to test 15 combinations of glycerol (7, 9, 11, 13, or 15%), glycerol equilibration times (1, 2, 4, 8, or 16 h) and thawing rates (water at 35 C for 15 s, 50 C for 13 s, 65 C for 11 s, 80 C for 9 s, or 95 C for 7 s). Semen was diluted in heated skim milk-glycerol, packaged in .3-ml. Continental U.S. straws and frozen in liquid nitrogen vapor. Based on post-thaw progressive sperm motility after storage at -196 C for 9 to 11 days, estimated optima from multiple regression were 10.7% for glycerol, 2.0 h for glycerol equilibration time, and 76 C for thawing bath temperature. Only the linear effect for each variable was significant. Much faster thawing rates and shorter glycerol equilibration times than those for freezing bull spermatozoa in glass ampules should be used for maximum post-thaw sperm motility in straws.

  6. Programming scale-free optics in disordered ferroelectrics.

    PubMed

    Parravicini, Jacopo; Conti, Claudio; Agranat, Aharon J; DelRe, Eugenio

    2012-06-15

    Using the history dependence of a dipolar glass hosted in a compositionally disordered lithium-enriched potassium tantalate niobate (KTN:Li) crystal, we demonstrate scale-free optical propagation at tunable temperatures. The operating equilibration temperature is determined by previous crystal spiralling in the temperature/cooling-rate phase space.

  7. Calculation of ground state rotational populations for kinetic gas homonuclear diatomic molecules including electron-impact excitation and wall collisions.

    PubMed

    Farley, David R

    2010-09-07

    A model has been developed to calculate the ground state rotational populations of homonuclear diatomic molecules in kinetic gases, including the effects of electron-impact excitation, wall collisions, and gas feed rate. The equations are exact within the accuracy of the cross sections used and of the assumed equilibrating effect of wall collisions. It is found that the inflow of feed gas and equilibrating wall collisions can significantly affect the rotational distribution in competition with nonequilibrating electron-impact effects. The resulting steady-state rotational distributions are generally Boltzmann for N≥3, with a rotational temperature between the wall and feed gas temperatures. The N=0,1,2 rotational level populations depend sensitively on the relative rates of electron-impact excitation versus wall collision and gas feed rates.

  8. Effect of storage temperature and equilibration time on polymethyl methacrylate (PMMA) bone cement polymerization in joint replacement surgery.

    PubMed

    Koh, Bryan T H; Tan, J H; Ramruttun, Amit Kumarsing; Wang, Wilson

    2015-11-17

    In cemented joint arthroplasty, the handling characteristics (doughing, working, and setting times) of polymethyl methacrylate (PMMA) bone cement is important as it determines the amount of time surgeons have to optimally position an implant. Storage conditions (temperature and humidity) and the time given for PMMA cement to equilibrate to ambient operating theater (OT) temperatures are often unregulated and may lead to inconsistencies in its handling characteristics. This has not been previously studied. Hence, the purpose of this study was to investigate the effect of storage temperatures on the handling characteristics of PMMA cement and the duration of equilibration time needed at each storage temperature to produce consistent and reproducible doughing, setting, and working times. SmartSet® HV cement was stored at three different controlled temperatures: 20 °C (control), 24 °C, and 28 °C for at least 24 h prior to mixing. The cement components were then brought into a room kept at 20 °C and 50 % humidity. Samples were allowed to equilibrate to ambient conditions for 15, 30, 45, and 60 min. The cement components were mixed and the dough time, temperature-versus-time curve (Lutron TM-947SD, Lutron Electronics, Inc., Coopersburg, PA), and setting time were recorded. Analysis was performed using the two-way ANOVA test (IBM SPSS Statistics V.22). At 20 °C (control) storage temperature, the mean setting time was 534 ± 17 s. At 24 °C storage temperature, the mean setting time was 414 ± 6 s (p < 0.001*) with 15 min of equilibration, 446 ± 11 s (p < 0.001*) with 30 min of equilibration, 501 ± 12 s (p < 0.001*) with 45 min of equilibration, and 528 ± 15 (p > 0.05) with 60 min of equilibration. At 28 °C storage temperature, the mean setting time was 381 ± 8 s (p < 0.001*) with 15 min of equilibration, 432 ± 30 s (p < 0.001*) with 30 min of equilibration, 487 ± 9 (p < 0.001*) with 45 min of equilibration, and 520 ± 16 s (p > 0.05) with 60 min of equilibration. This study reflects the extent to which storage temperatures and equilibration times can potentially affect the handling characteristics of PMMA cement. We recommend institutions to have a well-regulated temperature and humidity-controlled facility for storage of bone cements and a protocol to standardize the equilibration time of cements prior to use in the OT to improve consistency and reproducibility of the handling characteristics of PMMA cement.

  9. Experimentally Determined Subsolidus Metal-Olivine Element Partitioning with Applications to Pallasites.

    PubMed

    Donohue, Patrick H; Hill, Eddy; Huss, Gary R

    2018-02-01

    Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients ( K M ) increase in the order K Mn < K Cr < 1 < K Fe < K Co < K Ni , with five orders of magnitude separating K Mn from K Ni . Transition metals also become more siderophile with increasing experimental temperature (900 to 1550°C). The experiments incidentally produced diffusion profiles in olivine for these elements; Our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re- equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300°C/Myr.

  10. Experimentally determined subsolidus metal-olivine element partitioning with applications to pallasites

    NASA Astrophysics Data System (ADS)

    Donohue, Patrick H.; Hill, Eddy; Huss, Gary R.

    2018-02-01

    Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients (KM) increase in the order KMn < KCr < 1 < KFe < KCo < KNi, with five orders of magnitude separating KMn from KNi. Transition metals also become more siderophile with increasing experimental temperature (900-1550 °C). The experiments incidentally produced diffusion profiles in olivine for these elements; our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re-equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300 °C/Myr.

  11. Fast gradient separation by very high pressure liquid chromatography: reproducibility of analytical data and influence of delay between successive runs.

    PubMed

    Stankovicha, Joseph J; Gritti, Fabrice; Beaver, Lois Ann; Stevensona, Paul G; Guiochon, Georges

    2013-11-29

    Five methods were used to implement fast gradient separations: constant flow rate, constant column-wall temperature, constant inlet pressure at moderate and high pressures (controlled by a pressure controller),and programmed flow constant pressure. For programmed flow constant pressure, the flow rates and gradient compositions are controlled using input into the method instead of the pressure controller. Minor fluctuations in the inlet pressure do not affect the mobile phase flow rate in programmed flow. There producibilities of the retention times, the response factors, and the eluted band width of six successive separations of the same sample (9 components) were measured with different equilibration times between 0 and 15 min. The influence of the length of the equilibration time on these reproducibilities is discussed. The results show that the average column temperature may increase from one separation to the next and that this contributes to fluctuation of the results.

  12. Biomarkers of Exposure to Toxic Substances Volume 7: Identification of Potential Serum Protein Biomarkers Indicative of Low Level Kidney Degradation in Response to Toxin Exposures

    DTIC Science & Technology

    2009-05-01

    equilibrated for 4 min with Buffer A with a flow rate of 1 mL/min at room temperature. Once the HPLC lines and MARS column were flushed and equilibrated...ul 4 ) FT mouse control HPLC 10 ul 9) E mouse control Spin Column 10 ul 5) E mouse control HPLC 10 ul 10) Blue MW Standard The distinct...of Low Level Kidney Degradation in Response to Toxin Exposures Christopher L. Woolard Camilla A. Mauzy Biosciences and Protection

  13. Isochoric Burn, an Internally Consistent Method for the Reactant to Product Transformation in Reactive Flow

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Reaugh, J E; Lee, E L

    2002-07-01

    Mixture rules for partially reacted explosives differ amongst various models. For instance, JWL++ uses a partial pressure addition to compute an average zonal pressure, Ignition and Growth requires pressure equilibration and thermal equilibration of temperature dependent JWL EOSs, CHEETAH In Line RF also assumes temperature and pressure equilibration. It has been suggested in the past that a more realistic equilibration scheme should comprise isentropic pressure equilibration of the separate reacted and unreacted phases. This turns out not to be a proper path for equilibration. Rather, we find that the only internally consistent method is the evaluation of the equilibrium pressuremore » that satisfies the particular conditions of reactant and product resulting from deflagration in a fixed volume.« less

  14. Species variation in osmotic, cryoprotectant, and cooling rate tolerance in poultry, eagle, and Peregrine Falcon spermatozoa

    USGS Publications Warehouse

    Blanco, J.M.; Gee, G.; Wildt, D.E.; Donoghue, A.M.

    2000-01-01

    Potential factors influencing spermatozoa survival to cryopreservation and thawing were analyzed across a range of the following avian species: domestic chicken (Gallus domesticus), domestic turkey (Meleagris gallopavo), golden eagle (Aquila chrysaetos), Bonelli's eagle (Hieraaetus fasciatus), imperial eagle (Aquila adalberti), and peregrine falcon (Falco peregrinus). Studies focused on spermatozoa tolerance to the following: 1) osmotic stress, 2) different extracellular concentrations of the cryoprotectant dimethylacetamide (DMA), 3) equilibration times of 1 versus 4 h, 4) equilibration temperature of 4 versus 21 degrees C, and 5) rapid versus slow cooling before cryopreservation and standard thawing. Sperm viability was assessed with the live/dead stain (SYBR14/ propidium iodine). Sperm viability at osmolalities >/=800 mOsm was higher (P: /=2.06 M), experienced decreased (P: < 0.05) spermatozoa survival in all species, except the golden eagle and peregrine falcon. Number of surviving spermatozoa diminished progressively with increasing DMA concentrations in all species. Increased equilibration temperature (from 4 to 21 degrees C) markedly reduced (P: < 0.05) spermatozoa survival in all species except the Bonelli's eagle and turkey. Rapid cooling was detrimental (P: < 0.05) to spermatozoa from all species except the imperial eagle and the chicken. These results demonstrate that avian spermatozoa differ remarkably in response to osmotic changes, DMA concentrations, equilibration time, temperature, and survival after fast or slow freezing. These differences emphasize the need for species-specific studies in the development and enhancement of assisted breeding for poultry and endangered species.

  15. Multisystem Temperature Equilibration and the Second Law

    ERIC Educational Resources Information Center

    Leff, Harvey S.

    1977-01-01

    Shows that the entropy change during the temperature equilibration of an isolated collection of systems which may exchange heat (but not work) energy is positive when the constant-volume heat capacity of each system is a non-negative function of the temperature. (MLH)

  16. Crystallisation regimes and kinetics in experimentally decompressed dacitic magma

    NASA Astrophysics Data System (ADS)

    Blum-Oeste, N.; Schmidt, B. C.; Webb, S. L.

    2011-12-01

    Kinetic processes during magma ascent may have a strong influence on the eruption style. In water bearing dacitic magmas decompression induced exsolution of water and accompanying crystallisation of plagioclase are the main processes which drive the system towards a new equilibrium state. We present new data on the evolution of residual glass composition and crystal size distributions of plagioclase from decompression experiments. Experiments have been conducted in cold seal pressure vessels at 850°C on a natural dacite composition from Taapaca volcano (N. Chile). After an initial equilibration at 2kbar decompression rates between 6.3 and 450bar/h were applied to final pressures between 50 and 1550bar where samples were rapidly quenched. Complementary equilibrium experiments were done at corresponding pressures. The glass composition evolves from the initial state towards the equilibrium at the final pressure. The completeness of this re-equilibration depends on run duration and reaction rates. We introduce the "re-equilibration index" (REI), a fraction between 0 (initial state) and 1 (final state) which allows comparison of chemical components in terms of re-equilibration at different decompression rates. REI divided by the decompression duration gives the "re-equilibration rate" (RER). The REI varies among oxides and it decreases with increasing decompression rate. The highest REIs of ~0.9 have been found for MgO, K2O and Al2O3 at 6.3bar/h whereas Na2O shows the lowest number with 0.25 at this decompression rate. Towards faster decompression all REIs tend to decrease which shows a decreasing completeness of re-equilibration. At 450bar/h the highest REIs are ~0.25. RERs increase from below ~0.005/h at 6.3bar/h up to almost 0.08/h for Al2O3 at 450bar/h. The variability of RERs of different oxides also increases with decompression rates. At 450bar/h the RERs reach from <0.005/h up to 0.08/h. Although RERs strongly increase from low to high decompression rates, this does not compensate for the decreasing duration available for re-equilibration as REIs clearly show. The volume fraction of plagioclase decreases from ~21% at 6.3bar/h to ~16% at 450bar/h which fits the decrease in REIs. The population density of small crystals decreases whereas the population density of larger crystals increases from slow to fast decompression. This reflects a transition from nucleation controlled crystallisation at slow decompression to a growth dominated regime at fast decompression. As RERs show re-equilibration is faster in the growth dominated regime. Although this transition in nucleation processes might be counter-intuitive it can be explained by the observation of slightly higher water concentrations at fast decompression rates resulting in higher liquidus temperatures and thus lower undercooling.

  17. Ultrafast electronic relaxation in superheated bismuth

    NASA Astrophysics Data System (ADS)

    Gamaly, E. G.; Rode, A. V.

    2013-01-01

    Interaction of moving electrons with vibrating ions in the lattice forms the basis for many physical properties from electrical resistivity and electronic heat capacity to superconductivity. In ultrafast laser interaction with matter the electrons are heated much faster than the electron-ion energy equilibration, leading to a two-temperature state with electron temperature far above that of the lattice. The rate of temperature equilibration is governed by the strength of electron-phonon energy coupling, which is conventionally described by a coupling constant, neglecting the dependence on the electron and lattice temperature. The application of this constant to the observations of fast relaxation rate led to a controversial notion of ‘ultra-fast non-thermal melting’ under extreme electronic excitation. Here we provide theoretical grounds for a strong dependence of the electron-phonon relaxation time on the lattice temperature. We show, by taking proper account of temperature dependence, that the heating and restructuring of the lattice occurs much faster than were predicted on the assumption of a constant, temperature independent energy coupling. We applied the temperature-dependent momentum and energy transfer time to experiments on fs-laser excited bismuth to demonstrate that all the observed ultra-fast transformations of the transient state of bismuth are purely thermal in nature. The developed theory, when applied to ultrafast experiments on bismuth, provides interpretation of the whole variety of transient phase relaxation without the non-thermal melting conjecture.

  18. Electron-ion temperature equilibration in warm dense tantalum

    DOE PAGES

    Doppner, T; LePape, S.; Ma, T.; ...

    2014-11-05

    We present measurements of electron-ion temperature equilibration in proton-heated tantalum, under warm dense matter conditions. Our results agree with theoretical predictions for metals calculated using input data from ab initio simulations. Furthermore, the fast relaxation observed in the experiment contrasts with much longer equilibration times found in proton heated carbon, indicating that the energy flow pathways in warm dense matter are far from being fully understood.

  19. Short communication: Serum composition of milk subjected to re-equilibration by dialysis at different temperatures, after pH adjustments.

    PubMed

    Zhao, Zhengtao; Corredig, Milena

    2016-04-01

    The objective of this work was to investigate the properties of casein micelles after pH adjustment and their re-equilibration to the original pH and serum composition. Re-equilibration was carried out by dialyzing against skim milk at 2 different temperatures (4 or 22 °C). Turbidity, the average radius of the casein micelles, and the composition of the soluble phase were measured at different pH values, ranging between 5.5 and 8. Acidification led to the solubilization of colloidal calcium phosphate and decrease of the average radius of the micelles. With re-equilibration, casein dissociation occurred. In milk with pH values greater than 6.0, the average radius was recovered after re-equilibration. At pH values greater than neutral, an increase of the radius of casein micelles and increased dissociation of the casein were found. After re-equilibration, the radius of micelles and soluble protein in the serum decreased. The results were not affected by the temperature of re-equilibration. The changes to the calcium phosphate equilibrium and the dissociation of the micelles will have important consequences to the functionality of casein micelles. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  20. H2O Adsorption Kinetics on Smectites

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Quinn, Richard C.; Howard, Jeanie; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The adsorptive equilibration of H2O a with montomorillonite, a smectite clay has been measured. At low temperatures and pressures, equilibration can require many hours, effectively preventing smectites at the martian surface from responding rapidly to diurnal pressure and temperature variations.

  1. Implications for Metallographic Cooling Rates, Derived from Fine-Scale Analytical Traverses Across Kamacite, Taenite, and Tetrataenite in the Butler Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Ross, D. K.; Chabot, N. L.; Keller, L. P.

    2016-01-01

    The "M-shaped" Ni concentrations across Widmanstatten patterns in iron meteorites, mesosiderites, and ordinary chondrites are commonly used to calculate cooling rates. As Ni-poor kamacite exolves from Ni-rich taenite, Ni concentrations build up at the kamacite-taenite interface because of the sluggish diffusivity of Ni. Quantitative knowledge of experimentally-determined Ni diffusivities, coupled with the shape of the M-profile, have been used to allow calculation of cooling rates that pertained at low temperatures, less than or equal to 500 C. However, determining Ni metallographic cooling rates are challenging, due to the sluggish diffusivity of Ni at low temperatures. There are three potential difficulties in using Ni cooling rates at low temperatures: (i) Ni diffusivities are typically extrapolated from higher-temperature measurements; (ii) Phase changes occur at low temperatures that may be difficult to take into account; and (iii) It appears that Ge in kamacite and taenite has continued to equilibrate (or attempted to equilibrate) at temperatures below those that formed the M-shaped Ni profile. Combining Ni measurements with those of other elements has the potential to provide a way to confirm or challenge Ni-determined cooling rates, as well as provide insight into the partitioning behaviors of elements during the cooling of iron meteorites. Despite these benefits, studies that examine elemental profiles of Ni along with other elements in iron meteorites are limited, often due to the low concentration levels of the other elements and associated analytical challenges. The Butler iron meteorite provides a good opportunity to conduct a multi-element analytical study, due to the higher concentration levels of key elements in addition to Fe and Ni. In this work, we perform combined analysis for six elements in the Butler iron to determine the relative behaviors of these elements during the evolution of iron meteorites, with implications for metallographic cooling rates.

  2. Group II Xenoliths from Lunar Crater Volcanic Field, Central Nevada: Evidence for a Kinked Geotherm

    NASA Astrophysics Data System (ADS)

    Roden, M.; Mosely, J.; Norris, J.

    2015-12-01

    Group II xenoliths associated with the 140 Ka Easy Chair Crater, Lunar Crater volcanic field, NV, consist of amphibole rich-inclusions including amphibolites, pyroxenites, and gabbros. Abundant minerals in these inclusions are kaersutite, aluminous (7.3-9.7 wt% Al2O3), calcic clinopyroxene, primarily diopside, and olivine (Mg# 69-73) with accessory spinel, sulfide and apatite. Although most apatites are fluor-hydroxyapatite solid solutions, one xenolith contains Cl- and OH-rich apatite suggesting that Cl may have been an important constituent in the parent magma(s) . The xenoliths show abundant evidence for equilibration at relatively low temperatures including amphibole and orthopyroxene exsolution in clinopyroxene, and granules of magnetite in hercynite hosts. If latter texture is due to exsolution, then this particular Group II xenolith equilibrated at temperatures near or below 500oC or at a depth of about 15 km along a conductive geotherm. It may be that all the Group II xenoliths equilibrated at low temperatures given the abundant exsolution textures although Fe-Mg exchange relations suggest equilibration at temperatures in excess of 800oC. Low equilibration temperatures are in conflict with the unusually high equilibration temperatures, >1200oC (Smith, 2000) displayed by Group I xenoliths from this same volcanic field. Taken at face value, the geothermometric results indicate unusually high temperatures in the upper mantle, normal temperatures in the crust and the possibility of a kinked geotherm in the region. Curiously the LCVF lies in an area of "normal" heat flow, south of the Battle Mountain area of high heat flow but the number of heat flow measurements in the Lunar Crater area is very low (Humphreys et al., 2003; Sass, 2005). References: Humphreys et al., 2003, Int. Geol. Rev. 45: 575; Sass et al., 2005, http://pubs.usgs.gov/of/2005/1207/; Smith, 2000, JGR 105: 16769.

  3. Boar Semen Studies

    PubMed Central

    King, G. J.; Macpherson, J. W.

    1966-01-01

    A successful method for low temperature preservation of bull semen was modified for use with boar semen. Observations were made on the effects of varying cooling rate, equilibration time, freezing rate, glycerol concentration, method of glycerol addition, packaging containers, extender pH and tonicity. Observations indicate that boar semen should be cooled and frozen at a slower rate than bull semen. Within the ranges or methods examined, the other factors had little effect on recovery of motility after freezing. PMID:4226548

  4. Equilibrator: Modeling Chemical Equilibria with Excel

    ERIC Educational Resources Information Center

    Vander Griend, Douglas A.

    2011-01-01

    Equilibrator is a Microsoft Excel program for learning about chemical equilibria through modeling, similar in function to EQS4WIN, which is no longer supported and does not work well with newer Windows operating systems. Similar to EQS4WIN, Equilibrator allows the user to define a system with temperature, initial moles, and then either total…

  5. Modeling the movement and equilibrium of water in the body of ruminants in relation to estimating body composition by deuterium oxide dilution

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Arnold, R.N.

    1986-01-01

    Deuterium oxide (D/sub 2/O) dilution was evaluated for use in estimating body composition of ruminants. Empty body composition of cattle could not be accurately estimated by two- or three-compartment models when solved on the basis of clearance of D/sub 2/O from blood. A 29-compartment blood-flow model was developed from measured blood flow rates and water volumes of tissues of sheep. The rates of equilibration of water in tissues that were simulated by the blood-flow model were much faster than actual rates measured in sheep and cattle. The incorporation of diffusion hindrances for movement of water into tissues enabled the bloodmore » flow model to simulate the measured equilibration rates in tissues, but the values of the diffusion coefficients were different for each tissue. The D/sub 2/O-disappearance curve for blood simulated by the blood-flow model with diffusion limitations was comprised for four exponential components. The tissues and gastrointestinal tract contents were placed into five groups based upon the rate of equilibration. Water in the organs of the body equilibrated with water in blood within 3 min. Water in visceral fat, head, and some of the gastrointestinal tract tissues equilibrated within 8 to 16 min. Water in skeletal muscle, fat, and bone and the contents of some segments of the gastrointestinal tract equilibrated within 30 to 36 min. Water in the tissues and contents of the cecum and upper-large intestine equilibrated within 160 to 200 min. Water in ruminal tissue and contents equilibrated within 480 min.« less

  6. Re-equilibration after quenches in athermal martensites: Conversion delays for vapor-to-liquid domain-wall phases

    NASA Astrophysics Data System (ADS)

    Shankaraiah, N.; Murthy, K. P. N.; Lookman, T.; Shenoy, S. R.

    2015-06-01

    Entropy barriers and aging states appear in martensitic structural-transition models, slowly re-equilibrating after temperature quenches, under Monte Carlo dynamics. Concepts from protein folding and aging harmonic oscillators turn out to be useful in understanding these nonequilibrium evolutions. We show how the athermal, nonactivated delay time for seeded parent-phase austenite to convert to product-phase martensite arises from an identified entropy barrier in Fourier space. In an aging state of low Monte Carlo acceptances, the strain structure factor makes constant-energy searches for rare pathways to enter a Brillouin zone "golf hole" enclosing negative-energy states, and to suddenly release entropically trapped stresses. In this context, a stress-dependent effective temperature can be defined, that re-equilibrates to the quenched bath temperature.

  7. Exchange of organic solvents between the atmosphere and grass--the use of open top chambers.

    PubMed

    Binnie, J; Cape, J N; Mackie, N; Leith, I D

    2002-02-21

    Volatile organic compounds (VOC) are of increasing environmental significance as a result of continually increasing volumes of traffic on European roads. An open-top chamber fumigation system has been devised to investigate how these contaminants transfer between the atmosphere and the ground, and how they partition between and within air-plant-soil systems. Variation in chamber temperature, solar radiation in the chamber and chamber flow rate were identified as factors that affected final air concentrations. These were assessed and quantified for all individual chambers used--effectively characterising each chamber. The real-life VOC concentrations generated were stable and readily reproducible. Grass exposed to benzene, toluene, 1,1,1-trichloroethane and tetrachloroethene, respectively, equilibrated in response to a change in air concentration within hours. The rate of equilibration in exposed grass in all cases was independent of air temperature. 1,1,1-Trichloroethane and tetrachloroethene appear to be biologically inert demonstrating a simple physico-chemical approach to equilibrium, however, benzene and toluene do not appear independent of plant metabolic activity. Aqueous solubility can account for all of the toluene and benzene in the fumigated plant material.

  8. Effects of electron-ion temperature equilibration on inertial confinement fusion implosions.

    PubMed

    Xu, Barry; Hu, S X

    2011-07-01

    The electron-ion temperature relaxation essentially affects both the laser absorption in coronal plasmas and the hot-spot formation in inertial confinement fusion (ICF). It has recently been reexamined for plasma conditions closely relevant to ICF implosions using either classical molecular-dynamics simulations or analytical methods. To explore the electron-ion temperature equilibration effects on ICF implosion performance, we have examined two Coulomb logarithm models by implementing them into our hydrocodes, and we have carried out hydrosimulations for ICF implosions. Compared to the Lee-More model that is currently used in our standard hydrocodes, the two models predict substantial differences in laser absorption, coronal temperatures, and neutron yields for ICF implosions at the OMEGA Laser Facility [Boehly et al. Opt. Commun. 133, 495 (1997)]. Such effects on the triple-picket direct-drive design at the National Ignition Facility (NIF) have also been explored. Based on the validity of the two models, we have proposed a combined model of the electron-ion temperature-relaxation rate for the overall ICF plasma conditions. The hydrosimulations using the combined model for OMEGA implosions have shown ∼6% more laser absorption, ∼6%-15% higher coronal temperatures, and ∼10% more neutron yield, when compared to the Lee-More model prediction. It is also noticed that the gain for the NIF direct-drive design can be varied by ∼10% among the different electron-ion temperature-relaxation models.

  9. The Construction and Validation of All-Atom Bulk-Phase Models of Amorphous Polymers Using the TIGER2/TIGER3 Empirical Sampling Method

    PubMed Central

    Li, Xianfeng; Murthy, Sanjeeva; Latour, Robert A.

    2011-01-01

    A new empirical sampling method termed “temperature intervals with global exchange of replicas and reduced radii” (TIGER3) is presented and demonstrated to efficiently equilibrate entangled long-chain molecular systems such as amorphous polymers. The TIGER3 algorithm is a replica exchange method in which simulations are run in parallel over a range of temperature levels at and above a designated baseline temperature. The replicas sampled at temperature levels above the baseline are run through a series of cycles with each cycle containing four stages – heating, sampling, quenching, and temperature level reassignment. The method allows chain segments to pass through one another at elevated temperature levels during the sampling stage by reducing the van der Waals radii of the atoms, thus eliminating chain entanglement problems. Atomic radii are then returned to their regular values and re-equilibrated at elevated temperature prior to quenching to the baseline temperature. Following quenching, replicas are compared using a Metropolis Monte Carlo exchange process for the construction of an approximate Boltzmann-weighted ensemble of states and then reassigned to the elevated temperature levels for additional sampling. Further system equilibration is performed by periodic implementation of the previously developed TIGER2 algorithm between cycles of TIGER3, which applies thermal cycling without radii reduction. When coupled with a coarse-grained modeling approach, the combined TIGER2/TIGER3 algorithm yields fast equilibration of bulk-phase models of amorphous polymer, even for polymers with complex, highly branched structures. The developed method was tested by modeling the polyethylene melt. The calculated properties of chain conformation and chain segment packing agreed well with published data. The method was also applied to generate equilibrated structural models of three increasingly complex amorphous polymer systems: poly(methyl methacrylate), poly(butyl methacrylate), and DTB-succinate copolymer. Calculated glass transition temperature (Tg) and structural parameter profile (S(q)) for each resulting polymer model were found to be in close agreement with experimental Tg values and structural measurements obtained by x-ray diffraction, thus validating that the developed methods provide realistic models of amorphous polymer structure. PMID:21769156

  10. Defect chemistry and characterization of Hg(1-x)Cd(x)Te

    NASA Technical Reports Server (NTRS)

    Vydyanath, H. R.

    1981-01-01

    Undoped mercury cadmium telluride crystals were subjected to high temperature equilibration at temperatures ranging from 400 C to 655 C in various Hg atmospheres. Hall effect and mobility measurements were carried out on the crystals quenched to room temperature subsequent to the high temperature equilibration. The variation of the hole concentration in the cooled crystals at 77 K as a function of the partial pressure of Hg at the equlibration temperatures, together with a comparison of the hole mobility in the undoped samples with that in the copper and phosphorous doped samples yielded a defect model for the undoped crystals, according to which, the undoped crystals are essentially intrinsic at the equilibration temperatures and the native acceptor defects are doubly ionized. Native donor defects appear to be negligible in concentration, implying that the p to n conversion in these alloys is mainly due to residual foreign donor impurities. The thermodynamic constants for the intrinsic excitation process as well as for the incorporation of the doubly ionized native acceptor defects in the undoped crystals were obtained.

  11. A critical Examination of the Phenomenon of Bonding Area - Bonding Strength Interplay in Powder Tableting.

    PubMed

    Osei-Yeboah, Frederick; Chang, Shao-Yu; Sun, Changquan Calvin

    2016-05-01

    Although the bonding area (BA) and bonding strength (BS) interplay is used to explain complex tableting behaviors, it has never been experimentally proven. The purpose of this study is to unambiguously establish the distinct contributions of each by decoupling the contributions from BA and BS. To modulate BA, a Soluplus® powder was compressed into tablets at different temperatures and then broken following equilibration at 25°C. To modulate BS, tablets were equilibrated at different temperatures. To simultaneously modulate BA and BS, both powder compression and tablet breaking test were carried out at different temperatures. Lower tablet tensile strength is observed when the powder is compressed at a lower temperature but broken at 25°C. This is consistent with the increased resistance to polymer deformation at lower temperatures. When equilibrated at different temperatures, the tensile strength of tablets prepared under identical conditions increases with decreasing storage temperature, indicating that BS is higher at a lower temperature. When powder compression and tablet breaking are carried out at the same temperature, the profile with a maximum tensile strength at 4°C is observed due to the BA-BS interplay. By systematically varying temperature during tablet compression and breaking, we have experimentally demonstrated the phenomenon of BA-BS interplay in tableting.

  12. Thermogravimetric analysis for the determination of water release rate from microcrystalline cellulose dry powder and wet bead systems.

    PubMed

    Mayville, Francis C; Wigent, Rodney J; Schwartz, Joseph B

    2006-01-01

    The purpose of this work was to determine the total amount of water contained in dry powder and wet bead samples of microcrystalline cellulose, MCC, (Avicel PH-101), taken from various stages of the extrusion/marumerization process used to make beads and to determine the kinetic rates of water release from each sample. These samples were allowed to equilibrate in controlled humidity chambers at 25 degrees C. The total amount of water in each sample, after equilibration, was determined by thermogravimetric analysis (TGA) as a function of temperature. The rates of water release from these samples were determined by using isothermal gravimetric analysis (ITGA) as a function of time. Analysis of the results for these studies suggest that water was released from these systems by several different kinetic mechanisms. The water release mechanisms for these systems include: zero order, second order, and diffusion controlled kinetics. It is believed that all three kinetic mechanisms will occur at the same time, however; only one mechanism will be prominent. The prominent mechanism was based on the amount of water present in the sample.

  13. Accelerated aging in ultrathin films of a molecular glass former.

    PubMed

    Sepúlveda, A; Leon-Gutierrez, E; Gonzalez-Silveira, M; Rodríguez-Tinoco, C; Clavaguera-Mora, M T; Rodríguez-Viejo, J

    2011-07-08

    We report the thermodynamic measurement of the enthalpy released during the aging of supported films of a molecular glass former, toluene, at temperatures well below the glass transition temperature. By using microfabricated devices with very short equilibration times (below 1 s), we evidence a remarkable variation of the relaxation rate on decreasing film thickness from 100 nm down to a 7 nm thick film. Our results demonstrate that surface atoms are more efficient than bulk atoms in attaining low energy configurations within the potential energy landscape.

  14. Sensitivities of Earth's core and mantle compositions to accretion and differentiation processes

    NASA Astrophysics Data System (ADS)

    Fischer, Rebecca A.; Campbell, Andrew J.; Ciesla, Fred J.

    2017-01-01

    The Earth and other terrestrial planets formed through the accretion of smaller bodies, with their core and mantle compositions primarily set by metal-silicate interactions during accretion. The conditions of these interactions are poorly understood, but could provide insight into the mechanisms of planetary core formation and the composition of Earth's core. Here we present modeling of Earth's core formation, combining results of 100 N-body accretion simulations with high pressure-temperature metal-silicate partitioning experiments. We explored how various aspects of accretion and core formation influence the resulting core and mantle chemistry: depth of equilibration, amounts of metal and silicate that equilibrate, initial distribution of oxidation states in the disk, temperature distribution in the planet, and target:impactor ratio of equilibrating silicate. Virtually all sets of model parameters that are able to reproduce the Earth's mantle composition result in at least several weight percent of both silicon and oxygen in the core, with more silicon than oxygen. This implies that the core's light element budget may be dominated by these elements, and is consistent with ≤1-2 wt% of other light elements. Reproducing geochemical and geophysical constraints requires that Earth formed from reduced materials that equilibrated at temperatures near or slightly above the mantle liquidus during accretion. The results indicate a strong tradeoff between the compositional effects of the depth of equilibration and the amounts of metal and silicate that equilibrate, so these aspects should be targeted in future studies aiming to better understand core formation conditions. Over the range of allowed parameter space, core and mantle compositions are most sensitive to these factors as well as stochastic variations in what the planet accreted as a function of time, so tighter constraints on these parameters will lead to an improved understanding of Earth's core composition.

  15. Kinetics and Thermodynamics of Hydrogen Oxidation and Oxygen Reduction in Hydrophobic Room-Temperature Ionic Liquids

    PubMed Central

    Rollins, Julie B.; Conboy, John C.

    2010-01-01

    In this study 1-dodecyl-3-methylimidazolium (C12mim) bis(pentafluoroethylsulfonyl)imide (BETI) and 1-dodecylimidazolium (C12im) BETI hydrophobic room-temperature ionic liquids (RTILs) were synthesized and used as proton-conducting electrolytes in a nonhumidified feed gas electrochemical cell. The ionic conductivities of C12mimBETI and C12imBETI were similar and increased linearly with an increase in temperature from 20 to 130°C. However, when used in the electrochemical system the protic water-equilibrated C12imBETI had a larger maximum current and power density compared to the aprotic water-equilibrated C12mimBETI. The effect of water content on the reaction rates and thermodynamics of these hydrophobic RTILs was also examined. The efficiency of the C12mimBETI increased upon removal of water while that of the C12imBETI decreased in efficiency when water was removed. The water structure in these RTILs was examined using attenuated total internal reflection Fourier transform IR spectroscopy and depended on the chemical structure of the cation. These studies give further insight into the possible mechanism of proton transport in these RTIL systems. PMID:20414470

  16. Temperature-dependent dynamics of bovine casein micelles in the range 10-40 °C.

    PubMed

    Liu, Dylan Z; Weeks, Michael G; Dunstan, David E; Martin, Gregory J O

    2013-12-15

    Milk is a complex colloidal system that responds to changes in temperature imposed during processing. Whilst much has been learned about the effects of temperature on milk, little is known about the dynamic response of casein micelles to changes in temperature. In this study, a comprehensive physico-chemical study of casein micelles in skim milk was performed between 10 and 40 °C. When fully equilibrated, the amount of soluble casein, soluble calcium and the pH of skim milk all decreased as a function of increasing temperature, whilst the hydration and volume fraction of the casein micelles decreased. The effect of temperature on casein micelle size, as determined by dynamic light scattering and differential centrifugation, was less straightforward. Real-time measurements of turbidity and pH were used to investigate the dynamics of the system during warming and cooling of milk in the range 10-40 °C. Changes in pH are indicative of changes to the mineral system and the turbidity is a measure of alterations to the casein micelles. The pH and turbidity showed that alterations to both the casein micelles and the mineral system occurred very rapidly on warming. However, whilst mineral re-equilibration occurred very rapidly on cooling, changes to the casein micelle structure continued after 40 min of measurement, returning to equilibrium after 16 h equilibration. Casein micelle structure and the mineral system of milk were both dependent on temperature in the range 10-40 °C. The dynamic response of the mineral system to changes in temperature appeared almost instantaneous whereas equilibration of casein was considerably slower, particularly upon cooling. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Alkaline electrochemical cells and method of making

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1970-01-01

    Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

  18. An improved technique for the 2H/1H analysis of urines from diabetic volunteers

    USGS Publications Warehouse

    Coplen, T.B.; Harper, I.T.

    1994-01-01

    The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, ~ 1-2???, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, approximately 1-2%, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.

  19. Petit-spot as definitive evidence for partial melting in the asthenosphere caused by CO2

    NASA Astrophysics Data System (ADS)

    Machida, Shiki; Kogiso, Tetsu; Hirano, Naoto

    2017-02-01

    The deep carbon cycle plays an important role on the chemical differentiation and physical properties of the Earth's mantle. Especially in the asthenosphere, seismic low-velocity and high electrical conductivity due to carbon dioxide (CO2)-induced partial melting are expected but not directly observed. Here we discuss the experimental results relevant to the genesis of primitive CO2-rich alkali magma forming petit-spot volcanoes at the deformation front of the outer rise of the northwestern Pacific plate. The results suggest that primitive melt last equilibrated with depleted peridotite at 1.8-2.1 GPa and 1,280-1,290 °C. Although the equilibration pressure corresponds to the pressure of the lower lithosphere, by considering an equilibration temperature higher than the solidus in the volatile-peridotite system along with the temperature of the lower lithosphere, we conclude that CO2-rich silicate melt is always produced in the asthenosphere. The melt subsequently ascends into and equilibrates with the lower lithosphere before eruption.

  20. The effect of dietary neonicotinoid pesticides on non-flight thermogenesis in worker bumble bees (Bombus terrestris).

    PubMed

    Potts, Robert; Clarke, Rebecca M; Oldfield, Sophie E; Wood, Lisa K; Hempel de Ibarra, Natalie; Cresswell, James E

    2018-01-01

    For bumble bees (genus Bombus), the capacity for non-flight thermogenesis is essential for two fundamental processes undertaken by adult workers, namely recovery from torpor after chilling and brood incubation. Farmland bees can be widely exposed to dietary residues of neurotoxic neonicotinoid insecticides that appear in the nectar and pollen of treated bee-attractive crops, which may harm them. An earlier study shows that dietary neonicotinoids cause complex alterations to thermoregulation in honey bees, but their effect on the thermogenic capabilities of individual bumble bees has been untested previously. We therefore conducted laboratory trials involving separate dietary exposures of bumble bees to two neonicotinoids, imidacloprid and thiamethoxam, and we measured their effects on the thoracic temperatures of bees during recovery from chilling. Specifically, we used thermal imaging to measure the rates of rewarming by individual bees after chill-induced torpor and to quantify their equilibrated thoracic temperatures post-recovery. We found that both toxicants caused dose-dependent decreases in the rates of rewarming and in the equilibrated thoracic temperatures. As previously found in honey bees, the dose-response relationship for imidacloprid exhibited a biphasic hormesis with low-dose stimulation and high-dose inhibition, for which we propose a mechanism. Our present study is among the first to detect ecologically relevant effects on bees in neonicotinoid exposures involving dietary concentrations below 5 ppb. If the effects on thoracic temperatures that we observed over a short period were sustained, they could have ecologically significant impacts on farmland bumble bees. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Multi-point estimation of total energy expenditure: a comparison between zinc-reduction and platinum-equilibration methodologies.

    PubMed

    Sonko, Bakary J; Miller, Leland V; Jones, Richard H; Donnelly, Joseph E; Jacobsen, Dennis J; Hill, James O; Fennessey, Paul V

    2003-12-15

    Reducing water to hydrogen gas by zinc or uranium metal for determining D/H ratio is both tedious and time consuming. This has forced most energy metabolism investigators to use the "two-point" technique instead of the "Multi-point" technique for estimating total energy expenditure (TEE). Recently, we purchased a new platinum (Pt)-equilibration system that significantly reduces both time and labor required for D/H ratio determination. In this study, we compared TEE obtained from nine overweight but healthy subjects, estimated using the traditional Zn-reduction method to that obtained from the new Pt-equilibration system. Rate constants, pool spaces, and CO2 production rates obtained from use of the two methodologies were not significantly different. Correlation analysis demonstrated that TEEs estimated using the two methods were significantly correlated (r=0.925, p=0.0001). Sample equilibration time was reduced by 66% compared to those of similar methods. The data demonstrated that the Zn-reduction method could be replaced by the Pt-equilibration method when TEE was estimated using the "Multi-Point" technique. Furthermore, D equilibration time was significantly reduced.

  2. Shock Re-equilibration of Fluid Inclusions

    NASA Technical Reports Server (NTRS)

    Madden, M. E. Elwood; Horz, F.; Bodnar, R. J.

    2004-01-01

    Fluid inclusions (microscopic volumes of fluid trapped within minerals as they precipitate) are extremely common in terrestrial minerals formed under a wide range of geological conditions from surface evaporite deposits to kimberlite pipes. While fluid inclusions in terrestrial rocks are nearly ubiquitous, only a few fluid inclusion-bearing meteorites have been documented. The scarcity of fluid inclusions in meteoritic materials may be a result of (a) the absence of fluids when the mineral was formed on the meteorite parent body or (b) the destruction of fluid inclusions originally contained in meteoritic materials by subsequent shock metamorphism. However, the effects of impact events on pre-existing fluid inclusions trapped in target and projectile rocks has received little study. Fluid inclusions trapped prior to the shock event may be altered (re-equilibrated) or destroyed due to the high pressures, temperatures, and strain rates associated with impact events. By examining the effects of shock deformation on fluid inclusion properties and textures we may be able to better constrain the pressure-temperature path experienced by terrestrial and meteoritic shocked materials and also gain a clearer understanding of why fluid inclusions are rarely found in meteorite samples.

  3. Ultrafast equilibration of excited electrons in dynamical simulations.

    PubMed

    Lin, Zhibin; Allen, Roland E

    2009-12-02

    In our density-functional-based simulations of materials responding to femtosecond-scale laser pulses, we have observed a potentially useful phenomenon: the excited electrons automatically equilibrate to a Fermi-Dirac distribution within ∼100 fs, solely because of their coupling to the nuclear motion, even though the resulting electronic temperature is one to two orders of magnitude higher than the kinetic temperature defined by the nuclear motion. Microscopic simulations like these can then provide the separate electronic and kinetic temperatures, chemical potentials, pressures, and nonhydrostatic stresses as input for studies on larger lengths and timescales.

  4. Effect of increasing equilibration time of diluted bull semen up to 72 h prior to freezing on sperm quality parameters and calving rate following artificial insemination.

    PubMed

    Murphy, E M; Eivers, B; O'Meara, C M; Lonergan, P; Fair, S

    2018-03-01

    An equilibration period of approximately 3-4 h prior to semen cryopreservation is standard practice for maintaining membrane integrity and motility of bull sperm. However, a number of studies indicate that an overnight equilibration period prior to freezing results in improved post-thaw semen quality thus optimising pregnancy rates. The aim of this study was to assess the effect of increasing the equilibration time of bull semen up to 72 h before freezing on sperm quality parameters and calving rate (CR) following artificial insemination (AI) with frozen-thawed semen. The effect of holding semen at 4 °C for 6, 24, 48 or 72 h post dilution before freezing on subsequent post-thaw total and progressive motility (Experiment 1) and field fertility (n = 1640 inseminations, Experiment 2) of frozen-thawed semen was assessed. Equilibration time did not affect post-thaw total and progressive motility (P > 0.05). In addition, there was no effect (P > 0.05) of equilibration time on field fertility with a CR of 53.3, 50.5, 51.3 and 47.3 for the 6, 24, 48 and 72 h treatments, respectively. In conclusion, increasing the equilibration time of diluted bull semen from 6 to 72 h had no significant effect on CR, within the expected range of fertility outcomes, thus providing semen processing centres with flexibility in the time which semen can be held prior to freezing. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Oxygen isotope ratios in trees reflect mean annual temperature and humidity.

    PubMed

    Burk, R L; Stuiver, M

    1981-03-27

    Values of the oxygen isotope ratios (delta(18)O) in tree-ring cellulose closely reflect the delta(18)O values in atmospheric precipitation and hence mean annual temperature. The change in delta(18)O in cellulose is 0.41 per mil per degree Celsius for selected near-coastal stations. The values of delta(18)O in precipitation and cellulose also change with altitude, as demonstrated for Mount Rainier, Washington. A temperature lapse rate of 5.2 degrees +/- 0.5 degrees C per 1000 meters calculated from cellulose delta(18)O values agrees with the accepted mean annual lapse rate of 5 degrees C per 1000 meters for this region. Cellulose delta(18)O values and delta(18)O values of carbon dioxide equilibrated with leaf water differ by a fixed 16 per mil.

  6. Characterizing NZ equilibration in dynamically deformed system at 15, 25, 35 and 45 MeV/nucleon

    NASA Astrophysics Data System (ADS)

    Jedele, Andrea

    2017-09-01

    Neutron-proton equilibration is sensitive to the asymmetry energy in the nuclear equation of state. The process is governed by the contact time between the colliding nuclei and the gradient of the potential driving the equilibration. Recent work has shown NZ equilibration between the two largest fragments originating from the excited projectile-like fragment (PLF*) follows first-order kinetics in 70Zn, 64Zn and 64Ni symmetric reaction systems at 35 MeV/nucleon. The rate constant extracted was 3 zs-1, corresponding to a mean equilibration lifetime of 0.3 zs. An experiment has been proposed to examine the characteristics of NZ equilibration in 40Ca+ 64 , 70Zn at 15, 25, 35 and 45 MeV/nucleon with the NIMROD array.

  7. Testing charm quark equilibration in ultrahigh-energy heavy ion collisions with fluctuations

    NASA Astrophysics Data System (ADS)

    Graf, Thorben; Steinheimer, Jan; Bleicher, Marcus; Herold, Christoph

    2018-03-01

    Recent lattice QCD data on higher order susceptibilities of charm quarks provide the opportunity to explore charm quark equilibration in the early quark gluon plasma (QGP) phase. Here, we propose to use the lattice data on second- and fourth-order net charm susceptibilities to infer the charm quark equilibration temperature and the corresponding volume, in the early QGP stage, via a combined analysis of experimentally measured multiplicity fluctuations. Furthermore, the first perturbative results for the second- and fourth-order charm quark susceptibilities and their ratio are presented.

  8. Petit-spot as definitive evidence for partial melting in the asthenosphere caused by CO2

    PubMed Central

    Machida, Shiki; Kogiso, Tetsu; Hirano, Naoto

    2017-01-01

    The deep carbon cycle plays an important role on the chemical differentiation and physical properties of the Earth's mantle. Especially in the asthenosphere, seismic low-velocity and high electrical conductivity due to carbon dioxide (CO2)-induced partial melting are expected but not directly observed. Here we discuss the experimental results relevant to the genesis of primitive CO2-rich alkali magma forming petit-spot volcanoes at the deformation front of the outer rise of the northwestern Pacific plate. The results suggest that primitive melt last equilibrated with depleted peridotite at 1.8–2.1 GPa and 1,280–1,290 °C. Although the equilibration pressure corresponds to the pressure of the lower lithosphere, by considering an equilibration temperature higher than the solidus in the volatile–peridotite system along with the temperature of the lower lithosphere, we conclude that CO2-rich silicate melt is always produced in the asthenosphere. The melt subsequently ascends into and equilibrates with the lower lithosphere before eruption. PMID:28148927

  9. X-ray sensing materials stability: influence of ambient storage temperature on essential thermal properties of undoped vitreous selenium

    NASA Astrophysics Data System (ADS)

    Tonchev, D.; Mani, H.; Belev, G.; Kostova, I.; Kasap, S.

    2014-12-01

    Amorphous selenium (a-Se) is currently used in x-ray image detectors as an x-ray photoconductor. Normally a-Se films used in device applications are fabricated by the evaporation of vitreous bulk material loaded into boats in a typical vacuum deposition system. The resistance against crystallization is an important factor in both film and bulk forms of a-Se. Previous work has indicted that the resistance to crystallization is surprisingly more pronounced around 35 °C [1]. In this work we have therefore examined the essential thermal properties of vitreous selenium (99.999%) samples that have been stored at different temperatures. The thermal characterization experiments involved a series of DSC (Differential Scanning Calorimetry) measurements in which have monitored the glass transition and melting endotherms, and the crystallization exotherm in heating-cooling-heating scans. In DSC experiments, a sample would be heated to a temperature above the melting temperature, equilibrated, then cooled at a fixed rate down to 20 °C, then equilibrated and finally scanned again under a heating schedule. The samples were isothermally stored at temperatures corresponding to 18, 35 and 55 °C. The thermal analysis results show that there are distinct differences in the thermal properties. We have examined the stability in terms of the difference in the crystallization onset temperature (Tc) and the onset of glass transition temperature (Tg). We also examined the Hruby coefficient (Kgl) of these samples, that is Kgl = (Tc - Tg)/(Tm - Tc) where Tc is the crystallization onset temperature and Tm is the melting onset temperature. We have found Kgl to depend on the storage temperature. Surprisingly, we observed that the Hruby coefficient is actually larger at 35 °C compared to the values at 18 and 55 °C.

  10. Single Particle Jumps in Sheared SiO2

    NASA Astrophysics Data System (ADS)

    McMahon, Sean; Vollmayr-Lee, Katharina; Cookmeyer, Jonathan; Horbach, Juergen

    We study the dynamics of a sheared glass via molecular dynamics simulations. Using the BKS potential we simulate the strong glass former SiO2. The system is initially well equilibrated at a high temperature, then quenched to a temperature below the glass transition, and, after a waiting time at the desired low temperature, sheared with constant strain rate. We present preliminary results of an analysis of single particle trajectories of the sheared glass. We acknowledge the support via NSF REU Grant #PHY-1156964, DoD ASSURE program, and NSF-MRI CHE-1229354 as part of the MERCURY high-performance computer consortium. We thank G.P. Shrivastav, Ch. Scherer and B. Temelso.

  11. Interaction-induced backscattering in short quantum wires

    DOE PAGES

    Rieder, M. -T.; Micklitz, T.; Levchenko, A.; ...

    2014-10-06

    We study interaction-induced backscattering in clean quantum wires with adiabatic contacts exposed to a voltage bias. Particle backscattering relaxes such systems to a fully equilibrated steady state only on length scales exponentially large in the ratio of bandwidth of excitations and temperature. Here in this paper we focus on shorter wires in which full equilibration is not accomplished. Signatures of relaxation then are due to backscattering of hole excitations close to the band bottom which perform a diffusive motion in momentum space while scattering from excitations at the Fermi level. This is reminiscent to the first passage problem of amore » Brownian particle and, regardless of the interaction strength, can be described by an inhomogeneous Fokker-Planck equation. From general solutions of the latter we calculate the hole backscattering rate for different wire lengths and discuss the resulting length dependence of interaction-induced correction to the conductance of a clean single channel quantum wire.« less

  12. A critical analysis of the accuracy of several numerical techniques for combustion kinetic rate equations

    NASA Technical Reports Server (NTRS)

    Radhadrishnan, Krishnan

    1993-01-01

    A detailed analysis of the accuracy of several techniques recently developed for integrating stiff ordinary differential equations is presented. The techniques include two general-purpose codes EPISODE and LSODE developed for an arbitrary system of ordinary differential equations, and three specialized codes CHEMEQ, CREK1D, and GCKP4 developed specifically to solve chemical kinetic rate equations. The accuracy study is made by application of these codes to two practical combustion kinetics problems. Both problems describe adiabatic, homogeneous, gas-phase chemical reactions at constant pressure, and include all three combustion regimes: induction, heat release, and equilibration. To illustrate the error variation in the different combustion regimes the species are divided into three types (reactants, intermediates, and products), and error versus time plots are presented for each species type and the temperature. These plots show that CHEMEQ is the most accurate code during induction and early heat release. During late heat release and equilibration, however, the other codes are more accurate. A single global quantity, a mean integrated root-mean-square error, that measures the average error incurred in solving the complete problem is used to compare the accuracy of the codes. Among the codes examined, LSODE is the most accurate for solving chemical kinetics problems. It is also the most efficient code, in the sense that it requires the least computational work to attain a specified accuracy level. An important finding is that use of the algebraic enthalpy conservation equation to compute the temperature can be more accurate and efficient than integrating the temperature differential equation.

  13. Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

    USGS Publications Warehouse

    Gerlach, T.M.

    1993-01-01

    Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO2. The CO2-poor gases are typical of Type II volcanic gases (gerlach and Graeber, 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO2-rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical data shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032??C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the fO2 buffering process occurs by transfer of oxygen from the major species in the gas phase (H2O, CO2, SO2) to the lava during cooling and that the transfer of oxygen also controls the fugacities of several minor and trace species (H2, CO, H2S, S2, Cl2, F2), in addition to O2 during cooling. Gas/lava exchanges of other components are apparently insignificant and exert little influence, compared to oxygen exchange, during cooling. Oxygen transfer during cooling is variable, presumably reflecting short-term fluctuations in gas flow rates. Higher flow rates restrict the time available for gas/lava oxygen transfer and result in gases with higher equilibrium temperatures. Lower flow rates favor fO2-constrained equilibration by oxygen transfer down to lower temperatures. Thus, the chemical equilibrium preserved in these gases is a heterogeneous equilibrium constrained by oxygen fugacity, and the equilibrium temperatures implied by the compositions of the gases reflect the temperatures at which gas/lava oxygen exchange ceased. This conclusion challenges the common assumption that volcanic gases are released from lava in a state of chemical equilibrium and then continue equilibrating homogeneously with falling temperature until reaction rates are unable to keep pace with cooling. No evidence is found, moreover, that certain gas species are kinetically more responsive and able to equilibrate down to lower temperatures than those of the last gas/lava oxygen exchange. Homogeneous reaction rates in the gas phase are apparently slow compared to the time it took for the gases to move from the last site of gas/lava equilibration to the site of collection. An earlier set of data for higher temperature CO2-rich Type I volcanic gases, which come from sustained summit lava lake eruptions supplied by magma that experienced substantially shorter periods of crustal storage, shows fO2 buffering by oxygen transfer up to 1185??C. Oxygen fugacity measurements in drill holes into ponded lava flows suggest that buffering by oxygen transfer may control the fO2 of residual gases down to several hundred degrees below the solidus in the early stages of cooling. Although the details of the fO2 buffering mechanisms for oxygen transfer are unknown, the fact that fO2 buffering is effective from molten to subsolidus conditions suggests that the reaction mechanisms must change with cooling as the reactants change from predominantly melt, to melt plus crystals, to glass plus crystals. Mass balance calculations suggest that redox reactions between the gas and ferrous/ferric iron in the lava are plausible mechanisms for the oxygen transfer and that the fO2 of the gases is buffered by sliding ferrous/ferric equilibria in the erupting lavas. Contrary to expectations based on models predicting the oxidation of basalt by H2 and CO escape during crustal storage, CO2-rich Type I gases and CO2-poor Type II gases have identical oxygen fugacities despite greatly different crustal storage and degassing histories. Volcanic gas data give a tightly co

  14. Enhanced electron/fuel-ion equilibration through impurity ions: Studies applicable to NIF and Omega

    NASA Astrophysics Data System (ADS)

    Petrasso, R. D.; Sio, H.; Kabadi, N.; Lahmann, B.; Simpson, R.; Parker, C.; Frenje, J.; Gatu Johnson, M.; Li, C. K.; Seguin, F. H.; Rinderknecht, H.; Casey, D.; Grabowski, P.; Graziani, F.; Taitano, W.; Le, A.; Chacon, L.; Hoffman, N.; Kagan, G.; Simakov, A.; Zylstra, A.; Rosenberg, M.; Betti, R.; Srinivasan, B.; Mancini, R.

    2017-10-01

    In shock-driven exploding-pushers, a platform used extensively to study multi-species and kinetic effects, electrons and fuel ions are far out of equilibrium, as reflected by very different temperatures. However, impurity ions, even in small quantities, can couple effectively to the electrons, because of a Z2 dependence, and in turn, impurity ions can then strongly couple to the fuel ions. Through this mechanism, electrons and fuel-ions can equilibrate much faster than they otherwise would. This is a quantitative issue, depending upon the amount and Z of the impurity. For NIF and Omega, we consider the role of this process. Coupled non-linear equations, reflecting the temperatures of the three species, are solved for a range of conditions. Consideration is also given to ablatively driven implosions, since impurities can similarly affect the equilibration. This work was supported in part by DOE/NNSA DE-NA0002949 and DE-NA0002726.

  15. Ortho-para-hydrogen equilibration on Jupiter

    NASA Technical Reports Server (NTRS)

    Carlson, Barbara E.; Lacis, Andrew A.; Rossow, William B.

    1992-01-01

    Voyager IRIS observations reveal that the Jovian para-hydrogen fraction is not in thermodynamic equilibrium near the NH3 cloud top, implying that a vertical gradient exists between the high-temperature equilibrium value of 0.25 at depth and the cloud top values. The height-dependent para-hydrogen profile is obtained using an anisotropic multiple-scattering radiative transfer model. A vertical correlation is found to exist between the location of the para-hydrogen gradient and the NH3 cloud, strongly suggesting that paramagnetic conversion on NH3 cloud particle surfaces is the dominant equilibration mechanism. Below the NH3 cloud layer, the para fraction is constant with depth and equal to the high-temperature equilibrium value of 0.25. The degree of cloud-top equilibration appears to depend on the optical depth of the NH3 cloud layer. Belt-zone variations in the para-hydrogen profile seem to be due to differences in the strength of the vertical mixing.

  16. Some Thoughts on the Role of non-LTE Physics in ICF

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Colvin, J. D.

    An effort to develop sub-critical-density high-Z metal-doped and pure metal foams as laser-driven x-ray sources is described. The main idea is that the laser beams preferentially heat the electrons, and if the plasma is sufficiently low density so that the heating rate is greater than the equilibration rate via electron-ion collisions, then the electron temperature in the plasma is much greater than the ion temperature as long as the laser is on. In such a situation the plasma is not in local thermal equilibrium (LTE), it heats supersonically and volumetrically, and the conversion efficiency of laser beam energy to multi-keVmore » L-shell and K-shell radiation is much higher than what it would be in LTE plasma.« less

  17. Investigation of preparation techniques for δ2H analysis of keratin materials and a proposed analytical protocol

    USGS Publications Warehouse

    Qi, H.; Coplen, T.B.

    2011-01-01

    Accurate hydrogen isotopic measurements of keratin materials have been a challenge due to exchangeable hydrogen in the sample matrix and the paucity of appropriate isotopic reference materials for calibration. We found that the most reproducible δ2HVSMOW-SLAP and mole fraction of exchangeable hydrogen, x(H)ex, of keratin materials were measured with equilibration at ambient temperature using two desiccators and two different equilibration waters with two sets of the keratin materials for 6 days. Following equilibration, drying the keratin materials in a vacuum oven for 4 days at 60 °C was most critical. The δ2H analysis protocol also includes interspersing isotopic reference waters in silver tubes among samples in the carousel of a thermal conversion elemental analyzer (TC/EA) reduction unit. Using this analytical protocol, δ2HVSMOW-SLAP values of the non-exchangeable fractions of USGS42 and USGS43 human-hair isotopic reference materials were determined to be –78.5 ± 2.3 ‰ and –50.3 ± 2.8 ‰, respectively. The measured x(H)ex values of keratin materials analyzed with steam equilibration and N2 drying were substantially higher than those previously published, and dry N2 purging was unable to remove absorbed moisture completely, even with overnight purging. The δ2H values of keratin materials measured with steam equilibration were about 10 ‰ lower than values determined with equilibration in desiccators at ambient temperatures when on-line evacuation was used to dry samples. With steam equilibrations the x(H)ex of commercial keratin powder was as high as 28 %. Using human-hair isotopic reference materials to calibrate other keratin materials, such as hoof or horn, can introduce bias in δ2H measurements because the amount of absorbed water and the x(H)ex values may differ from those of unknown samples. Correct δ2HVSMOW-SLAP values of the non-exchangeable fractions of unknown human-hair samples can be determined with atmospheric moisture equilibration by normalizing with USGS42 and USGS43 human-hair reference materials when all materials have the same powder size.

  18. Fast analysis of curcuminoids from turmeric (Curcuma longa L.) by high-performance liquid chromatography using a fused-core column.

    PubMed

    Osorio-Tobón, J Felipe; Carvalho, Pedro I N; Barbero, Gerardo Fernández; Nogueira, Gislaine Chrystina; Rostagno, Mauricio Ariel; Meireles, Maria Angela de Almeida

    2016-06-01

    The recent development of fused-core technology in HPLC columns is enabling faster and highly efficient separations. This technology was evaluated for the development of a fast method for the analysis of main curcuminoids (curcumin, demethoxycurcumin and bisdemethoxycurcumin) present in extracts of turmeric (Curcuma longa L.). A step-by-step strategy was used to optimize temperature (40-55 °C), flow rate (1.0-2.5 mL min(-1)), mobile phase composition and equilibration time (1-5 min). A gradient method was developed using acidified water and acetonitrile combined with high column temperature (55 °C) and flow rate (2.5 mL min(-1)). Optimized conditions provided a method for the separation of these three curcuminoids in approximately 1.3 min with a total analysis time (sample-to-sample) of 7 min, including the clean-up and the re-equilibration of the column. Evaluation of chromatographic performance revealed excellent intraday and interday reproducibility (>99%), resolution (>2.23), selectivity (>1.12), peak symmetry (1.24-1.42) while presenting low limits of detection (<0.40 mg L(-1)) and quantification (<1.34 mg L(-1)). The robustness of the method was calculated according to the concentration/dilution of the sample and the injection volume. Several combinations of methanol and ethanol with water as sample solvents were evaluated and the best chromatographic results and extraction rate were obtained using 100% methanol. Finally, the developed method was validated with different extracts of turmeric rhizome and products that use turmeric in their formulation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. High temperature electronic excitation and ionization rates in gases

    NASA Technical Reports Server (NTRS)

    Hansen, Frederick

    1991-01-01

    The relaxation times for electronic excitation due to electron bombardment of atoms was found to be quite short, so that electron kinetic temperature (T sub e) and the electron excitation temperature (T asterisk) should equilibrate quickly whenever electrons are present. However, once equilibrium has been achieved, further energy to the excited electronic states and to the kinetic energy of free electrons must be fed in by collisions with heavy particles that cause vibrational and electronic state transitions. The rate coefficients for excitation of electronic states produced by heavy particle collision have not been well known. However, a relatively simple semi-classical theory has been developed here which is analytic up to the final integration over a Boltzmann distribution of collision energies; this integral can then be evaluated numerically by quadrature. Once the rate coefficients have been determined, the relaxation of electronic excitation energy can be evaluated and compared with the relaxation rates of vibrational excitation. Then the relative importance of these two factors, electronic excitation and vibrational excitation by heavy particle collision, on the transfer of energy to free electron motion, can be assessed.

  20. Extracting the Electron-Ion Temperature Relaxation Rate from Ion Stopping Experiments

    NASA Astrophysics Data System (ADS)

    Grabowski, Paul E.; Frenje, Johan A.; Benedict, Lorin X.

    2016-10-01

    Direct measurement of i-e equilibration rates at ICF-relevant conditions is a big challenge, as it is difficult to differentiate from other sinks and sources of energy, such as heat conduction and pdV work. Another method is to use information from ion stopping experiments. Such experiments at the OMEGA laser have made precision energy loss measurements of fusion products at these conditions. Combined with the multimonochromatic x-ray imager technique, which gives temporally and spatially resolved electron temperature and density, we have a robust stopping experiment. We propose to use such stopping measurements to assess the i-e temperature relaxation rate, since both processes involve energy exchange between electrons and ions. We require that the fusion products are 1) much faster than the thermal ions so that i-i collisions are negligible compared to i-e collisions and 2) slower than the thermal electrons so that the stopping obeys a linear friction law. Then the Coulomb logarithms associated with ion stopping and i-e temperature relaxation rate are identical and a measurement of the former provides the latter. Prepared by LLNL under Contract DE-AC52-07NA27344.

  1. Temporal response of hydraulic head, temperature, and chloride concentrations to sea-level changes, Floridan aquifer system, USA

    NASA Astrophysics Data System (ADS)

    Hughes, J. D.; Vacher, H. L.; Sanford, Ward E.

    2009-06-01

    Three-dimensional density-dependent flow and transport modeling of the Floridan aquifer system, USA shows that current chloride concentrations are not in equilibrium with current sea level and, second, that the geometric configuration of the aquifer has a significant effect on system responses. The modeling shows that hydraulic head equilibrates first, followed by temperatures, and then by chloride concentrations. The model was constructed using a modified version of SUTRA capable of simulating multi-species heat and solute transport, and was compared to pre-development conditions using hydraulic heads, chloride concentrations, and temperatures from 315 observation wells. Three hypothetical, sinusoidal sea-level changes occurring over 100,000 years were used to evaluate how the simulated aquifer responds to sea-level changes. Model results show that hydraulic head responses lag behind sea-level changes only where the Miocene Hawthorn confining unit is thick and represents a significant restriction to flow. Temperatures equilibrate quickly except where the Hawthorn confining unit is thick and the duration of the sea-level event is long (exceeding 30,000 years). Response times for chloride concentrations to equilibrate are shortest near the coastline and where the aquifer is unconfined; in contrast, chloride concentrations do not change significantly over the 100,000-year simulation period where the Hawthorn confining unit is thick.

  2. Fluid absorption solar energy receiver

    NASA Technical Reports Server (NTRS)

    Bair, Edward J.

    1993-01-01

    A conventional solar dynamic system transmits solar energy to the flowing fluid of a thermodynamic cycle through structures which contain the gas and thermal energy storage material. Such a heat transfer mechanism dictates that the structure operate at a higher temperature than the fluid. This investigation reports on a fluid absorption receiver where only a part of the solar energy is transmitted to the structure. The other part is absorbed directly by the fluid. By proportioning these two heat transfer paths the energy to the structure can preheat the fluid, while the energy absorbed directly by the fluid raises the fluid to its final working temperature. The surface temperatures need not exceed the output temperature of the fluid. This makes the output temperature of the gas the maximum temperature in the system. The gas can have local maximum temperatures higher than the output working temperature. However local high temperatures are quickly equilibrated, and since the gas does not emit radiation, local high temperatures do not result in a radiative heat loss. Thermal radiation, thermal conductivity, and heat exchange with the gas all help equilibrate the surface temperature.

  3. Temperature equilibration rate with Fermi-Dirac statistics.

    PubMed

    Brown, Lowell S; Singleton, Robert L

    2007-12-01

    We calculate analytically the electron-ion temperature equilibration rate in a fully ionized, weakly to moderately coupled plasma, using an exact treatment of the Fermi-Dirac electrons. The temperature is sufficiently high so that the quantum-mechanical Born approximation to the scattering is valid. It should be emphasized that we do not build a model of the energy exchange mechanism, but rather, we perform a systematic first principles calculation of the energy exchange. At the heart of this calculation lies the method of dimensional continuation, a technique that we borrow from quantum field theory and use in a different fashion to regulate the kinetic equations in a consistent manner. We can then perform a systematic perturbation expansion and thereby obtain a finite first-principles result to leading and next-to-leading order. Unlike model building, this systematic calculation yields an estimate of its own error and thus prescribes its domain of applicability. The calculational error is small for a weakly to moderately coupled plasma, for which our result is nearly exact. It should also be emphasized that our calculation becomes unreliable for a strongly coupled plasma, where the perturbative expansion that we employ breaks down, and one must then utilize model building and computer simulations. Besides providing different and potentially useful results, we use this calculation as an opportunity to explain the method of dimensional continuation in a pedagogical fashion. Interestingly, in the regime of relevance for many inertial confinement fusion experiments, the degeneracy corrections are comparable in size to the subleading quantum correction below the Born approximation. For consistency, we therefore present this subleading quantum-to-classical transition correction in addition to the degeneracy correction.

  4. Para hydrogen equilibration in the atmospheres of the outer planets

    NASA Technical Reports Server (NTRS)

    Conrath, Barney J.

    1986-01-01

    The thermodynamic behavior of the atmospheres of the Jovian planets is strongly dependent on the extent to which local thermal equilibration of the ortho and para states of molecular hydrogen is achieved. Voyager IRIS data from Jupiter imply substantial departures of the para hydrogen fraction from equilibrium in the upper troposphere at low latitudes, but with values approaching equilibrium at higher latitudes. Data from Saturn are less sensitive to the orth-para ratio, but suggest para hydrogen fractions near the equilibrium value. Above approximately the 200 K temperature level, para hydrogen conversion can enhance the efficiency of convection, resulting in a substantial increase in overturning times on all of the outer planets. Currently available data cannot definitively establish the ortho-para ratios in the atmospheres of Uranus and Neptune, but suggest values closer to local equilibrium than to the 3.1 normal ratio. Modeling of sub-millimeter wavelength measurements of these planets suggest thermal structures with frozen equilibrium lapse rates in their convective regions.

  5. Equilibration of energy in slow–fast systems

    PubMed Central

    Shah, Kushal; Gelfreich, Vassili; Rom-Kedar, Vered

    2017-01-01

    Ergodicity is a fundamental requirement for a dynamical system to reach a state of statistical equilibrium. However, in systems with several characteristic timescales, the ergodicity of the fast subsystem impedes the equilibration of the whole system because of the presence of an adiabatic invariant. In this paper, we show that violation of ergodicity in the fast dynamics can drive the whole system to equilibrium. To show this principle, we investigate the dynamics of springy billiards, which are mechanical systems composed of a small particle bouncing elastically in a bounded domain, where one of the boundary walls has finite mass and is attached to a linear spring. Numerical simulations show that the springy billiard systems approach equilibrium at an exponential rate. However, in the limit of vanishing particle-to-wall mass ratio, the equilibration rates remain strictly positive only when the fast particle dynamics reveal two or more ergodic components for a range of wall positions. For this case, we show that the slow dynamics of the moving wall can be modeled by a random process. Numerical simulations of the corresponding springy billiards and their random models show equilibration with similar positive rates. PMID:29183966

  6. Melt fracturing and healing: A mechanism for degassing and origin of silicic obsidian

    USGS Publications Warehouse

    Cabrera, A.; Weinberg, R.F.; Wright, H.M.N.; Zlotnik, S.; Cas, Ray A.F.

    2011-01-01

    We present water content transects across a healed fault in pyroclastic obsidian from Lami pumice cone, Lipari, Italy, using synchrotron Fourier transform infrared spectroscopy. Results indicate that rhyolite melt degassed through the fault surface. Transects define a trough of low water content coincident with the fault trace, surrounded on either side by high-water-content plateaus. Plateaus indicate that obsidian on either side of the fault equilibrated at different pressure-temperature (P-T) conditions before being juxtaposed. The curves into the troughs indicate disequilibrium and water loss through diffusion. If we assume constant T, melt equilibrated at pressures differing by 0.74 MPa before juxtaposition, and the fault acted as a low-P permeable path for H2O that diffused from the glass within time scales of 10 and 30 min. Assuming constant P instead, melt on either side could have equilibrated at temperatures differing by as much as 100 ??C, before being brought together. Water content on the fault trace is particularly sensitive to post-healing diffusion. Its preserved value indicates either higher temperature or lower pressure than the surroundings, indicative of shear heating and dynamic decompression. Our results reveal that water contents of obsidian on either side of the faults equilibrated under different P-T conditions and were out of equilibrium with each other when they were juxtaposed due to faulting immediately before the system was quenched. Degassing due to faulting could be linked to cyclical seismic activity and general degassing during silicic volcanic activity, and could be an efficient mechanism of producing low-water-content obsidian. ?? 2011 Geological Society of America.

  7. Paracetamol plasma and cerebrospinal fluid pharmacokinetics in children

    PubMed Central

    Anderson, B J; Holford, N H G; Woollard, G A; Chan, P L S

    1998-01-01

    Aims Paracetamol has a central action for both antipyresis and analgesia. Maximum temperature decrease and peak analgesia are reported at 1–2 h after peak plasma paracetamol concentration. We wished to determine the relationship between plasma and cerebrospinal fluid (CSF) pharmacokinetics in children. Methods Concentration-time profiles in plasma and CSF after nasogastric paracetamol 40 mg kg−1 were measured in nine children who had indwelling ventricular drains. Estimation of population pharmacokinetic parameters was made using both a standard two-stage population approach (MKMODEL) and a nonlinear mixed effect model (NONMEM). Results were standardized to a 70 kg person using an allometric power model. Results Both approaches gave similar estimates. NONMEM parameter estimates were clearance 10.2 l h−1 (CV 47%), volume of distribution 67.1 l (CV 58%) and absorption rate constant 0.77 h−1 (CV 49%). Cerebrospinal fluid concentrations lagged behind those of plasma. The equilibration half time was 0.72 h (CV 117%). The CSF/plasma partition coefficient was 1.18 (CV 8%). Conclusions Higher concentrations in the CSF probably reflect the lower free water volume of plasma. The CSF equilibration half time suggests that CSF kinetics approximate more closely to the effect compartment than plasma, but further time is required for paracetamol to exert its effects. Effect site concentrations equilibrate slowly with plasma. Paracetamol should be given 1–2 h before anticipated pain or fever in children. PMID:9764964

  8. Energy demand of cardioplegically perfused human hearts.

    PubMed

    Preusse, C J; Winter, J; Schulte, H D; Bircks, W

    1985-01-01

    Human adult hearts with aortic valve disease (n = 20) and hypertrophic obstructive cardiomyopathy (n = 1) were perfused intraoperatively with cold histidine buffered Bretschneider solution. During a seven minute cardioplegic perfusion the temperature level, the electrolyte level, the resistance of the left (LCA) and right coronary artery (RCA), and myocardial O2 consumption were analysed. Equilibration of K+ was terminated shortly after the start of the perfusion while Na+ equilibration lasted for about 5 minutes. Resistance of RCA did not change significantly, but that of the LCA was diminished significantly (p less than 0.025) within the perfusion period indicating a delayed washout of calcium from the extracellular space. Myocardial O2 consumption was reduced from 2.71 ml/min (1. minute) to 1.51 ml/min (4. minute) to 0.93 ml/min (7. minute) although the temperature had reached a low level after 3 minutes. The difference between 4. to 7. minutes is significant (p less than 0.001). By our results it is concluded that in adult hearts high-volume cardioplegic perfusion at a flow rate of 1 ml/min X gm at a perfusion pressure of 40 to 50 mmHg should be performed for at least 6 to 7 minutes to achieve a sufficient intra-ischemic myocardial protection.

  9. Two-temperature equilibration in warm dense hydrogen measured with x-ray scattering from the LCLS

    NASA Astrophysics Data System (ADS)

    Fletcher, Luke; High Energy Density Sciences Collaboration

    2017-10-01

    Understanding the properties of warm dense hydrogen plasmas is critical for modeling stellar and planetary interiors, as well as for inertial confinement fusion (ICF) experiments. Of central importance are the electron-ion collision and equilibration times that determine the microscopic properties in a high energy density state. Spectrally and angularly resolved x-ray scattering measurements from fs-laser heated hydrogen have resolved the picosecond evolution and energy relaxation from a two-temperature plasma towards thermodynamic equilibrium in the warm dense matter regime. The interaction of rapidly heated cryogenic hydrogen irradiated by a 400 nm, 5x1017 W/cm2 , 70 fs-laser is visualized with ultra-bright 5.5 kev x-ray pulses from the Linac Coherent Light (LCLS) source in 1 Hz repetition rate pump-probe setting. We demonstrate that the energy relaxation is faster than many classical binary collision theories that use ad hoc cutoff parameters used in the Landau-Spitzer determination of the Coulomb logarithm. This work was supported by the DOE Office of Science, Fusion Energy Science under contract No. SF00515 and supported under FWP 100182 and DOE Office of Basic Energy Sciences, Materials Sciences and Engineering Division, contract DE-AC02-76SF00515.

  10. Tolerance of brown bear spermatozoa to conditions of pre-freezing cooling rate and equilibration time.

    PubMed

    López-Urueña, E; Alvarez, M; Gomes-Alves, S; Martínez-Rodríguez, C; Borragan, S; Anel-López, L; de Paz, P; Anel, L

    2014-06-01

    Specific protocols for the cryopreservation of endangered Cantabrian brown bear spermatozoa are critical to create a genetic resource bank. The aim of this study was to assess the effect of cooling rates and equilibration time before freezing on post-thawed brown bear spermatozoa quality. Electroejaculates from 11 mature bears were extended to 100 × 10(6) spermatozoa/mL in a TES-Tris-Fructose-based extender, cryopreserved following performance of the respective cooling/equilibration protocol each sample was assigned to, and stored at -196 °C for further assessment. Before freezing, after thawing, and after 1 hour's incubation post-thawing at 37 °C (thermal stress test), the quality of the samples was assessed for motility by computer-assisted semen analysis, and for viability (SYBR-14/propidium iodide), acrosomal status (peanut agglutinin-fluorescein isothiocyanate /propidium iodide), and sperm chromatin stability (SCSA) by flow cytometry. In experiment 1, three cooling rates (0.25 °C/min, 1 °C/min, and 4 °C/min) to 5 °C were assessed. After thawing, total motility (%TM) was higher and percentage of damaged acrosomes (%dACR) was lower (P < 0.05) for 0.25 °C/min than for 4 °C/min. The thermal stress test data indicated equally poor quality (P < 0.05) for the 4 °C/min cooled samples in viability (%VIAB), %dACR, %TM, and progressive motility (%PM). In experiment 2, the effect of a pre-freezing equilibration period at 5 °C for 1 hour (cooling at 0.25 °C/min) was evaluated. Samples kept at 5 °C for 1 hour showed higher (P < 0.05) values than the nonequilibrated ones for both thawing (%dACR) and thermal stress test (%VIAB, %TM, and %PM). In experiment 3, samples stored without cooling and equilibration (direct freezing) were compared with the samples cooled at 0.25 °C/min and equilibrated for 1 hour (control freezing). Using thermal stress test, we observed that direct freezing causes damage in viability, acrosomal status, and motility of spermatozoa compared with the control group (P < 0.05). In conclusion, our results suggest that slow cooling rates to 5 °C and at least 1 hour equilibration time are necessary for the effective cryopreservation of brown bear sperm. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Temporal response of hydraulic head, temperature, and chloride concentrations to sea-level changes, Floridan aquifer system, USA

    USGS Publications Warehouse

    Hughes, J.D.; Vacher, H. Leonard; Sanford, W.E.

    2009-01-01

    Three-dimensional density-dependent flow and transport modeling of the Floridan aquifer system, USA shows that current chloride concentrations are not in equilibrium with current sea level and, second, that the geometric configuration of the aquifer has a significant effect on system responses. The modeling shows that hydraulic head equilibrates first, followed by temperatures, and then by chloride concentrations. The model was constructed using a modified version of SUTRA capable of simulating multi-species heat and solute transport, and was compared to pre-development conditions using hydraulic heads, chloride concentrations, and temperatures from 315 observation wells. Three hypothetical, sinusoidal sea-level changes occurring over 100,000 years were used to evaluate how the simulated aquifer responds to sea-level changes. Model results show that hydraulic head responses lag behind sea-level changes only where the Miocene Hawthorn confining unit is thick and represents a significant restriction to flow. Temperatures equilibrate quickly except where the Hawthorn confining unit is thick and the duration of the sea-level event is long (exceeding 30,000 years). Response times for chloride concentrations to equilibrate are shortest near the coastline and where the aquifer is unconfined; in contrast, chloride concentrations do not change significantly over the 100,000-year simulation period where the Hawthorn confining unit is thick. ?? US Government 2008.

  12. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chlistunoff, Jerzy; Pivovar, Bryan

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared andmore » equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.« less

  13. Analytic Methods for Predicting Significant Multi-Quanta Effects in Collisional Molecular Energy Transfer

    NASA Technical Reports Server (NTRS)

    Bieniek, Ronald J.

    1996-01-01

    Collision-induced transitions can significantly affect molecular vibrational-rotational populations and energy transfer in atmospheres and gaseous systems. This, in turn. can strongly influence convective heat transfer through dissociation and recombination of diatomics. and radiative heat transfer due to strong vibrational coupling. It is necessary to know state-to-state rates to predict engine performance and aerothermodynamic behavior of hypersonic flows, to analyze diagnostic radiative data obtained from experimental test facilities, and to design heat shields and other thermal protective systems. Furthermore, transfer rates between vibrational and translational modes can strongly influence energy flow in various 'disturbed' environments, particularly where the vibrational and translational temperatures are not equilibrated.

  14. The Perils of Partition: Difficulties in Retrieving Magma Compositions from Chemically Equilibrated Basaltic Meteorites

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.

    1996-01-01

    The chemical compositions of magmas can be derived from the compositions of their equilibrium minerals through mineral/magma partition coefficients. This method cannot be applied safely to basaltic rocks, either solidified lavas or cumulates, which have chemically equilibrated or partially equilibrated at subsolidus temperatures, i.e., in the absence of magma. Applying mineral/ melt partition coefficients to mineral compositions from such rocks will typically yield 'magma compositions' that are strongly fractionated and unreasonably enriched in incompatible elements (e.g., REE's). In the absence of magma, incompatible elements must go somewhere; they are forced into minerals (e.g., pyroxenes, plagioclase) at abundance levels far beyond those established during normal mineral/magma equilibria. Further, using mineral/magma partition coefficients with such rocks may suggest that different minerals equilibrated with different magmas, and the fractionation sequence of those melts (i.e., enrichment in incompatible elements) may not be consistent with independent constraints on the order of crystallization. Subsolidus equilibration is a reasonable cause for incompatible- element-enriched minerals in some eucrites, diogenites, and martian meteorites and offers a simple alternative to petrogenetic schemes involving highly fractionated magmas or magma infiltration metasomatism.

  15. Quantum glassiness in clean strongly correlated systems: an example of topological overprotection

    NASA Astrophysics Data System (ADS)

    Chamon, Claudio

    2005-03-01

    Describing matter at near absolute zero temperature requires understanding a system's quantum ground state and the low energy excitations around it, the quasiparticles, which are thermally populated by the system's contact to a heat bath. However, this paradigm breaks down if thermal equilibration is obstructed. I present solvable examples of quantum many-body Hamiltonians of systems that are unable to reach their ground states as the environment temperature is lowered to absolute zero. These examples, three dimensional generalizations of quantum Hamiltonians proposed for topological quantum computing, 1) have no quenched disorder, 2) have solely local interactions, 3) have an exactly solvable spectrum, 4) have topologically ordered ground states, and 5) have slow dynamical relaxation rates akin to those of strong structural glasses.

  16. Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

    PubMed

    Rubinstein, Leon I.; Pignolet, Louis H.

    1996-11-06

    The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2)-D(2) equilibration is general for 18-electron hydrido Pt-AuPPh(3) clusters.

  17. A relativistic dissipative hydrodynamic description for systems including particle number changing processes

    NASA Astrophysics Data System (ADS)

    El, Andrej; Muronga, Azwinndini; Xu, Zhe; Greiner, Carsten

    2010-12-01

    Relativistic dissipative hydrodynamic equations are extended by taking into account particle number changing processes in a gluon system, which expands in one dimension boost-invariantly. Chemical equilibration is treated by a rate equation for the particle number density based on Boltzmann equation and Grad's ansatz for the off-equilibrium particle phase space distribution. We find that not only the particle production, but also the temperature and the momentum spectra of the gluon system, obtained from the hydrodynamic calculations, are sensitive to the rates of particle number changing processes. Comparisons of the hydrodynamic calculations with the transport ones employing the parton cascade BAMPS show the inaccuracy of the rate equation at large shear viscosity to entropy density ratio. To improve the rate equation, Grad's ansatz has to be modified beyond the second moments in momentum.

  18. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    NASA Astrophysics Data System (ADS)

    Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

    2016-09-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

  19. Circadian rhythm asynchrony in man during hypokinesis.

    NASA Technical Reports Server (NTRS)

    Winget, C. M.; Vernikos-Danellis, J.; Cronin, S. E.; Leach, C. S.; Rambaut, P. C.; Mack, P. B.

    1972-01-01

    Posture and exercise were investigated as synchronizers of certain physiologic rhythms in eight healthy male subjects in a defined environment. Four subjects exercised during bed rest. Body temperature (BT), heart rate, plasma thyroid hormone, and plasma steroid data were obtained from the subjects for a 6-day ambulatory equilibration period before bed rest, 56 days of bed rest, and a 10-day recovery period after bed rest. The results indicate that the mechanism regulating the circadian rhythmicity of the cardiovascular system is rigorously controlled and independent of the endocrine system, while the BT rhythm is more closely aligned to the endocrine system.

  20. Investigating catalyst coated membrane equilibration time for polymer electrolyte membrane fuel cell manufacturing

    NASA Astrophysics Data System (ADS)

    Cote, Philippe

    Mercedes-Benz Canada Inc., Fuel Cell Division, manufactures polymer electrolyte membrane fuel cell stacks for use in vehicles. The manufacturing line is being optimized for efficiency and quality control, in order to uphold the high standards of Mercedes-Benz Inc. vehicles. In an operating polymer electrolyte membrane fuel cell, the catalyst coated membrane facilitates the electrochemical reaction that generates electricity. This research examines the equilibration of catalyst coated membrane rolls to controlled temperature and humidity conditions, before they are used in the manufacturing of polymer electrolyte membrane fuel cells. Equilibration involves allowing the water content in the catalyst coated membrane to stabilize at the controlled conditions, in order to reduce mechanical stress in the material for better manufacturability. Initial equilibration measurements were conducted on discrete catalyst coated membrane samples using novel electronic conductivity measurements of the catalyst layer, and compared to ionic conductivity measurements of the membrane. Electronic conductivity measurements are easier to implement in the manufacturing environment than the more complex ionic conductivity measurements. When testing discrete catalyst coated membrane samples in an environmental chamber, the equilibration trends for the measured ionic and electronic conductivity signals were similar enough to permit us to adapt the electronic conductivity measurements for catalyst coated membrane in roll form. Equilibration measurements of catalyst coated membrane rolls were optimized to achieve a robust and repeatable procedure which could be used in the manufacturing environment at Mercedes-Benz Canada Inc., Fuel Cell Division.

  1. Numerical quantification of habitability in serpentinizing systems

    NASA Astrophysics Data System (ADS)

    Som, S.; Alperin, M. J.; Hoehler, T. M.

    2012-12-01

    The likely presence of liquid water in contact with olivine-bearing rocks on Mars, the detection of serpentine minerals and of methane emissions possibly consistent with serpentinization, and the observation of serpentine-associated methane-cycling communities on Earth have all led to excitement over the potential of such systems to host life on Mars, even into the present day. However, the habitability of subsurface serpentinizing systems on Mars does not necessarily follow from these qualitative observations. In particular, while the production of H2 during serpentinization could provide methanogens with a needed substrate, the alkaline conditions and corresponding potential for carbon limitation that arise in concert are negatives against which H2 supply must be balanced. We considered this balance via a coupled geochemical-bioenergetic model that weighs the outputs of serpentinization against the metabolic requirements of methanogenesis, in an energetic frame of reference. Serpentinization is modeled using the "Geochemist's Workbench" (GWB) whereby ultramafic harzburgite rocks are reacted with oxygen and sulfate depleted seawater. Reaction kinetics are not explicitly considered, but comparable effects of partial reaction are approximated by assuming post-reaction dilution of equilibrated fluids. The output of GWB serves as the input to the bioenergetic model, which calculates methanogenic energy yields based on spherically-symmetrical diffusion of substrates to a cell followed by reaction at the diffusion-limited rate. Membrane selectivity for substrate transport is explicitly considered. Results will be report updates for two scenarios: (i) High temperature serpentinization followed by cooling and transport of equilibrated fluid to a lower temperature regime accessible to biology; (ii) Serpentinization within the biologically-tolerated range of temperatures. Such coupled models demonstrate that environmental variability with respect to both water-rock reaction, temperature, and biologically-mediated methanogenesis drive orders of magnitude variability in the energy available in methanogenic metabolism.

  2. [Cryopreservation of mouse embryos in ethylene glycol-based solutions: a search for the optimal and simple protocols].

    PubMed

    Luo, Ming-Jiu; Liu, Na; Miao, De-Qiang; Lan, Guo-Cheng; Suo-Feng; Chang, Zhong-Le; Tan, Jing-He

    2005-09-01

    Although ethylene glycol (EG) has been widely used for embryo cryopreservation in domestic animals, few attempts were made to use this molecule to freeze mouse and human embryos. In the few studies that used EG for slow-freezing of mouse and human embryos, complicated protocols for human embryos were used, and the protocols need to be simplified. Besides, freezing mouse morula with EG as a cryoprotectant has not been reported. In this paper, we studied the effects of embryo stages, EG concentration, duration and procedure of equilibration, sucrose supplementation and EG removal after thawing on the development of thawed mouse embryos, using the simple freezing and thawing procedures for bovine embryos. The blastulation and hatching rates (81.92% +/- 2.24% and 68.56% +/- 2.43%, respectively) of the thawed late compact morulae were significantly (P < 0.05) higher than those of embryos frozen-thawed at other stages. When mouse late compact morulae were frozen with different concentrations of EG, the highest rates of blastocyst formation and hatching were obtained with 1.8mol/L EG. The blastulation rate was significantly higher when late morulae were equilibrated in 1.8 mol/L EG for 10 min prior to freezing than when they were equilibrated for 30 min, and the hatching rate of embryos exposed to EG for 10 min was significantly higher than that of embryos exposed for 20 and 30 min. Both rates of blastocyst formation and hatching obtained with two-step equilibration were higher (P < 0.05) than with one-step equilibration in 1.8 mol/L EG. Addition of sucrose to the EG-based solution had no beneficial effects. On the contrary, an increased sucrose level (0.4 mol/L) in the solution impaired the development of the frozen-thawed embryos. In contrast, addition of 0.1 mol/L sucrose to the propylene glycol (PG)-based solution significantly improved the development of the frozen-thawed embryos. Elimination of the cryoprotectant after thawing did not improve the development of the thawed embryos. The cell numbers were less (P < 0.05) in blastocysts developed from the thawed morulae than in the in vivo derived ones. In summary, embryo stage, EG concentration, duration and procedure of equilibration and sucrose supplementation had marked effects on development of the thawed mouse embryos, and a protocol for cryopreservation of mouse embryos is recommended in which the late morulae are frozen in 1.8 mol/L EG using the simple freezing and thawing procedures of bovine embryos after a two-step equilibration and the embryos can be cultured or transferred without EG removal after thawing.

  3. Fast equilibration protocol for million atom systems of highly entangled linear polyethylene chains

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sliozberg, Yelena R.; TKC Global, Inc., Aberdeen Proving Ground, Maryland 21005; Kröger, Martin

    Equilibrated systems of entangled polymer melts cannot be produced using direct brute force equilibration due to the slow reptation dynamics exhibited by high molecular weight chains. Instead, these dense systems are produced using computational techniques such as Monte Carlo-Molecular Dynamics hybrid algorithms, though the use of soft potentials has also shown promise mainly for coarse-grained polymeric systems. Through the use of soft-potentials, the melt can be equilibrated via molecular dynamics at intermediate and long length scales prior to switching to a Lennard-Jones potential. We will outline two different equilibration protocols, which use various degrees of information to produce the startingmore » configurations. In one protocol, we use only the equilibrium bond angle, bond length, and target density during the construction of the simulation cell, where the information is obtained from available experimental data and extracted from the force field without performing any prior simulation. In the second protocol, we moreover utilize the equilibrium radial distribution function and dihedral angle distribution. This information can be obtained from experimental data or from a simulation of short unentangled chains. Both methods can be used to prepare equilibrated and highly entangled systems, but the second protocol is much more computationally efficient. These systems can be strictly monodisperse or optionally polydisperse depending on the starting chain distribution. Our protocols, which utilize a soft-core harmonic potential, will be applied for the first time to equilibrate a million particle system of polyethylene chains consisting of 1000 united atoms at various temperatures. Calculations of structural and entanglement properties demonstrate that this method can be used as an alternative towards the generation of entangled equilibrium structures.« less

  4. Intrauterine temperature during intrapartum amnioinfusion: a prospective observational study.

    PubMed

    Tomlinson, T M; Schaecher, C; Sadovsky, Y; Gross, G

    2012-07-01

    To determine the influence of routine intrapartum amnioinfusion (AI) on intrauterine temperature. Prospective observational study. Maternity unit, Barnes Jewish Hospital, St Louis, MO, USA. Forty women with singleton gestations and an indication for intrapartum intrauterine pressure catheter placement. Using a temperature probe, we digitally recorded intrauterine temperature every 10 minutes during labour. Amnioinfusion was administered according to a standard protocol using saline equilibrated to the ambient temperature. Mean intrauterine temperature during labour. Participants were monitored for a mean of 280 minutes (range 20-820). A total of 164 intrauterine temperature readings in the AI cohort were compared with 797 control measurements. When compared with controls, we observed a lower intrauterine temperature in the AI cohort (36.4 versus 37.4°C, P<0.01). More measurements in the AI cohort were recorded in the presence of intrapartum fever (40% versus 30%). A subgroup analysis of measurements recorded in afebrile parturients revealed an even greater effect of AI (1.5°C decrease, 37.3 versus 35.8°C, P<0.01). Routine intrapartum AI using saline equilibrated to a mean ambient temperature of 25.0°C reduces intrauterine temperature and may thereby affect fetal core temperature. © 2012 The Authors BJOG An International Journal of Obstetrics and Gynaecology © 2012 RCOG.

  5. A conceptual geochemical model of the geothermal system at Surprise Valley, CA

    NASA Astrophysics Data System (ADS)

    Fowler, Andrew P. G.; Ferguson, Colin; Cantwell, Carolyn A.; Zierenberg, Robert A.; McClain, James; Spycher, Nicolas; Dobson, Patrick

    2018-03-01

    Characterizing the geothermal system at Surprise Valley (SV), northeastern California, is important for determining the sustainability of the energy resource, and mitigating hazards associated with hydrothermal eruptions that last occurred in 1951. Previous geochemical studies of the area attempted to reconcile different hot spring compositions on the western and eastern sides of the valley using scenarios of dilution, equilibration at low temperatures, surface evaporation, and differences in rock type along flow paths. These models were primarily supported using classical geothermometry methods, and generally assumed that fluids in the Lake City mud volcano area on the western side of the valley best reflect the composition of a deep geothermal fluid. In this contribution, we address controls on hot spring compositions using a different suite of geochemical tools, including optimized multicomponent geochemistry (GeoT) models, hot spring fluid major and trace element measurements, mineralogical observations, and stable isotope measurements of hot spring fluids and precipitated carbonates. We synthesize the results into a conceptual geochemical model of the Surprise Valley geothermal system, and show that high-temperature (quartz, Na/K, Na/K/Ca) classical geothermometers fail to predict maximum subsurface temperatures because fluids re-equilibrated at progressively lower temperatures during outflow, including in the Lake City area. We propose a model where hot spring fluids originate as a mixture between a deep thermal brine and modern meteoric fluids, with a seasonally variable mixing ratio. The deep brine has deuterium values at least 3 to 4‰ lighter than any known groundwater or high-elevation snow previously measured in and adjacent to SV, suggesting it was recharged during the Pleistocene when meteoric fluids had lower deuterium values. The deuterium values and compositional characteristics of the deep brine have only been identified in thermal springs and groundwater samples collected in proximity to structures that transmit thermal fluids, suggesting the brine may be thermal in nature. On the western side of the valley at the Lake City mud volcano, the deep brine-meteoric water mixture subsequently boils in the shallow subsurface, precipitates calcite, and re-equilibrates at about 130 °C. On the eastern side of the valley, meteoric fluid mixes to a greater extent with the deep brine, cools conductively without boiling, and the composition is modified as dissolved elements are sequestered by secondary minerals that form along the cooling and outflow path at temperatures <130 °C. Re-equilibration of geothermal fluids at lower temperatures during outflow explains why subsurface temperature estimates based on classical geothermometry methods are highly variable, and fail to agree with temperature estimates based on dissolved sulfate-oxygen isotopes and results of classical and multicomponent geothermometry applied to reconstructed deep well fluids. The proposed model is compatible with the idea suggested by others that thermal fluids on the western and eastern side of the valley have a common source, and supports the hypothesis that low temperature re-equilibration during west to east flow is the major control on hot spring fluid compositions, rather than dilution, evaporation, or differences in rock type.

  6. Neutral Gas Temperature Estimates in an Inductively Coupled CF4 Plasma by Fitting Diatomic Emission Spectra

    NASA Technical Reports Server (NTRS)

    Cruden, Brett A.; Rao, M. V. V. S.; Sharma, Surendra P.; Meyyappan, M.

    2001-01-01

    This work examines the accuracy of plasma neutral temperature estimates by fitting the rotational band envelope of different diatomic species in emission. Experiments are performed in an inductively coupled CF4 plasma generated in a Gaseous Electronics Conference reference cell. Visible and ultraviolet emission spectra are collected at a power of 300 W (approximately 0.7 W/cc) and pressure of 30 mtorr. The emission bands of several molecules (CF, CN, C2, CO, and SiF) are fit simultaneously for rotational and vibrational temperatures and compared. Four different rotational temperatures are obtained: 1250 K for CF and CN, 1600 K for CO, 1800 K for C2, and 2300 K for SiF. The vibrational temperatures obtained vary from 1750-5950 K, with the higher vibrational temperatures generally corresponding to the lower rotational temperatures. These results suggest that the different species have achieved different degrees of equilibration between the rotational and vibrational modes and may not be equilibrated with the translational temperatures. The different temperatures are also related to the likelihood that the species are produced by ion bombardment of the surface, with etch products like SiF, CO, and C2 having higher temperatures than species expected to have formed in the gas phase.

  7. High mobility, dual layer, c-axis aligned crystalline/amorphous IGZO thin film transistor

    NASA Astrophysics Data System (ADS)

    Chung, Chen-Yang; Zhu, Bin; Greene, Raymond G.; Thompson, Michael O.; Ast, Dieter G.

    2015-11-01

    We demonstrate a dual layer IGZO thin film transistor (TFT) consisting of a 310 °C deposited c-axis aligned crystal (CAAC) 20 nm thick channel layer capped by a second, 30 nm thick, 260 °C deposited amorphous IGZO layer. The TFT exhibits a saturation field-effect mobility of ˜20 cm2/V s, exceeding the mobility of 50 nm thick single layer reference TFTs fabricated with either material. The deposition temperature of the second layer influences the mobility of the underlying transport layer. When the cap layer is deposited at room temperature (RT), the mobility in the 310 °C deposited CAAC layer is initially low (6.7 cm2/V s), but rises continuously with time over 58 days to 20.5 cm2/V s, i.e., to the same value as when the second layer is deposited at 260 °C. This observation indicates that the two layers equilibrate at RT with a time constant on the order of 5 × 106 s. An analysis based on diffusive transport indicates that the room temperature diffusivity must be of the order of 1 × 10-18 cm2 s-1 with an activation enthalpy EA < 0.2 eV for the mobility limiting species. The findings are consistent with a hypothesis that the amorphous layer deposited on top of the CAAC has a higher solubility for impurities and/or structural defects than the underlying nanocrystalline transport layer, and that the equilibration of the mobility limiting species is rate limited by hydrogen diffusion, whose known diffusivity fits these estimates.

  8. Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

    NASA Astrophysics Data System (ADS)

    Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

    2012-12-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the "onion-skin" texture observed in weathered obsdians, with large hydration stresses leading to spheroidal fracture. Long-term experiments derived from archaeological samples, however, suggest that there remain significant uncertainties. Analysis of younger samples (< 2500 years) from the Chalco site in Mexico yield results consistent with laboratory experients where diffusion rates are proportional to t0.4235, and suggest small changes in the average paleo-hydration temperature. Older samples, however, from the complexly stratified site of Çatalhöyük, central Anatolia, Turkey, suggest near linear-with-time rates. This is consistent with other observations of realtively old samples. The two trends observed in the latter, however, do not necessarily correlate with sourcing data. The origin of these differences remains unexplained. Effort by LMA and DRC was supported by research sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy.

  9. Numerical experiments on evaporation and explosive boiling of ultra-thin liquid argon film on aluminum nanostructure substrate

    NASA Astrophysics Data System (ADS)

    Wang, Weidong; Zhang, Haiyan; Tian, Conghui; Meng, Xiaojie

    2015-04-01

    Evaporation and explosive boiling of ultra-thin liquid film are of great significant fundamental importance for both science and engineering applications. The evaporation and explosive boiling of ultra-thin liquid film absorbed on an aluminum nanostructure solid wall are investigated by means of molecular dynamics simulations. The simulated system consists of three regions: liquid argon, vapor argon, and an aluminum substrate decorated with nanostructures of different heights. Those simulations begin with an initial configuration for the complex liquid-vapor-solid system, followed by an equilibrating system at 90 K, and conclude with two different jump temperatures, including 150 and 310 K which are far beyond the critical temperature. The space and time dependences of temperature, pressure, density number, and net evaporation rate are monitored to investigate the phase transition process on a flat surface with and without nanostructures. The simulation results reveal that the nanostructures are of great help to raise the heat transfer efficiency and that evaporation rate increases with the nanostructures' height in a certain range.

  10. Numerical experiments on evaporation and explosive boiling of ultra-thin liquid argon film on aluminum nanostructure substrate.

    PubMed

    Wang, Weidong; Zhang, Haiyan; Tian, Conghui; Meng, Xiaojie

    2015-01-01

    Evaporation and explosive boiling of ultra-thin liquid film are of great significant fundamental importance for both science and engineering applications. The evaporation and explosive boiling of ultra-thin liquid film absorbed on an aluminum nanostructure solid wall are investigated by means of molecular dynamics simulations. The simulated system consists of three regions: liquid argon, vapor argon, and an aluminum substrate decorated with nanostructures of different heights. Those simulations begin with an initial configuration for the complex liquid-vapor-solid system, followed by an equilibrating system at 90 K, and conclude with two different jump temperatures, including 150 and 310 K which are far beyond the critical temperature. The space and time dependences of temperature, pressure, density number, and net evaporation rate are monitored to investigate the phase transition process on a flat surface with and without nanostructures. The simulation results reveal that the nanostructures are of great help to raise the heat transfer efficiency and that evaporation rate increases with the nanostructures' height in a certain range.

  11. The Thermal History of Enstatite Chondrites

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Benoit, P. H.; Sears, D. W. G.

    1992-07-01

    In an attempt to decipher the complicated thermal history of the enstatite chondrites, the CaS enstatite (Larimer and Buseck, 1974; Fogel et al., 1989), cubic sulfide (Skinner and Luce, 1971) and sphalerite (Kissin, 1989; El Goresy and Ehlers, 1989) systems have been applied, but the results have not been straightforward. The CaS-En thermometer gives metamorphic temperatures which appear reasonable, but which do not correlate well with petrologic type. The cubic sulfides yield reasonable temperatures for the EH chondrites, but the values for EL chondrites are very low. To some extent, the problem has been the lack of low petrologic type EL chondrites. Here we discuss data for the recently discovered EL3 chondrites (Chang et al., 1992) and we examine the applicability of the Fe-Ni-P system for thermometry. The CaS-En thermometer uses three reactions including equilibria between metal, CaS, SiO2, enstatite and FeS. The method is crucially dependent on the activity coefficients for Si and CaSiO3 which are in solid solutions with metal and enstatite, respectively. The cubic sulfide thermometer uses the solubility of FeS in MgS and MnS, while the ZnS thermometer (which is pressure-dependent) uses the solubility of FeS in ZnS. Current equilibration temperature estimates for enstatite chondrites including the EL3 chondrites are listed in Table 1. Table 1. Estimates of equilibration temperatures (degrees C) for enstatite chondrites.* Petrologic type EH EL System 3 4 5 6 3 4 5 6 En-CaS 1030 950 830 - 830 - - 1025 Cubic sulf 400 680 600 - <<400 - - <400 ZnS 410 (1859)+ - - 500 - - 550 Fe-Ni-P <450 500 550 - <<450 - - <450 *Literature data (see text), present data (bold type). +Heavily shocked. In an attempt to use the Fe-Ni-P system as a thermometer for enstatite chondrites, we used the phase diagram of Doan and Goldstein (1970). Like the other systems, this required extrapolation to lower temperatures (Fig. 1). The temperatures calculated from this system mirror those of the sulfides, suggesting major differences in the thermal history of the EL and EH chondrites. Two points may be made from the data in Table 1. The EH3 and EL3 chondrites have similar En-CaS equilibration temperatures to those of the higher petrologic types which we suspect reflect pre-metamorphic equilibria. Second, both the cubic sulfides and the phosphides yield metamorphic temperatures for the EH chondrites which are similar to those for ordinary chondrites, while EL chondrites yield very low temperatures. The EL chondrite parent body must have cooled at especially slow rates, perhaps because it was much larger than the EH parent body, or maybe the cooling rate on EL body was governed by the attenuation of the heat source rather than burial depth. Chang Y., Benoit P.H. and Sears D.W.G. (1992) Lunar and Planet. Sci. 23, 217-218. Doan A.S. and Goldstein J.I. (1970) Met. Trans. 1, 1759-1767. El Goresy A. and Ehlers K (1989) Geochim. Cosmochim. Acta 53, 1657-1668. Fogel R.A., Hess P.C. and Rutherford M.C. (1989) Geochim. Cosmochim. Acta 53, 2735-2746. Kissin S.A.(1989) Geochim. Cosmochim. Acta 53, 1649-1655. Larimer J.W. and Buseck P.R. (1974) Geochim. Cosmochim. Acta 38, 471-477. Skinner B.J. and Luce F.D. (1971) Amer. Min. 56, 1269-1296. Figure 1, which in the hard copy appears here, shows isotherm from the Fe-Ni-P phase diagram with data for enstatite chondrites superimposed.

  12. Biophase equilibration times.

    PubMed

    Veng-Pedersen, P; Mandema, J W; Danhof, M

    1991-09-01

    Various methods for describing how quickly a drug equilibrates at the biophase are proposed. The biophase equilibration time (BET) is the time it takes the biophase drug level to reach a given percentage (p) of its predicted steady state in a drug administration that leads to a steady-state condition. The time to reach biophase equilibrium may be defined as the BET value for p = 95, and the 50% biophase equilibration time is obtained when p = 50. Biophase equilibration profiles (BEPs), obtained by plotting p versus BET, give a dynamic representation of the approach to equilibrium and may serve as an indicator of the rate of drug delivery to the biophase. A pharmacodynamic system analysis method is proposed to determine BETs and BEPs from the biophase conduction function. The approach is demonstrated using pharmacodynamic data from the CNS effect of amobarbital evaluated by an aperiodic analysis of EEG recordings. The relevance of the BET and/or BEP principles in optimal computer-controlled drug infusion, drug design, and evaluation of targeted drug delivery is discussed. Both vascular and extravascular drug administrations are considered in the analysis.

  13. Thermodynamic Structure of Collision-Dominated Expanding Plasma: Heating of Interplanetary Coronal Mass Injections

    NASA Technical Reports Server (NTRS)

    Liu, Y.; Richardson, J. D.; Belcher, J. W.; Kasper, J. C.; Elliott, H. A.

    2006-01-01

    We investigate the thermodynamic structure of interplanetary coronal mass ejections (ICMEs) using combined surveys of the ejecta between 0.3 and 20 AU. ICMEs are shown to have a moderate expansion in the solar wind compared with theoretical predictions. The expansion seems to be governed by a polytrope with gamma approx. 1.3 in this distance range. We find that Coulomb collisions are important contributors to the ion-ion equilibration process in the ICME plasma. The alpha-proton differential speed quickly drops to below 10 km/s due to strong Coulomb collisions. However, the two species of particles are far from thermal equilibrium with a temperature ratio T(sub alpha/T(sub p) = 4-6, suggestive of a preferential heating of alpha particles. The plasma heating rate as a function of heliocentric &stance required for the temperature profile is deduced by taking into account the expansion and energy transfer between protons and alphas via Coulomb collisions. The turbulence dissipation rate is also inferred from the inertial range power spectrum of magnetic fluctuations within ICMEs. Comparison of the turbulence dissipation rate with the required heating rate shows that turbulence dissipation seems sufficient to explain the ICME heating. Sources powering the turbulence are also investigated by examining the instabilities induced by temperature anisotropies and energy deposition by pickup ions.

  14. Equilibration and nonclassicality of a double-well potential

    NASA Astrophysics Data System (ADS)

    Campbell, Steve; de Chiara, Gabriele; Paternostro, Mauro

    2016-01-01

    A double well loaded with bosonic atoms represents an ideal candidate to simulate some of the most interesting aspects in the phenomenology of thermalisation and equilibration. Here we report an exhaustive analysis of the dynamics and steady state properties of such a system locally in contact with different temperature reservoirs. We show that thermalisation only occurs ‘accidentally’. We further examine the nonclassical features and energy fluxes implied by the dynamics of the double-well system, thus exploring its finite-time thermodynamics in relation to the settlement of nonclassical correlations between the wells.

  15. Triplet Excitation Transfer between Carotenoids in the LH2 Complex from Photosynthetic Bacterium Rhodopseudomonas palustris.

    PubMed

    Feng, Juan; Wang, Qian; Wu, Yi-Shi; Ai, Xi-Cheng; Zhang, Xu-Jia; Huang, You-Guo; Zhang, Xing-Kang; Zhang, Jian-Ping

    2004-01-01

    We have studied, by means of sub-microsecond time-resolved absorption spectroscopy, the triplet-excited state dynamics of carotenoids (Cars) in the intermediate-light adapted LH2 complex (ML-LH2) from Rhodopseudomonas palustris containing Cars with different numbers of conjugated double bonds. Following pulsed photo-excitation at 590 nm at room temperature, rapid spectral equilibration was observed either as a red shift of the isosbestic wavelength on a time scale of 0.6-1.0 mus, or as a fast decay in the shorter-wavelength side of the T(n)<--T(1) absorption of Cars with a time constant of 0.5-0.8 mus. Two major spectral components assignable to Cars with 11 and 12 conjugated double bonds were identified. The equilibration was not observed in the ML-LH2 at 77 K, or in the LH2 complex from Rhodobacter sphaeroides G1C containing a single type of Car. The unique spectral equilibration was ascribed to temperature-dependent triplet excitation transfer among different Car compositions. The results suggest that Cars of 11 and 12 conjugated bonds, both in close proximity of BChls, may coexist in an alpha,beta-subunit of the ML-LH2 complex.

  16. Oxygen isotope thermometry of quartz-Al2SiO5veins in high-grade metamorphic rocks on Naxos island (Greece)

    NASA Astrophysics Data System (ADS)

    Putlitz, Benita; Valley, John; Matthews, Alan; Katzir, Yaron

    2002-04-01

    Diffusion models predict that peak metamorphic temperatures are best recorded by the oxygen isotope fractionation between minerals in a bi-mineralic rock in which a refractory accessory mineral with slow oxygen diffusion rate is modally minor to a mineral with a faster diffusion rate. This premise is demonstrated for high-grade metamorphism on the island of Naxos, Greece, where quartz-kyanite oxygen isotope thermometry from veins in high-grade metamorphic pelites gives temperatures of 635-690 °C. These temperatures are in excellent agreement with independent thermometry for the regional M2 peak metamorphic conditions and show that the vein minerals isotopically equilibrated at the peak of metamorphism. Quartz-sillimanite fractionations in the same veins give similar temperatures (680+/-35 °C) and suggest that the veins grew near to the kyanite-sillimanite boundary, corresponding to pressures of 6.5 to 7.5 kbar for temperatures of 635-685 °C. By contrast, quartz-kyanite and quartz-biotite pairs in the host rocks yield lower temperature estimates than the veins (590-600 and 350-550 °C, respectively). These lower apparent temperatures are also predicted from calculations of diffusional resetting in the polyphase host-rock system. The data demonstrate that bimineralic vein assemblages can be used as accurate thermometers in high-temperature rocks whereas retrograde exchange remains a major problem in many polymineralic rocks.

  17. Stability of chromium (III) sulfate in atmospheres containing oxygen and sulfur

    NASA Technical Reports Server (NTRS)

    Jacob, K. T.; Rao, B. D.; Nelson, H. G.

    1978-01-01

    The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).

  18. Very high pressure liquid chromatography using fully porous particles: quantitative analysis of fast gradient separations without post-run times.

    PubMed

    Stankovich, Joseph J; Gritti, Fabrice; Stevenson, Paul G; Beaver, Lois Ann; Guiochon, Georges

    2014-01-10

    Using a column packed with fully porous particles, four methods for controlling the flow rates at which gradient elution runs are conducted in very high pressure liquid chromatography (VHPLC) were tested to determine whether reproducible thermal conditions could be achieved, such that subsequent analyses would proceed at nearly the same initial temperature. In VHPLC high flow rates are achieved, producing fast analyses but requiring high inlet pressures. The combination of high flow rates and high inlet pressures generates local heat, leading to temperature changes in the column. Usually in this case a post-run time is input into the analytical method to allow the return of the column temperature to its initial state. An alternative strategy involves operating the column without a post-run equilibration period and maintaining constant temperature variations for subsequent analysis after conducting one or a few separations to bring the column to a reproducible starting temperature. A liquid chromatography instrument equipped with a pressure controller was used to perform constant pressure and constant flow rate VHPLC separations. Six replicate gradient separations of a nine component mixture consisting of acetophenone, propiophenone, butyrophenone, valerophenone, hexanophenone, heptanophenone, octanophenone, benzophenone, and acetanilide dissolved in water/acetonitrile (65:35, v/v) were performed under various experimental conditions: constant flow rate, two sets of constant pressure, and constant pressure operation with a programmed flow rate. The relative standard deviations of the response factors for all the analytes are lower than 5% across the methods. Programming the flow rate to maintain a fairly constant pressure instead of using instrument controlled constant pressure improves the reproducibility of the retention times by a factor of 5, when plotting the chromatograms in time. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Equilibration and aging of dense soft-sphere glass-forming liquids

    NASA Astrophysics Data System (ADS)

    Sánchez-Díaz, Luis Enrique; Ramírez-González, Pedro; Medina-Noyola, Magdaleno

    2013-05-01

    The recently developed nonequilibrium extension of the self-consistent generalized Langevin equation theory of irreversible relaxation [Ramírez-González and Medina-Noyola, Phys. Rev. E10.1103/PhysRevE.82.061503 82, 061503 (2010); Ramírez-González and Medina-Noyola, Phys. Rev. E10.1103/PhysRevE.82.061504 82, 061504 (2010)] is applied to the description of the irreversible process of equilibration and aging of a glass-forming soft-sphere liquid that follows a sudden temperature quench, within the constraint that the local mean particle density remains uniform and constant. For these particular conditions, this theory describes the nonequilibrium evolution of the static structure factor S(k;t) and of the dynamic properties, such as the self-intermediate scattering function FS(k,τ;t), where τ is the correlation delay time and t is the evolution or waiting time after the quench. Specific predictions are presented for the deepest quench (to zero temperature). The predicted evolution of the α-relaxation time τα(t) as a function of t allows us to define the equilibration time teq(ϕ), as the time after which τα(t) has attained its equilibrium value ταeq(ϕ). It is predicted that both, teq(ϕ) and ταeq(ϕ), diverge as ϕ→ϕ(a), where ϕ(a) is the hard-sphere dynamic-arrest volume fraction ϕ(a)(≈0.582), thus suggesting that the measurement of equilibrium properties at and above ϕ(a) is experimentally impossible. The theory also predicts that for fixed finite waiting times t, the plot of τα(t;ϕ) as a function of ϕ exhibits two regimes, corresponding to samples that have fully equilibrated within this waiting time (ϕ≤ϕ(c)(t)), and to samples for which equilibration is not yet complete (ϕ≥ϕ(c)(t)). The crossover volume fraction ϕ(c)(t) increases with t but saturates to the value ϕ(a).

  20. Simulated oil release from oil-contaminated marine sediment in the Bohai Sea, China.

    PubMed

    Yuan, Lingling; Han, Longxi; Bo, Wenjie; Chen, Hua; Gao, Wenshen; Chen, Bo

    2017-05-15

    There is a high degree of heavy oil partitioning into marine sediments when an oil spill occurs. Contaminated sediment, as an endogenous pollution source, can re-pollute overlying water slowly. In this study, a static oil release process and its effects in marine sediment was investigated through a series of experiments with reproductive heavy oil-contaminated marine sediment. The oil release process was accurately simulated with a Lagergren first-order equation and reached equilibration after 48h. The fitted curve for equilibrium concentration (C 0 ) and first-order rate constant (k 1 ) for sediment pollution levels exhibited a first-order log relationship. The instantaneous release rate (dC t dt) was also calculated. The C 0 increased with increases in temperature and dissolved organic matter (DOM), and decreasing salinity. The k 1 increased with temperature, but was not affected by DOM and salinity. These results can be used to better understand the fate of heavy oil in contaminated sediments of the Bohai Sea. Copyright © 2017. Published by Elsevier Ltd.

  1. Effects of ionomer morphology on oxygen reduction on Pt

    DOE PAGES

    Chlistunoff, Jerzy; Pivovar, Bryan

    2015-05-21

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared andmore » equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.« less

  2. Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation.

    PubMed

    Halonen, Roope; Zapadinsky, Evgeni; Vehkamäki, Hanna

    2018-04-28

    We present a comparison between Monte Carlo (MC) results for homogeneous vapour-liquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations, the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study, not only a primarily velocity scaling thermostat is considered, but also Nosé-Hoover, Berendsen, and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ϵ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures, the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].

  3. Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation

    NASA Astrophysics Data System (ADS)

    Halonen, Roope; Zapadinsky, Evgeni; Vehkamäki, Hanna

    2018-04-01

    We present a comparison between Monte Carlo (MC) results for homogeneous vapour-liquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations, the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study, not only a primarily velocity scaling thermostat is considered, but also Nosé-Hoover, Berendsen, and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ɛ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures, the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].

  4. Effects of an extension of the equilibration period up to 96 hours on the characteristics of cryopreserved bull semen.

    PubMed

    Fleisch, A; Malama, E; Witschi, U; Leiding, C; Siuda, M; Janett, F; Bollwein, H

    2017-02-01

    This study was designed to investigate the effects of an equilibration period up to 96 hours and three extenders (AndroMed, OPTIXcell, and Triladyl) on the quality of cryopreserved bull semen and to evaluate, whether an extension of the equilibration time to 72 hours does affect fertility in the field. One ejaculate of 17 bulls was collected and divided into three equal aliquots and diluted, respectively, with the three extenders. Each aliquot was again divided into five parts and equilibrated for 4, 24, 48, 72, and 96 hours before freezing in an automatic freezer. Sperm motility, plasma membrane and acrosome integrity (PMAI), and DNA fragmentation index (% DFI) were measured during equilibration. In addition to the parameters measured during equilibration, the percentage of viable sperm cells with high mitochondrial membrane potential (HMMP) was measured immediately after thawing, and after 3 hours of incubation at 37 °C. Sperm motility was assessed using CASA, and PMAI, HMMP, and % DFI were measured using flow cytometry. Equilibration time did affect all parameters before freezing (P < 0.01), and also the extender affected all parameters except HMMP (P < 0.05). After thawing, all parameters except HMMP immediately after thawing were influenced by the equilibration period (P < 0.001), whereas all parameters except % DFI immediately after thawing were influenced by the extender (P < 0.001). The changes of semen characteristics during 3 hours of incubation were also dependent on the equilibration time and the extender used in all parameters (P < 0.01). In the field study, semen of nine bulls was collected thrice weekly, processed using Triladyl egg yolk extender, and frozen in 0.25 mL straws with 15 × 10 6 spermatozoa per straw. In total, the nonreturn rates on Day 90 after insemination (NRR90) of 263,816 inseminations in two periods were evaluated. Whereas semen collected on Mondays and Wednesdays was equilibrated for 24 hours in both periods, semen collected on Fridays was equilibrated for 4 hours in period one and equilibrated for 72 hours in period 2. No differences in NRR90 could be found (P > 0.05). In conclusion, extension of the equilibration time from 4 hours to 24-72 hours can improve motility and viability of cryopreserved semen after thawing. The extent of improvement in semen quality is dependent on the extender used. Prolongation of the equilibration period from 4 hours to 72 hours had no effect on fertility in the field. Copyright © 2016 Elsevier Inc. All rights reserved.

  5. Radon as a tracer of biogenic gas equilibration and transport from methane-saturated sediments

    NASA Technical Reports Server (NTRS)

    Martens, Christopher S.; Chanton, Jeffrey P.

    1989-01-01

    Data on Rn-222 activity in methane-rich gas bubbles from anoxic coastal sediments of Cape Lookout Bight, North Carolina, were used to determine gas equilibration with pore waters and the rates of ebullitive stripping and transport of gases to overlying waters and the atmosphere. Results showed that, during summer months, the bubble ebullition process strips and transports 1.9-4.8 percent/day of the standing crop of radon (and, by inference, other gases equilibrated with gas bubbles) in surface sediments of Cape Lookout Bight to the troposphere. Thus, the ebullitive mode of gas transport represents an effective mechanism for delivering reduced biogenic gases directly to the atmosphere.

  6. The effect of elevated methane pressure on methane hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

  7. Classification of Thermal Patterns at Karst Springs and Cave Streams

    USGS Publications Warehouse

    Luhmann, A.J.; Covington, M.D.; Peters, Albert J.; Alexander, S.C.; Anger, C.T.; Green, J.A.; Runkel, Anthony C.; Alexander, E.C.

    2011-01-01

    Thermal patterns of karst springs and cave streams provide potentially useful information concerning aquifer geometry and recharge. Temperature monitoring at 25 springs and cave streams in southeastern Minnesota has shown four distinct thermal patterns. These patterns can be divided into two types: those produced by flow paths with ineffective heat exchange, such as conduits, and those produced by flow paths with effective heat exchange, such as small fractures and pore space. Thermally ineffective patterns result when water flows through the aquifer before it can equilibrate to the rock temperature. Thermally ineffective patterns can be either event-scale, as produced by rainfall or snowmelt events, or seasonal scale, as produced by input from a perennial surface stream. Thermally effective patterns result when water equilibrates to rock temperature, and the patterns displayed depend on whether the aquifer temperature is changing over time. Shallow aquifers with seasonally varying temperatures display a phase-shifted seasonal signal, whereas deeper aquifers with constant temperatures display a stable temperature pattern. An individual aquifer may display more than one of these patterns. Since karst aquifers typically contain both thermally effective and ineffective routes, we argue that the thermal response is strongly influenced by recharge mode. ?? 2010 The Author(s). Journal compilation ?? 2010 National Ground Water Association.

  8. Vocal function and upper airway thermoregulation in five different environmental conditions.

    PubMed

    Sandage, Mary J; Connor, Nadine P; Pascoe, David D

    2014-02-01

    Phonation threshold pressure and perceived phonatory effort were hypothesized to increase and upper airway temperature to decrease following exposure to cold and/or dry air. Greater changes were expected with mouth versus nose breathing. In a within-participant repeated measures design, 15 consented participants (7 men, 8 women) completed 20-min duration trials to allow for adequate thermal equilibration for both nose and mouth breathing in 5 different environments: 3 temperatures (°C) matched for relative humidity (% RH), cold (15 °C, 40% RH), thermally neutral (25 °C, 40% RH), and hot (35 °C, 40% RH); and 2 temperatures with variable relative humidity to match vapor pressure for the neutral environment (25 °C, 40% RH), cold (15 °C, 74% RH) and hot (35 °C, 23% RH). Following each equilibration trial, measures were taken in this order: upper airway temperature (transnasal thermistor probe), phonation threshold pressure, and perceived phonatory effort. Data were analyzed using repeated measures analysis of variance, and no significant differences were established. The study hypotheses were not supported. Findings suggest that the upper airway is tightly regulated for temperature when challenged by a realistic range of temperature and relative humidity environments. This is the first study of its kind to include measurement of upper airway temperature in conjunction with measures of vocal function.

  9. 40 CFR 86.331-79 - Hydrocarbon analyzer calibration.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... concentration. It is permitted to use additional concentrations. (5) Perform a linear least square regression on... least one-half hour after the oven has reached temperature for the system to equilibrate. (c) Initial...

  10. Effects of various combinations of cryoprotectants and cooling speed on the survival and further development of mouse oocytes after vitrification

    PubMed Central

    Cha, Soo Kyung; Kim, Bo Yeun; Kim, Mi Kyung; Kim, You Shin; Lee, Woo Sik

    2011-01-01

    Objective The objectives of this study were to analyze efficacy of immature and mature mouse oocytes after vitrification and warming by applying various combinations of cryoprotectants (CPAs) and/or super-rapid cooling using slush nitrogen (SN2). Methods Four-week old ICR female mice were superovulated for GV- and MII-stage oocytes. Experimental groups were divided into two groups. Ethylene glycol (EG) only group: pre-equilibrated with 1.5 M EG for 2.5 minutes and then equilibrated with 5.5 M EG and 1.0 M sucrose for 20 seconds. EG+dimethylsulfoxide (DMSO) group: pre-equilibrated with 1.3 M EG+1.1 M DMSO for 2.5 minutes and equilibrated with 2.7 M EG+2.1 M DMSO+0.5 M sucrose for 20 seconds. The oocytes were loaded onto grids and plunged into SN2 or liquid nitrogen (LN2). Stored oocytes were warmed by a five-step method, and then their survival, maturation, cleavage, and developmental rates were observed. Results The EG only and EG+DMSO groups showed no significant difference in survival of immature oocytes vitrified after warming. However, maturation and cleavage rates after conventional insemination were greater in the EG only group than in the EG+DMSO group. In mature oocytes, survival, cleavage, and blastocyst formation rates after warming showed no significant difference when EG only or EG+DMSO was applied. Furthermore, cleavage and blastocyst formation rates of MII oocytes vitrified using SN2 were increased in both the EG only and EG+DMSO groups. Conclusion A combination of CPAs in oocyte cryopreservation could be formulated according to the oocyte stage. In addition, SN2 may improve the efficiency of vitrification by reducing cryoinjury. PMID:22384414

  11. Shock temperature dependent rate law for plastic bonded explosives

    NASA Astrophysics Data System (ADS)

    Aslam, Tariq D.

    2018-04-01

    A reactive flow model for the tri-amino-tri-nitro-benzene (TATB) based plastic bonded explosive PBX 9502 (95% TATB, 5% polymeric binder Kel-F 800) is presented. This newly devised model is based primarily on the shock temperature of the material, along with local pressure, and accurately models a broader range of detonation and initiation scenarios. Specifically, sensitivity changes to the initial explosive temperature are accounted for naturally and with a single set of parameters. The equation of state forms for the reactants and products, as well as the thermodynamic closure of pressure and temperature equilibration, are carried over from the Wescott-Stewart-Davis (WSD) model [Wescott et al., J. Appl. Phys. 98, 053514 (2005) and "Modeling detonation diffraction and dead zones in PBX-9502," in Proceedings of the Thirteenth International Detonation Symposium (2006)]. This newly devised model, with Arrhenius state dependence on the shock temperature, based on the WSD equation of states, is denoted by AWSD. Modifying an existing implementation of the WSD model to the AWSD model in a hydrocode is a rather straightforward procedure.

  12. A new fundamental bioheat equation for muscle tissue--part II: Temperature of SAV vessels.

    PubMed

    Zhu, Liang; Xu, Lisa X; He, Qinghong; Weinbaum, Sheldon

    2002-02-01

    In this study, a new theoretical framework was developed to investigate temperature variations along countercurrent SAV blood vessels from 300 to 1000 microm diameter in skeletal muscle. Vessels of this size lie outside the range of validity of the Weinbaum-Jiji bioheat equation and, heretofore, have been treated using discrete numerical methods. A new tissue cylinder surrounding these vessel pairs is defined based on vascular anatomy, Murray's law, and the assumption of uniform perfusion. The thermal interaction between the blood vessel pair and surrounding tissue is investigated for two vascular branching patterns, pure branching and pure perfusion. It is shown that temperature variations along these large vessel pairs strongly depend on the branching pattern and the local blood perfusion rate. The arterial supply temperature in different vessel generations was evaluated to estimate the arterial inlet temperature in the modified perfusion source term for the s vessels in Part I of this study. In addition, results from the current research enable one to explore the relative contribution of the SAV vessels and the s vessels to the overall thermal equilibration between blood and tissue.

  13. Impact of holding and equilibration time on post-thaw quality of shipped boar semen.

    PubMed

    Schäfer, J; Waberski, D; Jung, M; Schulze, M

    2017-12-01

    Cryopreservation of boar semen is of growing interest for breeding companies. Overnight-shipping of pre-diluted ejaculates to specialized laboratories offers a practicable method, but requires fine-tuned protocols. In this study, the impact of holding post shipping at 17°C for 2 or 24h (n=10 samples) and of equilibration in lactose-egg yolk extender without glycerol at 5°C for 2, 4, 24 or 48h (n=11 samples) before freezing was investigated. Sperm-rich fractions of ejaculates from 21 mature Pietrain boars were collected at a single boar stud. After pre-dilution (1+1, v:v) with Beltsville thawing solution, samples were sent to the laboratory. Temperature profiles during transport and initial equilibration time were recorded. Semen quality post-thaw (PT) was evaluated using CASA and flow cytometry. Holding of 2h after shipping resulted in higher sperm motility (P=0.013) and beat cross frequency (BCF; P=0.047) compared to 24h. Differences between both groups vanished with prolonged incubation at 38°C PT. Equilibration at 5°C for 4h yielded the highest motility and BCF, whereas the equilibration for 48h impaired sperm motility. Membrane integrity, mitochondrial activity and DNA fragmentation index were not affected by any protocol modification. In conclusion, processing of pre-diluted boar semen shipped overnight within 2h after arrival at the laboratory is preferred to 24h of additional holding at 17°C. Extending the equilibration period in lactose-egg yolk extender without glycerol at 5°C from 2h to 4h before freezing is recommended. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Scattering of charge and spin excitations and equilibration of a one-dimensional Wigner crystal

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Matveev, K. A.; Andreev, A. V.; Klironomos, A. D.

    2014-07-01

    We study scattering of charge and spin excitations in a system of interacting electrons in one dimension. At low densities, electrons form a one-dimensional Wigner crystal. To a first approximation, the charge excitations are the phonons in the Wigner crystal, and the spin excitations are described by the Heisenberg model with nearest-neighbor exchange coupling. This model is integrable and thus incapable of describing some important phenomena, such as scattering of excitations off each other and the resulting equilibration of the system. We obtain the leading corrections to this model, including charge-spin coupling and the next-nearest-neighbor exchange in the spin subsystem.more » We apply the results to the problem of equilibration of the one-dimensional Wigner crystal and find that the leading contribution to the equilibration rate arises from scattering of spin excitations off each other. We discuss the implications of our results for the conductance of quantum wires at low electron densities« less

  15. Osmotic tolerance of avian spermatozoa: Influence of time, temperature, cryoprotectant and membrane ion pump function on sperm viability

    USGS Publications Warehouse

    Blanco, J.M.; Long, J.A.; Gee, G.; Donoghue, A.M.; Wildt, D.E.

    2008-01-01

    Potential factors influencing sperm survival under hypertonic conditions were evaluated in the Sandhill crane (Grus canadensis) and turkey (Meleagridis gallopavo). Sperm osmotolerance (300-3000 mOsm/kg) was evaluated after: (1) equilibration times of 2, 10, 45 and 60 min at 4 ?C versus 21 ?C; (2) pre-equilibrating with dimethylacetamide (DMA) or dimethylsulfoxide (Me2SO) at either 4 ?C or 21 ?C; and (3) inhibition of the Na+/K+ and the Na+/H+ antiporter membrane ionic pumps. Sperm viability was assessed using the eosin-nigrosin live/dead stain. Species-specific differences occurred in response to hypertonic conditions with crane sperm remaining viable under extreme hypertonicity (3000 mOsm/kg), whereas turkey sperm viability was compromised with only slightly hypertonic (500 mOsm/kg) conditions. The timing of spermolysis under hypertonic conditions was also species-specific, with a shorter interval for turkey (2 min) than crane (10 min) sperm. Turkey sperm osmotolerance was slightly improved by lowering the incubation temperature from 21 to 4 ?C. Pre-equilibrating sperm with DMA reduced the incidence of hypertonic spermolysis only in the crane, at both room and refrigeration temperature. Inhibiting the Na+/K+ and the Na+/H+ antiporter membrane ion pumps did not impair resistance of crane and turkey spermatozoa to hypertonic stress; pump inhibition actually increased turkey sperm survival compared to control sperm. Results demonstrate marked species specificity in osmotolerance between crane and turkey sperm, as well as in the way temperature and time of exposure affect sperm survival under hypertonic conditions. Differences are independent of the role of osmotic pumps in these species.

  16. Slow equilibration of reversed-phase columns for the separation of ionized solutes.

    PubMed

    Marchand, D H; Williams, L A; Dolan, J W; Snyder, L R

    2003-10-10

    Reversed-phase columns that have been stored in buffer-free solvents can exhibit pronounced retention-time drift when buffered, low-pH mobile phases are used with ionized solutes. Whereas non-ionized compounds exhibit constant retention times within 20 min of the beginning of mobile phase flow, the retention of ionized compounds can continue to change (by 20% or more) for several hours. If mobile phase pH is changed from low to high and back again, an even longer time may be required before the column reaches equilibration at low pH. The speed of column equilibration for ionized solutes can vary significantly among different reversed-phase columns and is not affected by flow rate.

  17. Concentration and Mobility of Electrically-Conducting Defects in Olivine

    NASA Astrophysics Data System (ADS)

    Constable, S.; Roberts, J.; Duba, A.

    2002-12-01

    We have collected measurements of electrical conductivity and thermopower as a function of temperature and oxygen fugacity (f O2) on a sample of San Quintin dunite (95% olivine), and measurements of electrical conductivity equilibration after changes in f O2 on Mt.Porndon lherzolite (65% olivine). Both data sets have been analysed using nonlinear parameter inversion of mathematical models relating conductivity, thermopower, and diffusion kinetics to temperature, f O2, time, and defect concentration and mobility. From the dunite thermopower/conductivity data we are able to estimate the concentration and mobilities of electrically conducting defects. Our model allows electrons, small polarons (Fe+++ on Fe++ sites), and magnesium vacancies (V'' Mg) to contribute to conduction, but only polarons and V'' Mg are required by our data. Polarons dominate conduction below 1300°~C; at this temperature conduction, is equal for the two defects at all f O2 tested. Thermopower measurements allow us to estimate defect concentration independently from mobility, and so we can back out polaron mobility as 12.2x 10-6 exp(-1.05~eV/kT) m2V-1s-1 and magnesium vacancy mobility as 2.72x 10-6 exp(-1.09~eV/kT) m2V-1s-1. Electrical conductivity of the lherzolite, measured as a function of time after changes in the oxygen fugacity of the surrounding CO2/CO atmosphere, is used to infer the diffusivity of the point defects associated with the oxidation reactions. An observed f O2 dependence in the time constants associated with equilibration implies two species of fixed diffusivity, each with f O2-dependent concentrations. Although the rate-limiting step may not necessarily be associated with conducting defects, when time constants are converted to mobilities, the magnitudes and activation energies agree extremely well with the model presented above for the dunite, after one free parameter (effective grain size) is fit at a plausible 1.6~mm diameter. Not only does this study represent one of the few direct measurements of polaron mobility, but the very good agreement between two independent measurement techniques (thermopower versus equilibration kinetics) and two independent samples (dunite versus lherzolite) provides some level of confidence in the results. We are currently extending these modeling techniques to study olivine defect mobility anisotropy.

  18. Moisture absorption and bakeout characteristics of rigid-flexible multilayer printed wiring boards

    NASA Astrophysics Data System (ADS)

    Lula, J. W.

    1991-01-01

    Moisture absorption and bakeout characteristics of rigid flexible printed wiring boards were determined. It was found that test specimens had absorbed 0.95 weight percent moisture when equilibrated to a 50 percent RH, 25 C environment. Heating those equilibrated specimens in a 120 C static air oven removed 92 percent of this absorbed moisture in 24 h. Heating the samples in a 80 C static air oven removed only 64 percent of the absorbed moisture at the end of 24 h. A 120 C vacuum bake removed moisture at essentially the same rate with parylene slowed the absorption rate by approximately 50 percent but did not appreciably affect the equilibrium moisture content or the drying rate.

  19. Stability of sugar solutions: a novel study of the epimerization kinetics of lactose in water.

    PubMed

    Jawad, Rim; Drake, Alex F; Elleman, Carole; Martin, Gary P; Warren, Frederick J; Perston, Benjamin B; Ellis, Peter R; Hassoun, Mireille A; Royall, Paul G

    2014-07-07

    This article reports on the stereochemical aspects of the chemical stability of lactose solutions stored between 25 and 60 °C. The lactose used for the preparation of the aqueous solutions was α-lactose monohydrate with an anomer purity of 96% α and 4% β based on the supplied certificate of analysis (using a GC analytical protocol), which was further confirmed here by nuclear magnetic resonance (NMR) analysis. Aliquots of lactose solutions were collected at different time points after the solutions were prepared and freeze-dried to remove water and halt epimerization for subsequent analysis by NMR. Epimerization was also monitored by polarimetry and infrared spectroscopy using a specially adapted Fourier transform infrared attenuated total reflectance (FTIR-ATR) method. Hydrolysis was analyzed by ion chromatography. The three different analytical approaches unambiguously showed that the epimerization of lactose in aqueous solution follows first order reversible kinetics between 25 to 60 °C. The overall rate constant was 4.4 × 10(-4) s(-1) ± 0.9 (± standard deviation (SD)) at 25 °C. The forward rate constant was 1.6 times greater than the reverse rate constant, leading to an equilibrium constant of 1.6 ± 0.1 (±SD) at 25 °C. The rate of epimerization for lactose increased with temperature and an Arrhenius plot yielded an activation energy of +52.3 kJ/mol supporting the hypothesis that the mechanism of lactose epimerization involves the formation of extremely short-lived intermediate structures. The main mechanism affecting lactose stability is epimerization, as no permanent hydrolysis or chemical degradation was observed. When preparing aqueous solutions of lactose, immediate storage in an ice bath at 0 °C will allow approximately 3 min (180 s) of analysis time before the anomeric ratio alters significantly (greater than 1%) from the solid state composition of the starting material. In contrast a controlled anomeric composition (~38% α and ~62% β) will be achieved if an aqueous solution is left to equilibrate for over 4 h at 25 °C, while increasing the temperature up to 60 °C rapidly reduces the required equilibration time.

  20. The rate of equilibration of viscous aerosol particles

    NASA Astrophysics Data System (ADS)

    O'Meara, Simon; Topping, David O.; McFiggans, Gordon

    2016-04-01

    The proximity of atmospheric aerosol particles to equilibrium with their surrounding condensable vapours can substantially impact their transformations, fate and impacts and is the subject of vibrant research activity. In this study we first compare equilibration timescales estimated by three different models for diffusion through aerosol particles to assess any sensitivity to choice of model framework. Equilibration times for diffusion coefficients with varying dependencies on composition are compared for the first time. We show that even under large changes in the saturation ratio of a semi-volatile component (es) of 1-90 % predicted equilibration timescales are in agreement, including when diffusion coefficients vary with composition. For condensing water and a diffusion coefficient dependent on composition, a plasticising effect is observed, leading to a decreased estimated equilibration time with increasing final es. Above 60 % final es maximum equilibration times of around 1 s are estimated for comparatively large particles (10 µm) containing a relatively low diffusivity component (1 × 10-25 m2 s-1 in pure form). This, as well as other results here, questions whether particle-phase diffusion through water-soluble particles can limit hygroscopic growth in the ambient atmosphere. In the second part of this study, we explore sensitivities associated with the use of particle radius measurements to infer diffusion coefficient dependencies on composition using a diffusion model. Given quantified similarities between models used in this study, our results confirm considerations that must be taken into account when designing such experiments. Although quantitative agreement of equilibration timescales between models is found, further work is necessary to determine their suitability for assessing atmospheric impacts, such as their inclusion in polydisperse aerosol simulations.

  1. Equilibration of quantum hall edge states and its conductance fluctuations in graphene p-n junctions

    NASA Astrophysics Data System (ADS)

    Kumar, Chandan; Kuiri, Manabendra; Das, Anindya

    2018-02-01

    We report an observation of conductance fluctuations (CFs) in the bipolar regime of quantum hall (QH) plateaus in graphene (p-n-p/n-p-n) devices. The CFs in the bipolar regime are shown to decrease with increasing bias and temperature. At high temperature (above 7 K) the CFs vanishes completely and the flat quantized plateaus are recovered in the bipolar regime. The values of QH plateaus are in theoretical agreement based on full equilibration of chiral channels at the p-n junction. The amplitude of CFs for different filling factors follows a trend predicted by the random matrix theory. Although, there are mismatch in the values of CFs between the experiment and theory but at higher filling factors the experimental values become closer to the theoretical prediction. The suppression of CFs and its dependence has been understood in terms of time dependent disorders present at the p-n junctions.

  2. Nucleation of Organic Molecules via a Hot Precursor State: Pentacene on Amorphous Mica

    PubMed Central

    2013-01-01

    Organic thin films have attracted considerable interest due to their applicability in organic electronics. The classical scenario for thin film nucleation is the diffusion-limited aggregation (DLA). Recently, it has been shown that organic thin film growth is better described by attachment-limited aggregation (ALA). However, in both cases, an unusual relationship between the island density and the substrate temperature was observed. Here, we present an aggregation model that goes beyond the classical DLA or ALA models to explain this behavior. We propose that the (hot) molecules impinging on the surface cannot immediately equilibrate to the substrate temperature but remain in a hot precursor state. In this state, the molecules can migrate considerable distances before attaching to a stable or unstable island. This results in a significantly smaller island density than expected by assuming fast equilibration and random diffusion. We have applied our model to pentacene film growth on amorphous Muscovite mica. PMID:24340130

  3. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

    DOE PAGES

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

    2018-04-24

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-Molecular Dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients; we use this approach to examine atomic condensation onto 6-56 atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity ( v) between atom and cluster andmore » the initial impact parameter ( b). In all cases there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms, and for 14 atom and 28 atom Mg clusters, as cluster equilibration temperature increases the condensation rate coefficient drops to values below the hard sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (> 1000 m s -1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). In conclusion, the presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.« less

  4. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations.

    PubMed

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J

    2018-04-28

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s -1 ) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

  5. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-Molecular Dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients; we use this approach to examine atomic condensation onto 6-56 atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity ( v) between atom and cluster andmore » the initial impact parameter ( b). In all cases there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms, and for 14 atom and 28 atom Mg clusters, as cluster equilibration temperature increases the condensation rate coefficient drops to values below the hard sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (> 1000 m s -1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). In conclusion, the presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.« less

  6. Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

    NASA Astrophysics Data System (ADS)

    Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

    2018-04-01

    In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s-1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

  7. Experimental Evidence for Fast Lithium Diffusion and Isotope Fractionation in Water-bearing Rhyolitic Melts at Magmatic Conditions

    NASA Astrophysics Data System (ADS)

    Cichy, S. B.; Till, C. B.; Roggensack, K.; Hervig, R. L.; Clarke, A. B.

    2015-12-01

    The aim of this work is to extend the existing database of experimentally-determined lithium diffusion coefficients to more natural cases of water-bearing melts at the pressure-temperature range of the upper crust. In particular, we are investigating Li intra-melt and melt-vapor diffusion and Li isotope fractionation, which have the potential to record short-lived magmatic processes (seconds to hours) in the shallow crust, especially during decompression-induced magma degassing. Hydrated intra-melt Li diffusion-couple experiments on Los Posos rhyolite glass [1] were performed in a piston cylinder at 300 MPa and 1050 °C. The polished interfaces between the diffusion couples were marked by addition of Pt powder for post-run detection. Secondary ion mass spectrometry analyses indicate that lithium diffuses extremely fast in the presence of water. Re-equilibration of a hydrated ~2.5 mm long diffusion-couple experiment was observed during the heating period from room temperature to the final temperature of 1050 °C at a rate of ~32 °C/min. Fractionation of ~40‰ δ7Li was also detected in this zero-time experiment. The 0.5h and 3h runs show progressively higher degrees of re-equilibration, while the isotope fractionation becomes imperceptible. Li contamination was observed in some experiments when flakes filed off Pt tubing were used to mark the diffusion couple boundary, while the use of high purity Pt powder produced better results and allowed easier detection of the diffusion-couple boundary. The preliminary lithium isotope fractionation results (δ7Li vs. distance) support findings from [2] that 6Li diffuses substantially faster than 7Li. Further experimental sets are in progress, including lower run temperatures (e.g. 900 °C), faster heating procedure (~100 °C/min), shorter run durations and the extension to mafic systems. [1] Stanton (1990) Ph.D. thesis, Arizona State Univ., [2] Richter et al. (2003) GCA 67, 3905-3923.

  8. Optimization of conditions for the cryopreservation of yellow catfish (Pelteobagrus fulvidraco) sperm.

    PubMed

    Yang, Sen; Han, Linqiang; Huang, Rushou; Liufu, Yongzhong; Meng, Zining; Lin, Haoran

    2017-06-01

    Yellow catfish (Pelteobagrus fulvidraco) is a promising aquaculture species in China with an increasing market demand. To serve the growing demand of male broodstock for artificial fertilization and the preservation of valuable strains for selective breeding, we tried to develop a species-specific cryopreservation protocol for yellow catfish sperm in this study. Important factors such as cryoprotectant, freezing height above the liquid nitrogen (LN) surface, dilution ratio, equilibration time, thawing temperature and cool storage before freezing were standardized. Among the cryoprotectants tested here, 10% Me 2 SO was the most suitable for sperm cryopreservation. Freezing at 7 cm above the LN surface for 10 min yielded the highest post-thaw motility. Further evaluation showed that dilution ratio of 1:3 and 1:5 produced higher post-thaw motility than semen diluted at 2:1, 1:1, 1:9 or 1:19. Equilibration times from 0 to 30 min did not cause significant differences in both equilibrated and post-thaw motility. Also, cool storage up to 24 h did not affect the suitability of sperm for cryopreservation. After thawing, sperm could be stored at 4 °C for 2 h without a reduction in motility parameters. With the combination of optimized freezing conditions, the fertilization and hatching rate of cryopreserved sperm were 87.1 ± 5.2% and 78.5 ± 7.4%, respectively, which were similar to those of fresh sperm (91.8 ± 3.5% and 83.7 ± 2.5%). In general, the cryopreservation protocol optimized here would facilitate breeding practice and hatchery operation in this economically important fish. Copyright © 2017. Published by Elsevier Inc.

  9. Vocal Function and Upper Airway Thermoregulation in Five Different Environmental Conditions

    PubMed Central

    Sandage, Mary J.; Connor, Nadine P.; Pascoe, David D.

    2013-01-01

    Purpose Phonation threshold pressure and perceived phonatory effort were hypothesized to increase and upper airway temperature decrease following exposure to cold and/or dry air. Greater changes were expected with mouth versus nose breathing. Method Using a within-participant repeated measures design, 15 consented participants (7 men, 8 women) completed 20-minute duration trials to allow for adequate thermal equilibration for both nose and mouth breathing in five different environments: three temperatures (°C) matched for relative humidity (%RH): cold (15°C/40% RH), thermally neutral (25°C/40% RH), and hot (35°C/40% RH); and two temperatures with variable relative humidity to match vapor pressure for the neutral environment (25°C/40% RH): cold (15°C/74% RH) and hot (35°C; 23% RH). Following each equilibration trial, measures were taken in this order: upper airway temperature (transnasal thermistor probe), phonation threshold pressure, and perceived phonatory effort. Results Data were analyzed using repeated measures analysis of variance and no significant differences were established. Conclusions The study hypotheses were not supported. Findings suggest that the upper airway is tightly regulated for temperature when challenged by a realistic range of temperature/relative humidity environments. This is the first study of its kind to include measurement of upper airway temperature in conjunction with measures of vocal function. PMID:23900031

  10. Low-Ca pyroxenes from LL group chondritic meteorites: Crystal structural studies and implications for their thermal histories

    NASA Astrophysics Data System (ADS)

    Artioli, G.; Davoli, G.

    1994-12-01

    Crystal structural refinements of one orthorhombic (Pbca) and two monoclinic (P21/c) single crystals, from chondrules of low-Ca pyroxenes from unequilibrated chondritic meteorites of the LL group, were carried out. The intracrystalline Fe-Mg distribution between the M1 and M2 crystallographic sites of the Parnallee (LL-3) orthoenstatite is suggestive of very rapid cooling, whereas both the structural state and intracrystalline Fe-Mg distribution in the Soko Banja (LL-4) and Jolomba (LL-6) clinoenstaties indicate rapid cooling from the high temperature polymorphs, with no significant re-equilibration at lower temperatures. These results imply that thermal metamorphism in the parent body, if present, was insufficient to allow re-equilibration of the pyroxene minerals to low temperature, ordered crystal structures. The data also indicate that, assuming low or mild pressure and shock effects, there is no well defined correlation between equilibrium temperature of the mineral phases and the alleged petrologic type of the meteorites. This evidence is consistent with a rubble pile model for the parent body accretional history, or with an onion shell model with very low thermal peak metamorphism, as is assumed for a very small object.

  11. Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

    NASA Astrophysics Data System (ADS)

    Lassiter, J. C.

    2016-12-01

    The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

  12. Voice Function Differences Following Resting Breathing vs. Submaximal Exercise

    PubMed Central

    Sandage, Mary J.; Connor, Nadine P.; Pascoe, David D.

    2013-01-01

    Objectives/Hypothesis There is little known about how physical exercise may alter physiological parameters of voice production. In this investigation, vocal function and upper airway temperature were examined following a bout of submaximal exercise and compared with a resting breathing condition. It was hypothesized that phonation threshold pressure and perceived phonatory effort would increase, and pharyngeal temperature would decrease following an exercise bout. Study Design Using a within-participant repeated measures design, 18 consented participants (9 men, 9 women) completed the study. Methods A 20-minute equilibration task was immediately followed by 8 minutes of submaximal exercise on a stationary bike in a thermally neutral environment (25°C/40% RH). At the end of the equilibration trial and the exercise trial measures were taken in the following order: pharyngeal temperature, phonation threshold pressure, and perceived phonatory effort. Data were analyzed using paired t-tests with significance set at α<0.05. Results Significantly increased phonation threshold pressure and perceived phonatory effort and significantly decreased pharyngeal temperature (1.9°C) were found, supporting the initial hypotheses. Conclusions Findings from this investigation support the widely held belief that voice use associated with physical activity requires additional laryngeal effort and closure forces. The effect of the temperature reduction in the upper airway on voice function requires further study. PMID:23849683

  13. An apparatus for sequentially combining microvolumes of reagents by infrasonic mixing.

    PubMed

    Camien, M N; Warner, R C

    1984-05-01

    A method employing high-speed infrasonic mixing for obtaining timed samples for following the progress of a moderately rapid chemical reaction is described. Drops of 10 to 50 microliter each of two reagents are mixed to initiate the reaction, followed, after a measured time interval, by mixing with a drop of a third reagent to quench the reaction. The method was developed for measuring the rate of denaturation of covalently closed, circular DNA in NaOH at several temperatures. For this purpose the timed samples were analyzed by analytical ultracentrifugation. The apparatus was tested by determination of the rate of hydrolysis of 2,4-dinitrophenyl acetate in an alkaline buffer. The important characteristics of the method are (i) it requires very small volumes of sample and reagents; (ii) the components of the reaction mixture are pre-equilibrated and mixed with no transfer outside the prescribed constant temperature environment; (iii) the mixing is very rapid; and (iv) satisfactorily precise measurements of relatively short time intervals (approximately 2 sec minimum) between sequential mixings of the components are readily obtainable.

  14. Effect of Equilibrated pH and Indigenous Spoilage Microorganisms on the Inhibition of Proteolytic Clostridium botulinum Toxin Production in Experimental Meals under Temperature Abuse.

    PubMed

    Golden, Max C; Wanless, Brandon J; David, Jairus R D; Lineback, D Scott; Talley, Ryan J; Kottapalli, Bala; Glass, Kathleen A

    2017-08-01

    Clostridium botulinum is a foreseeable biological hazard in prepared refrigerated meals that needs to be addressed in food safety plans. The objective of this study was to evaluate the effect of product composition and storage temperature on the inhibition of botulinum toxin formation in nine experimental meals (meat, vegetable, or carbohydrate based). Treatments were inoculated with proteolytic C. botulinum, vacuum packaged, cooked at 90°C for 10 min, and assayed for botulinum toxin in samples stored at 25°C for up to 96 h for phase 1, or at 25°C for 12 h and then transferred to 12.5°C for up to 12 and 6 weeks in phases 1 and 2, respectively. For phase 1, none of the treatments (equilibrated pH 5.8) supported toxin production when stored at 25°C for 48 h, but toxin production was observed in all treatments at 72 h. For the remaining experiments with storage at 12.5°C, toxin production was dependent on equilibrated pH, storage time, and growth of indigenous spoilage microorganisms. In phase 1, no gross spoilage and no botulinum toxin was detected for any treatment (pH ≤5.8) stored at 12.5°C for 12 weeks. In phase 2, gross spoilage varied by commodity, with the brussels sprouts meal with pH 6.5 showing the most rapid spoilage within 2 weeks and botulinum toxin detected at 5 and 6 weeks for the control and cultured celery juice treatments, respectively. In contrast, spoilage microbes decreased the pH of a pH 5.9 beef treatment by 1.0 unit, potentially inhibiting C. botulinum through 6 weeks at 12.5°C. None of the other treatments with pH 5.8 or below supported toxin production or spoilage. This study provides validation for preventive controls in refrigerated meals. These include equilibrated product pH and storage temperature and time to inhibit toxin formation by proteolytic C. botulinum, but the impact of indigenous microflora on safety and interpretation of challenge studies is also highlighted.

  15. An evaluation of fluid bed drying of aqueous granulations.

    PubMed

    Hlinak, A J; Saleki-Gerhardt, A

    2000-01-01

    The purpose of the work described was twofold: (a) to apply heat and mass balance approaches to evaluate the fluid bed drying cycle of an aqueous granulation, and (b) to determine the effect of the temperature and relative humidity of the drying air on the ability to meet a predetermined moisture content specification. Water content determinations were performed using Karl Fischer titration, and Computrac and Mark 1 moisture analyzers. The water vapor sorption isotherms were measured using a gravimetric moisture sorption apparatus with vacuum-drying capability. Temperature, relative humidity, and air flow were measured during the drying cycle of a production-scale fluid bed dryer. Heat and mass balance equations were used to calculate the evaporation rates. Evaporation rates calculated from heat and mass balance equations agreed well with the experimental data, whereas equilibrium moisture content values provided useful information for determination of the upper limit for inlet air humidity. Increasing the air flow rate and inlet temperature reduced the drying time through the effect on the primary driving force. As expected, additional drying of granules during the equilibration period did not show a significant impact on reducing the final moisture content of granules. Reducing the drying temperature resulted in measurement of higher equilibrium moisture content for the granules, which was in good agreement with the water vapor sorption data. Heat and mass balance equations can be used to successfully model the fluid bed drying cycle of aqueous granulations. The water vapor sorption characteristics of granules dictate the final moisture content at a given temperature and relative humidity.

  16. Time-Separating Heating and Sensor Functions of Thermistors in Precision Thermal Control Applications

    NASA Technical Reports Server (NTRS)

    Cho, Hyung J.; Sukhatme, Kalyani G.; Mahoney, John C.; Penanen, Konstantin Penanen; Vargas, Rudolph, Jr.

    2010-01-01

    A method allows combining the functions of a heater and a thermometer in a single device, a thermistor, with minimal temperature read errors. Because thermistors typically have a much smaller thermal mass than the objects they monitor, the thermal time to equilibrate the thermometer to the temperature of the object is typically much shorter than the thermal time of the object to change its temperature in response to an external perturbation.

  17. Repeated use of ion-exchange resin membranes in calcareous soils

    USGS Publications Warehouse

    Sherrod, S.K.; Belnap, Jayne; Miller, M.E.

    2003-01-01

    This study compared the consistency of nutrient extraction among repeated cycles of ion-exchange resin membrane use. Two sandy calcareous soils and different equilibration temperatures were tested. No single nutrient retained consistent values from cycle to cycle in all treatments, although both soil source and temperature conferred some influence. It was concluded that the most conservative use of resin membranes is single-use.

  18. The uniquely high-temperature character of Cullinan diamonds: A signature of the Bushveld mantle plume?

    NASA Astrophysics Data System (ADS)

    Korolev, N. M.; Kopylova, M.; Bussweiler, Y.; Pearson, D. G.; Gurney, J.; Davidson, J.

    2018-04-01

    The mantle beneath the Cullinan kimberlite (formerly known as "Premier") is a unique occurrence of diamondiferous cratonic mantle where diamonds were generated contemporaneously and shortly following a mantle upwelling that led to the formation of a Large Igneous Province that produced the world's largest igneous intrusion - the 2056 Ma Bushveld Igneous Complex (BIC). We studied 332 diamond inclusions from 202 Cullinan diamonds to investigate mantle thermal effects imposed by the formation of the BIC. The overwhelming majority of diamonds come from three parageneses: (1) lithospheric eclogitic (69%), (2) lithospheric peridotitic (21%), and (3) sublithospheric mafic (9%). The lithospheric eclogitic paragenesis is represented by clinopyroxene, garnet, coesite and kyanite. Main minerals of the lithospheric peridotitic paragenesis are forsterite, enstatite, Cr-pyrope, Cr-augite and spinel; the sublithospheric mafic association includes majorite, CaSiO3 phases and omphacite. Diamond formation conditions were calculated using an Al-in-olivine thermometer, a garnet-clinopyroxene thermometer, as well as majorite and Raman barometers. The Cullinan diamonds may be unique on the global stage in recording a cold geotherm of 40 mW/m2 in cratonic lithosphere that was in contact with underlying convecting mantle at temperatures of 1450-1550 °C. The studied Cullinan diamonds contain a high proportion of inclusions equilibrated at temperatures exceeding the ambient 1327 °C adiabat, i.e. 54% of eclogitic diamonds and 41% of peridotitic diamonds. By contrast, ≤ 1% of peridotitic diamond inclusions globally yield equally high temperatures. We propose that the Cullinan diamond inclusions recorded transient, slow-dissipating thermal perturbations associated with the plume-related formation of the 2 Ga Bushveld igneous province. The presence of inclusions in diamond from the mantle transition zone at 300-650 km supports this view. Cullinan xenoliths indicative of the thermal state of the cratonic lithosphere at 1.2 Ga are equilibrated at the relatively low temperatures, not exceeding adiabatic. The ability of diamonds to record super-adiabatic temperatures may relate to their entrainment from the deeper, hotter parts of the upper mantle un-sampled by the kimberlite in the form of xenoliths or their equilibration in a younger lithosphere after a decay of the thermal disturbance.

  19. Exact infinite-time statistics of the Loschmidt echo for a quantum quench.

    PubMed

    Campos Venuti, Lorenzo; Jacobson, N Tobias; Santra, Siddhartha; Zanardi, Paolo

    2011-07-01

    The equilibration dynamics of a closed quantum system is encoded in the long-time distribution function of generic observables. In this Letter we consider the Loschmidt echo generalized to finite temperature, and show that we can obtain an exact expression for its long-time distribution for a closed system described by a quantum XY chain following a sudden quench. In the thermodynamic limit the logarithm of the Loschmidt echo becomes normally distributed, whereas for small quenches in the opposite, quasicritical regime, the distribution function acquires a universal double-peaked form indicating poor equilibration. These findings, obtained by a central limit theorem-type result, extend to completely general models in the small-quench regime.

  20. Effect of temperature and humidity on formaldehyde emissions in temporary housing units.

    PubMed

    Parthasarathy, Srinandini; Maddalena, Randy L; Russell, Marion L; Apte, Michael G

    2011-06-01

    The effect of temperature and humidity on formaldehyde emissions from samples collected from temporary housing units (THUs) was studied. The THUs were supplied by the U.S. Federal Emergency Management Administration (FEMA) to families that lost their homes in Louisiana and Mississippi during the Hurricane Katrina and Rita disasters. On the basis of a previous study, four of the composite wood surface materials that dominated contributions to indoor formaldehyde were selected to analyze the effects of temperature and humidity on the emission factors. Humidity equilibration experiments were carried out on two of the samples to determine how long the samples take to equilibrate with the surrounding environmental conditions. Small chamber experiments were then conducted to measure emission factors for the four surface materials at various temperature and humidity conditions. The samples were analyzed for formaldehyde via high-performance liquid chromatography. The experiments showed that increases in temperature or humidity contributed to an increase in emission factors. A linear regression model was built using the natural log of the percent relative humidity (RH) and inverse of temperature (in K) as independent variables and the natural log of emission factors as the dependent variable. The coefficients for the inverse of temperature and log RH with log emission factor were found to be statistically significant for all of the samples at the 95% confidence level. This study should assist in retrospectively estimating indoor formaldehyde exposure of occupants of THUs.

  1. Measurement of the relaxation rate of the magnetization in Mn12O12-acetate using proton NMR echo

    PubMed

    Jang; Lascialfari; Borsa; Gatteschi

    2000-03-27

    We present a novel method to measure the relaxation rate W of the magnetization of Mn 12O (12)-acetate (Mn12) magnetic molecular cluster in its S = 10 ground state at low T. It is based on the observation of an exponential growth in time of the proton NMR signal during the thermal equilibration of the magnetization of the molecules. We can explain the novel effect with a simple model which relates the intensity of the proton echo signal to the microscopic reversal of the magnetization of each individual Mn12 molecule during the equilibration process. The method should find wide application in the study of magnetic molecular clusters in off-equilibrium conditions.

  2. Considerations for the measurement of core, skin and mean body temperatures.

    PubMed

    Taylor, Nigel A S; Tipton, Michael J; Kenny, Glen P

    2014-12-01

    Despite previous reviews and commentaries, significant misconceptions remain concerning deep-body (core) and skin temperature measurement in humans. Therefore, the authors have assembled the pertinent Laws of Thermodynamics and other first principles that govern physical and physiological heat exchanges. The resulting review is aimed at providing theoretical and empirical justifications for collecting and interpreting these data. The primary emphasis is upon deep-body temperatures, with discussions of intramuscular, subcutaneous, transcutaneous and skin temperatures included. These are all turnover indices resulting from variations in local metabolism, tissue conduction and blood flow. Consequently, inter-site differences and similarities may have no mechanistic relationship unless those sites have similar metabolic rates, are in close proximity and are perfused by the same blood vessels. Therefore, it is proposed that a gold standard deep-body temperature does not exist. Instead, the validity of each measurement must be evaluated relative to one's research objectives, whilst satisfying equilibration and positioning requirements. When using thermometric computations of heat storage, the establishment of steady-state conditions is essential, but for clinically relevant states, targeted temperature monitoring becomes paramount. However, when investigating temperature regulation, the response characteristics of each temperature measurement must match the forcing function applied during experimentation. Thus, during dynamic phases, deep-body temperatures must be measured from sites that track temperature changes in the central blood volume. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Long Range Materials Research. Appendix 1. Synthesis and Characterization of Supported Organometallic Rhodium (I) Catalysts

    DTIC Science & Technology

    1974-06-30

    hydrosilates, 130 including irradiation by ultraviolet light, elevated temperatures (up to 3500) in sealed tubes, and free radical initiators (up to 10 mol...to 160 ml dry pyridine and stirred at 00 in a 250 ml Erlenmeyer flask fitted with a septum. After the temperature had equilibrated, p-toluene sulfonyl...chloride (80 g, 0.41 mol) was added slowly, carefully maintaining the temperature below 100. The vessel was tightly capped, the mixture stirred an

  4. New findings for the equilibrated enstatite chondrite Grein 002

    NASA Astrophysics Data System (ADS)

    Patzer, Andrea; Schlüter, Jochen; Schultz, Ludolf; Tarkian, M.; Hill, Dolores H.; Boynton, William V.

    2004-09-01

    We report new petrographic and chemical data for the equilibrated EL chondrite Grein 002, including the occurrence of osbornite, metallic copper, abundant taenite, and abundant diopside. As inferred from low Si concentrations in kamacite, the presence of ferroan alabandite, textural deformation, chemical equilibration of mafic silicates, and a subsolar noble gas component, we concur with Grein 002's previous classification as an EL4-5 chondrite. Furthermore, the existence of pockets consisting of relatively coarse, euhedral enstatite crystals protruding large patches of Fe-Ni alloys suggests to us that this EL4-5 chondrite has been locally melted. We suspect impact induced shock to have triggered the formation of the melt pockets. Mineralogical evidence indicates that the localized melting of metal and adjacent enstatite must have happened relatively late in the meteorite's history. The deformation of chondrules, equilibration of mafic silicates, and generation of normal zoning in Fe, Zn-sulfides took place during thermal alteration before the melting event. Following parent body metamorphism, daubreelite was exsolved from troilite in response to a period of slow cooling at subsolidus temperatures. Exsolution of schreibersite from the coarse metal patches probably occurred during a similar period of slow cooling subsequent to the event that induced the formation of the melt pockets. Overall shock features other than localized melting correspond to stage S2 and were likely established by the final impact that excavated the Grein 002 meteoroid.

  5. H2O Adsorption on Smectites: Application to the Diurnal Variation of H2O in the Martian Atmosphere

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Howard, J.; Quinn, R. C.

    2000-01-01

    Observations of the Martian planetary boundary layer lead to interpretations that are baffling and contradictory. In this paper, we specifically address the question of whether or not water vapor finds a substantial diurnal reservoir in the Martian regolith. To address this issue, we have measured H2O adsorption kinetics on SWy-1, a Na-rich montmorillonite from Wyoming. The highest-temperature (273 K) data equilibrates rapidly. Data gathered at realistic H2O partial pressures and temperatures appropriate to early morning show two phenomena that preclude a significant role for smectites in diurnally exchanging a large column abundance. First, the equilibration timescale is longer than a sol. Second, the equilibrium abundances are a small fraction of that predicted by earlier adsorption isotherms. The explanation for this phenomenon is that smectite clay actually increases its surface area as a function of adsorptive coverage. At Mars-like conditions, we show that the interlayer sites of smectites are likely to be unavailable.

  6. Gas chemistry and thermometry of the Cerro Prieto, Mexico, geothermal field

    USGS Publications Warehouse

    Nehring, N.L.; D'Amore, F.

    1984-01-01

    Gas compositions of Cerro Prieto wells in 1977 reflected strong boiling in the reservoir around wells M-20 and M-25. This boiling zone appeared to be collapsing in 1982 when a number of wells in this area of the field were shut-in. In 1977 and 1982, gas compositions also showed boiling zones corresponding to faults H and L postulated by Halfman et al. (1982). Four gas geothermometers were applied, based on reservoir equilibria and calculated fugacities. The Fisher - Tropsch reaction predicted high temperatures and appeared to re-equilibrate slowly, whereas the H2S reaction predicted low temperatures and appeared to re-equilibrate rapidly. Hydrogen and NH3 reactions were intermediate. Like gas compositions, the geothermometers reflected reservoir processes, such as boiling. Surface gas compositions are related to well compositions, but contain large concentrations of N2 originating from air dissolved in groundwater. The groundwater appears to originate in the east and flow over the production field before mixing with reservoir gases near the surface. ?? 1984.

  7. Opaque Assemblages in CK and CV Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Neff, K. E.; Righter, K.

    2006-01-01

    CK carbonaceous chondrites are the only group of carbonaceous chondrites that exhibit thermal metamorphism. As a result, CKs display features of metamorphism such as silicate darkening, recrystallization and shock veins. Calcium Aluminum Inclusions and Fe-Ni metal are rare. CV carbonaceous chondrites are unequilibrated and have two subgroups; oxidized and reduced. The CV and CK carbonaceous chondrite groups have been compared to each other often because of petrographic similarities, such as overlapping oxygen isotopic ratios. Scientists have suggested the two groups of carbonaceous chondrites formed from the same parent body and CKs are equilibrated CV chondrites [1, 2]. The oxidized CV group has been most closely related to CKs. This study examines the petrology and mineralogy of CKs and CVs focusing on opaque minerals found in the meteorites. Using the oxide, metal and sulfide assemblages, constraints can be placed on the temperature and oxygen fugacity at which the meteorites equilibrated. The temperature and oxygen fugacity of the CK and CV chondrites can be compared in order to help define their formation history.

  8. Use of Inert Gases to Study the Interaction of Blood Flow and Diffusion during Passive Absorption from the Gastrointestinal Tract of the Rat

    PubMed Central

    Levitt, Michael D.; Levitt, David G.

    1973-01-01

    Measurement of the relative absorption rates of inert gases (H2, He, CH4, SF6, and 133Xe) was used to investigate the interaction between diffusion and blood flow during passive absorption from the stomach, small bowel, and colon of the rat. If uptake is blood flow limited, the gases should be absorbed in proportion to their solubilities in blood, but if diffusion limited, uptake should be proportional to the diffusion rate of the gases in mucosal tissues. The observed absorption data were fitted to a series of models of interaction between perfusion and diffusion. A simple model accurately predicted the absorption rates of the gases from all segments of bowel. In this model, gas is absorbed into two distinct blood flows: one which flows in proximity to the lumen and completely equilibrates with the lumen, and a second which is sufficiently rapid and distant from the lumen that its gas uptake is entirely diffusion limited. The fraction of the total absorption attributable to the equilibrating flow can be readily calculated and equalled 93%, 77%, and 33% for the small bowel, colon, and stomach, respectively. Thus the rate of passive absorption of gases from the small bowel is limited almost entirely by the blood flow to the mucosa, and absorption from the stomach is largely limited by the diffusion rate of the gases. The flow which equilibrates with the lumen can be quantitated, and this flow may provide a useful measure of “effective” mucosal blood flow. Images PMID:4719667

  9. Underthrusting of passive margin strata into deep crustal hot zones associated with Cretaceous arc magmatism in North America: links and timescales of magmatic vs. tectonic thickening

    NASA Astrophysics Data System (ADS)

    Chin, E. J.; Lee, C.; Tollstrup, D. L.; Xie, L.; Wimpenny, J.; Yin, Q.

    2011-12-01

    The North American Cordillera experienced lithospheric thickening during the Cretaceous as a result of subduction-induced magmatism and tectonic shortening. Several studies suggest correlations between increased plate convergence rates and crustal underthrusting with apparent magmatic flux and evolved isotopic excursions, yet questions still remain regarding causality between tectonic and magmatic thickening. Here, we use lower crustal garnet-bearing metaquartzite (80% SiO2) xenoliths hosted in late Miocene basalts in the central Sierra Nevada Batholith, California to constrain the P-T-t (pressure-temperature-time) history of crustal thickening. The xenoliths are equigranular in texture and are comprised of >50% quartz, ~10% metamorphic garnet, <40% plagioclase, and trace rutile, kyanite, and biotite. High quartz mode, abundant well-rounded detrital zircons, and oriented graphite laths demonstrating sedimentary or metamorphic layering point to a supracrustal sedimentary protolith. However, final equilibration temperatures using titanium-in-quartz thermometry are 700 - 800 °C, and final equilibration pressures using the GASP barometer yield 0.9 - 1.3 GPa, indicating the metaquartzites equilibrated within a hot lower crust (18 - 45 km). Low whole-rock REE totals, lack of whole-rock HREE enrichment relative to LREE and MREE, and absence of positive Eu anomalies suggest that significant melting in the garnet or plagioclase fields did not occur. The whole-rock trace element geochemistry is also consistent with an initially garnet-free protolith. Simultaneous LA-ICP-MS measurements of U-Pb and Hf isotopes in detrital zircons show that all zircons have discordant U-Pb with variable upper intercept ages (1.7, 2.7, 3.3 Ga; consistent with Hf model ages), but common lower intercept ages (100 Ma). The above indicate that protoliths of the metaquartzites were North American Proterozoic to Paleozoic passive margin sediments which were simultaneously emplaced into the lower crust at ~100 Ma, during the peak of Cretaceous arc magmatism. We envision underthrusting of N. American lithosphere beneath the active Sierran arc as the mechanism for transporting these sediments to high P, T conditions, but underthrusting cold continental lithosphere alone cannot explain the xenoliths' high final temperatures. An additional heat source, derived from deep crustal magmatic "hot zones", seems required. We are currently exploring diffusion modeling in garnet porphyroblasts as a way to estimate rates of thickening. Because the protoliths were initially garnet-free, growth of metamorphic garnet can potentially record the length of time it took the metaquartzites to achieve their high P, T conditions. We will also use Ti zonation in detrital zircons as an added constraint on timescales involved in thickening. So far, our results indicate firsthand that tectonic underthrusting of continental supracrustal rocks extends all the way into deep magmatic zones beneath arcs, implying that magmatic differentiation alone is not the only mechanism by which continental crust achieves its felsic composition.

  10. Cryopreservation of sperm in Grey mullet Mugil cephalus (Linnaeus, 1758).

    PubMed

    Balamurugan, Ramachandran; Munuswamy, Natesan

    2017-10-01

    The aim of this study was to document the effects of cryopreservation on sperm motility and viability in Grey mullet Mugil cephalus. Cryopreservation of sperm was attempted by using two extenders ringer solution for marine fish (RSMF) and V2 extender (V2E) and cryoprotectants dimethylacetamide (DMA), dimethylsulfoxide (DMSO), ethylene glycol (EG), glycerol (GLY), propylene glycol (PG) and methanol (MeOH). Cryoprotectants were assessed at different concentrations individually as well as in combination with varying equilibration times (10 and 30min). For optimization of freezing rate, four freezing protocols (-5, -10, -20 and -30°C/min) were evaluated. After achieving final temperature, samples were plunged in liquid nitrogen (-196°C) and stored for a week. Samples were subsequently thawed in a water bath at 30°C for assessment of sperm motility and viability. Results indicated that cryomedium constituting of V2E extender+10% glycerol with a dilution ratio of 1:1 (sperm: cryomedium) at an equilibration time of 5 to- 10min and freezing rate of -20°C/min was more desirable compared with other factors that were assessed. Use of this protocol resulted in retaining the greatest sperm motility grade 3.0±0.0 (50%-80% sperm movement, fast swimming) and 48.19±3.12% of sperm viability. The results of the present study, therefore, provide base-line data for establishing a protocol for sperm cryopreservation in M.cephalus. Further studies are, however, required for optimization of most suitable sperm cryopreservation protocol. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Temperature uniformity of the bulk medium produced in relativistic heavy-ion collisions

    NASA Astrophysics Data System (ADS)

    Ray, Lanny

    2006-10-01

    The success of hydrodynamic models of elliptic flow in relativistic heavy ion collisions is often touted as evidence for rapid thermal equilibration. However, large momentum scale two-particle correlations indicate that a significant fraction of the final-state hadrons retain jet-like correlation structure associated with early stage, non-equilibrated low-Q^2 partons [1]. In addition, correlations on transverse momentum (pt1xpt2) suggest that low-Q^2 parton momentum is partially dissipated causing fluctuations in the effective temperature (thermal and/or collective motion) of the bulk medium[2]. We first show that both global and local temperature fluctuation models describe the available (pt1xpt2) correlation data equally well. Results of an analytical model are then presented which tests the sensitivity of (pt1xpt2) correlations to the first few lower-order cumulants of the two-point temperature distribution for the event ensemble. Unique signatures in the predicted (pt1xpt2) correlations are observed for each cumulant term studied. The prospects for direct measurement of the absolute temperature distribution in the bulk medium produced in relativistic heavy-ion collisions using (pt1xpt2) and other correlation measures are discussed. [1] J. Adams et al., Phys. Rev. C 73, 064907 (2006); J. Phys.G. 32, L37 (2006). [2]J. Adams et al., nucl-ex/0408012.

  12. Entanglement tsunami: universal scaling in holographic thermalization.

    PubMed

    Liu, Hong; Suh, S Josephine

    2014-01-10

    We consider the time evolution of entanglement entropy after a global quench in a strongly coupled holographic system, whose subsequent equilibration is described in the gravity dual by the gravitational collapse of a thin shell of matter resulting in a black hole. In the limit of large regions of entanglement, the evolution of entanglement entropy is controlled by the geometry around and inside the event horizon of the black hole, resulting in regimes of pre-local-equilibration quadratic growth (in time), post-local-equilibration linear growth, a late-time regime in which the evolution does not carry memory of the size and shape of the entangled region, and a saturation regime with critical behavior resembling those in continuous phase transitions. Collectively, these regimes suggest a picture of entanglement growth in which an "entanglement tsunami" carries entanglement inward from the boundary. We also make a conjecture on the maximal rate of entanglement growth in relativistic systems.

  13. Temperature dependency of state of charge inhomogeneities and their equalization in cylindrical lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Osswald, P. J.; Erhard, S. V.; Rheinfeld, A.; Rieger, B.; Hoster, H. E.; Jossen, A.

    2016-10-01

    The influence of cell temperature on the current density distribution and accompanying inhomogeneities in state of charge (SOC) during cycling is analyzed in this work. To allow for a detailed insight in the electrochemical behavior of the cell, commercially available 26650 cells were modified to allow for measuring local potentials at four different, nearly equidistant positions along the electrodes. As a follow-up to our previous work investigating local potentials within a cell, we apply this method for studying SOC deviations and their sensitivity to cell temperature. The local potential distribution was studied during constant current discharge operations for various current rates and discharge pulses in order to evoke local inhomogeneities for temperatures ranging from 10 °C to 40 °C. Differences in local potentials were considered for estimating local SOC variations within the electrodes. It could be observed that even low currents such as 0.1C can lead to significant inhomogeneities, whereas a higher cell temperature generally results in more pronounced inhomogeneities. A rapid SOC equilibration can be observed if the variation in the SOC distribution corresponds to a considerable potential difference defined by the open circuit voltage of either the positive or negative electrode. With increasing temperature, accelerated equalization effects can be observed.

  14. Thermal History of Ordinary Chondrites: Comparison and Evaluation of Chronological Tools

    NASA Astrophysics Data System (ADS)

    Manhes, G.; Gopel, C.

    1993-07-01

    The structure and the thermal history of ordinary chondrites is disputed, because there is no agreement as to whether radiometric ages, metallographic cooling rates (MTCR) [1], fission-track cooling rates (FTCR) [2], and petrographic observations correlate [3,4]. The comparison of these published data is discussed in the case of the H chondrites with reference to the Pb/Pb systematics determined in their phosphates [5]. It is assumed that the age derived from each chronometer defines the time period after which the material reached its closure temperature, cooling down from higher temperatures. What is of interest for the Pb/Pb systematics is the time resolution of 10^6 yr and the knowledge of the closure temperature of the U/Pb system in the phosphates derived from experimental studies [6]: 710 K for a cooling rate of 5 K/m.y. 1. The Pb/Pb systematics define a time interval of 6 x 10^6 yr for the thermal processing of equilibrated H chondrites; this is coherent with the estimation previously derived from the Rb/Sr [7,8], Ar/Ar [9], and Pu chronologies [10]. 2. When the different metamorphic grades of equilibrated H chondrites are considered, no significant correlation exists between the Pb/Pb systematics and the Ar/Ar chronology; the chronology is based on the Sr initial method and the I-Xe systematics, whereas a positive correlation with the metallographic and fission-track cooling rates is seen. 3. The chronological tools (Pb/Pb, Ar/Ar, FTCR, MCR) are compared in the best- documented chondrites (H6 Guarena, H6 Kernouve, H5 Richardton) taking into account the estimated closure temperatures, which range from 900 to 380 K. This comparison does not point out either a monotonic cooling regime occurring in a parent body with a preserved layered structure or a two-step cooling regime (fast cooling at temperatures higher than 770 K and slower cooling at lower temperatures). Such an attempt to reconstruct the thermal history of ordinary chondrites is based on the interpretation of the radiochronometric data as translating the thermal closure of the different isotopic systems. This basic interpretation may be incorrect for some chondrites and must be evaluated before the chronometric informations are applied as precise time constraints in the 4.56- 4.4 aeon interval. References: [1] Taylor G. J. et al. (1987) Icarus, 69, 1-13. [2] Lipschutz M. E. et al. (1989) In Asteroids II (R. Binzel et al., eds.), 740-778, Univ. of Arizona. [3] Hutchison R. et al. (1980) Nature, 287, 787-790. [4] Christophe MichelLevy M. (1981) EPSL, 54, 67-80. [5] Gopel C. et al. (1990) Meteoritics, 25, 367-368. [6] Cherniak D. et al. (1991) GCA, 55, 1663-1673. [7] Minster J. F. et al. (1982) Nature, 300, 414-419. [8] Podosek F. A. and Brannon J. C. (1991) Meteoritics, 26, 145-152. [9] Turner G. et al. (1978) Proc. LPSC 9th, 989-1025. [10] Pellas P. and Storzer D. (1981) Proc. R. Soc. London, A374, 253-270.

  15. Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

    NASA Technical Reports Server (NTRS)

    Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.

    2017-01-01

    Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

  16. Study of density distribution in a near-critical simple fluid (19-IML-1)

    NASA Technical Reports Server (NTRS)

    Michels, Teun

    1992-01-01

    This experiment uses visual observation, interferometry, and light scattering techniques to observe and analyze the density distribution in SF6 above and below the critical temperature. Below the critical temperature, the fluid system is split up into two coexisting phases, liquid and vapor. The spatial separation of these phases on earth, liquid below and vapor above, is not an intrinsic property of the fluid system; it is merely an effect of the action of the gravity field. At a fixed temperature, the density of each of the coexisting phases is in principle fixed. However, near T sub c where the fluid is strongly compressible, gravity induced hydrostatic forces will result in a gradual decrease in density with increasing height in the sample container. This hydrostatic density profile is even more pronounced in the one phase fluid at temperatures slightly above T sub c. The experiment is set up to study the intrinsic density distributions and equilibration rates of a critical sample in a small container. Interferometry will be used to determine local density and thickness of surface and interface layers. The light scattering data will reveal the size of the density fluctuations on a microscopic scale.

  17. Determination of enzyme thermal parameters for rational enzyme engineering and environmental/evolutionary studies.

    PubMed

    Lee, Charles K; Monk, Colin R; Daniel, Roy M

    2013-01-01

    Of the two independent processes by which enzymes lose activity with increasing temperature, irreversible thermal inactivation and rapid reversible equilibration with an inactive form, the latter is only describable by the Equilibrium Model. Any investigation of the effect of temperature upon enzymes, a mandatory step in rational enzyme engineering and study of enzyme temperature adaptation, thus requires determining the enzymes' thermodynamic parameters as defined by the Equilibrium Model. The necessary data for this procedure can be collected by carrying out multiple isothermal enzyme assays at 3-5°C intervals over a suitable temperature range. If the collected data meet requirements for V max determination (i.e., if the enzyme kinetics are "ideal"), then the enzyme's Equilibrium Model parameters (ΔH eq, T eq, ΔG (‡) cat, and ΔG (‡) inact) can be determined using a freely available iterative model-fitting software package designed for this purpose.Although "ideal" enzyme reactions are required for determination of all four Equilibrium Model parameters, ΔH eq, T eq, and ΔG (‡) cat can be determined from initial (zero-time) rates for most nonideal enzyme reactions, with substrate saturation being the only requirement.

  18. Speculative and Hedging Interaction Model in Oil and U.S. Dollar Markets—Phase Transition

    NASA Astrophysics Data System (ADS)

    Campbell, Michael; Carfì, David

    2018-01-01

    We show that there is a phase transition in the bounded rational Carfì-Musolino model, and the possibility of a market crash. This model has two types of operators: a real economic subject (Air) and one or more investment banks (Bank). It also has two markets: oil spot market and US dollar futures. Bank agents react to Air and equilibrate much more quickly than Air. Thus Air is an acting external agent due to its longer-term investing, whereas the action of the banks equilibrates before Air makes its next transaction. This model constitutes a potential game, and agents crowd their preferences into one of the markets at a critical temperature when air makes no purchases of oil futures.

  19. Metamorphism of brecciated ANT rocks - Anorthositic troctolite 72559 and norite 78527. [Anorthositic-Noritic-Troctolitic

    NASA Technical Reports Server (NTRS)

    Nehru, C. E.; Warner, R. D.; Keil, K.; Taylor, G. J.

    1978-01-01

    Rake samples 72559 and 78527 are annealed rocks of ANT-suite mineralogy and bulk composition. The rocks were presumably derived from ancient lunar highland ANT rocks of cumulate origin. Sample 72559 is polymict and its precursors were anorthositic-troctolitic in composition. Sample 78527 is monomict and of noritic derivation. The precursors were brecciated due to impact processes; 72559 shows evidence of some impact melting. The samples were thermally metamorphosed forming rocks with granoblastic matrix textures. Coexisting matrix pyroxenes indicate equilibration temperatures of 950-1000 C for both rocks. Accessory opaque oxide minerals in the rocks show rather wide compositional variations. These probably primarily reflect compositional ranges inherited from the precursor/s with little integranular equilibration among them during metamorphism.

  20. Acceleration of Lateral Equilibration in Mixed Lipid Bilayers Using Replica Exchange with Solute Tempering

    PubMed Central

    2015-01-01

    The lateral heterogeneity of cellular membranes plays an important role in many biological functions such as signaling and regulating membrane proteins. This heterogeneity can result from preferential interactions between membrane components or interactions with membrane proteins. One major difficulty in molecular dynamics simulations aimed at studying the membrane heterogeneity is that lipids diffuse slowly and collectively in bilayers, and therefore, it is difficult to reach equilibrium in lateral organization in bilayer mixtures. Here, we propose the use of the replica exchange with solute tempering (REST) approach to accelerate lateral relaxation in heterogeneous bilayers. REST is based on the replica exchange method but tempers only the solute, leaving the temperature of the solvent fixed. Since the number of replicas in REST scales approximately only with the degrees of freedom in the solute, REST enables us to enhance the configuration sampling of lipid bilayers with fewer replicas, in comparison with the temperature replica exchange molecular dynamics simulation (T-REMD) where the number of replicas scales with the degrees of freedom of the entire system. We apply the REST method to a cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayer mixture and find that the lateral distribution functions of all molecular pair types converge much faster than in the standard MD simulation. The relative diffusion rate between molecules in REST is, on average, an order of magnitude faster than in the standard MD simulation. Although REST was initially proposed to study protein folding and its efficiency in protein folding is still under debate, we find a unique application of REST to accelerate lateral equilibration in mixed lipid membranes and suggest a promising way to probe membrane lateral heterogeneity through molecular dynamics simulation. PMID:25328493

  1. Acceleration of Lateral Equilibration in Mixed Lipid Bilayers Using Replica Exchange with Solute Tempering.

    PubMed

    Huang, Kun; García, Angel E

    2014-10-14

    The lateral heterogeneity of cellular membranes plays an important role in many biological functions such as signaling and regulating membrane proteins. This heterogeneity can result from preferential interactions between membrane components or interactions with membrane proteins. One major difficulty in molecular dynamics simulations aimed at studying the membrane heterogeneity is that lipids diffuse slowly and collectively in bilayers, and therefore, it is difficult to reach equilibrium in lateral organization in bilayer mixtures. Here, we propose the use of the replica exchange with solute tempering (REST) approach to accelerate lateral relaxation in heterogeneous bilayers. REST is based on the replica exchange method but tempers only the solute, leaving the temperature of the solvent fixed. Since the number of replicas in REST scales approximately only with the degrees of freedom in the solute, REST enables us to enhance the configuration sampling of lipid bilayers with fewer replicas, in comparison with the temperature replica exchange molecular dynamics simulation (T-REMD) where the number of replicas scales with the degrees of freedom of the entire system. We apply the REST method to a cholesterol and 1,2-dipalmitoyl- sn -glycero-3-phosphocholine (DPPC) bilayer mixture and find that the lateral distribution functions of all molecular pair types converge much faster than in the standard MD simulation. The relative diffusion rate between molecules in REST is, on average, an order of magnitude faster than in the standard MD simulation. Although REST was initially proposed to study protein folding and its efficiency in protein folding is still under debate, we find a unique application of REST to accelerate lateral equilibration in mixed lipid membranes and suggest a promising way to probe membrane lateral heterogeneity through molecular dynamics simulation.

  2. Choice of 17O Abundance Correction Affects Δ47 and Thus Calibrations for Paleothermometry

    NASA Astrophysics Data System (ADS)

    Kelson, J.; Schauer, A. J.; Huntington, K. W.; Saenger, C.; Lechler, A. R.

    2016-12-01

    The clumped isotope composition of CO2 derived from carbonate (Δ47) varies with temperature, making it a valuable geothermometer with broad applications. However, its accuracy is limited by inter-laboratory discrepancies of carbonate reference materials and disagreement among Δ47-temperature calibrations. Here we use a suite of CO2-H2O equilibrations at known temperatures with a wide range in 13C and 18O compositions to show how the correction for the abundance of 17O impacts Δ47 and potentially explains these discrepancies. When a traditional value of 0.5164 is used for the fractionation between 17O and 18O (λ), corrected Δ47 in 23 °C CO2-H2O equilibrations exhibits a dependence on 13C composition that is equivalent to 20 ºC (Δ47 range of 0.06 ‰). In contrast, these discrepancies are effectively removed when λ=0.528, as in global meteoric waters. Furthermore, carbonate standards with identical formation temperatures have significantly different Δ47 when corrected using λ=0.5164, but agree within error when λ=0.528. The choice of λ affects the accuracy of all sample Δ47 values, unless the sample CO2, mass spectrometer reference gas, and equilibrated gases share the same 13C composition. The sensitivity of Δ47 to the choice of λ, and the apparent dependence on 13C when 0.5164 is used, are relevant to the abiogenic experiments used in Δ47-temperature calibrations given that precipitation methods involving CO2 bubbling produce carbonates depleted in 13C by tens of permil relative to methods that mix salts. We evaluate the influence of 17O correction on Δ47-temperature calibrations using a suite of 58 abiogenic carbonates precipitated at 4-85 ºC using CO2 bubbling and the mixing of salts. Aliquots of precipitated carbonates were digested at 25 and 90ºC, but all other preparatory and analytical variables were held constant. When corrected using λ=0.5164, various precipitation methods yield sub-parallel Δ47-temperature relationships with slopes of 0.034-0.044 (x 106/T2), but offset intercepts. Conversely, Δ47-temperature relationships overlap within error when λ=0.528. This suggests that the method used to correct for 17O abundance likely contributes to observed calibration discrepancies and that adopting λ=0.528 may reduce the uncertainty in Δ47 temperature reconstructions.

  3. Limitations of heterogeneous models of liquid dynamics: very slow rate exchange in the excess wing.

    PubMed

    Samanta, Subarna; Richert, Ranko

    2014-02-07

    For several molecular glass formers, the nonlinear dielectric effects (NDE's) are investigated for the so-called excess wing regime, i.e., for the relatively high frequencies between 10(2) and 10(7) times the peak loss frequency. It is found that significant nonlinear behavior persists across the entire frequency window of this study, and that its magnitude traces the temperature dependence of the activation energy. A time resolved measurement of the dielectric loss at fields up to 480 kV/cm across tens of thousands of periods reveals that it takes an unexpectedly long time for the steady state NDE to develop. For various materials and at different temperatures and frequencies, it is found that the average structural relaxation with time scale τα governs the equilibration of these fast modes that are associated with time constants τ which are up to 10(7) times shorter than τα. It is argued that true indicators of structural relaxation (such as rate exchange and aging) of these fast modes are slaved to macroscopic softening on the time scale of τα, and thus many orders of magnitude slower than the time constant of the mode itself.

  4. Voltage Quench Dynamics of a Kondo System.

    PubMed

    Antipov, Andrey E; Dong, Qiaoyuan; Gull, Emanuel

    2016-01-22

    We examine the dynamics of a correlated quantum dot in the mixed valence regime. We perform numerically exact calculations of the current after a quantum quench from equilibrium by rapidly applying a bias voltage in a wide range of initial temperatures. The current exhibits short equilibration times and saturates upon the decrease of temperature at all times, indicating Kondo behavior both in the transient regime and in the steady state. The time-dependent current saturation temperature connects the equilibrium Kondo temperature to a substantially increased value at voltages outside of the linear response. These signatures are directly observable by experiments in the time domain.

  5. Temperature Gradients on the Cell Wall in the Critical Viscosity Experiment

    NASA Technical Reports Server (NTRS)

    Berg, Robert F.; Moldover, Michael R.

    1993-01-01

    Because of the diverging susceptibility delta rho/delta Tau near the liquid-vapor critical point, temperature gradients must be kept small to maintain adequate sample homogeneity. In our Science Requirements Document we paid particular attention to radial density gradients caused by equilibration of the xenon sample. Axial density gradients were addressed through the requirement that the cell's copper wall have a gradient less than 22 microK/m. This report re-examines the cell wall's temperature distribution in more detail by estimating all known significant contributions to temperature differences on the cell's wall.

  6. Co/Ni ratios at taenite/kamacite interfaces and relative cooling rates in iron meteorites

    NASA Astrophysics Data System (ADS)

    Wasson, John T.; Hoppe, Peter

    2012-05-01

    We report a pilot study of a new technique to use the distribution of Co between kamacite and taenite to infer relative cooling rates of iron meteorites; data of Widge and Goldstein (1977) showed that the distribution is temperature dependent. A plot of the logarithm of the double ratio [(Co/Ni)kamacite/(Co/Ni)taenite] (abbreviated Rαγ) against inverse temperature yields a linear equation showing that the ratio ranges from ˜2.5 at 1080 K to ˜30 at 710 K. Thus, a measurement of Rαγ in the kamacite and taenite near the interface offers information about relative cooling rates; the higher Rαγ, the lower the cooling rate. A major advantage of this technique is that it is mainly affected by the final (low-temperature) cooling rate, just before the sample cooled to the blocking temperature where diffusion became insignificant. To test this method we used the NanoSIMS ion probe to measure Rαγ in two IVA and two IIIAB irons; members of each pair differ by large factors in elemental composition and in published metallographic cooling rates (Yang and Goldstein, 2006; Yang et al., 2008). Despite differing by a factor of 25 in estimated metallographic cooling rate, the two IVA irons showed similar Rαγ values of ˜22. If experimental uncertainties are considered this implies that, at low temperatures, their cooling rates differ by less than a factor of 5 with 95% confidence, i.e., significantly less than the range in metallographic cooling rates. In contrast, the IIIAB irons have different ratios; Rαγ in Haig is 29 whereas that in Cumpas, with a reported cooling rate 4.5 times lower, is 22, the opposite of that expected from the published cooling rates. A reevaluation of the Yang-Goldstein IIIAB data set shows that Haig has anomalous metallographic properties. We suggest that both the high Rαγ in Haig and the systematically low taenite central Ni contents are the result of impact-produced fractures in the taenite that allowed equilibration with kamacite down to lower temperatures but shut down Ni transport to the interiors of taenite lamellae. Our observations of similar Rαγ values in IVA irons differing by a factor of 25 in metallographic cooling rates implies that there was, in fact, only a comparatively small difference in low-temperature cooling rates in IVA irons; because we studied only two IVA irons, this conclusion will remain tentative until further studies can be completed.

  7. Cook and Chill: Effect of Temperature on the Performance of Nonequilibrated Blood Glucose Meters.

    PubMed

    Deakin, Sherine; Steele, Dominic; Clarke, Sarah; Gribben, Cathryn; Bexley, Anne-Marie; Laan, Remmert; Kerr, David

    2015-08-20

    Exposure to extreme temperature can affect the performance of blood glucose monitoring systems. The aim was to determine the non-equilibrated performance of these systems at extreme high and low temperatures that can occur in daily life. The performances of 5 test systems, (1) Abbott FreeStyle Freedom Lite, (2) Roche AccuChek Aviva, (3) Bayer Contour, (4) LifeScan OneTouch Verio, and (5) Sanofi BG Star, were compared after "cooking" (50°C for 1 hour) or "chilling" (-5°C for 1 hour) with room temperature controls (23°C) using whole blood with glucose concentrations of 50, 100, and 200 mg/dl. The equilibration period (time from the end of incubation to when the test system is operational) was between 1 and 8 minutes, and each test system took between 15 and 30 minutes after incubation to obtain stable measurements at room temperature. Incubating the strips at -5°C or 50°C had little effect on the glucose measurement, whereas incubating the meters introduced bias in performance between 0 and 15 minutes but not subsequently, compared to room temperature controls and at all 3 glucose levels. Compensating technologies embedded within blood glucose monitoring systems studied here perform well at extreme temperatures. People with diabetes need to be alerted to this feature to avoid perceptions of malperformance of their devices and the possible inability to get blood glucose readings on short notice (eg, during time of suspected rapid change or before an unplanned meal). © 2015 Diabetes Technology Society.

  8. Application of Silicon Micromachining to Thermal Dissipation Issues in Wafer Scale Integrated Circuits

    DTIC Science & Technology

    1991-12-01

    the cartesian coordinate system, ( hkl ) is the general mathematical representation for a crystal plane. The planar densities of a crystal and the...furnace’s temperature was pre-equilibrated to the pre- set oxidation temperature of 1075 °C. Oxygen was bubbled through DIW at 95 °C to promote the growth...to the pre-set oxidation temperature of 1075 °C. An oxygen flow was initiated at 1 liter per minute to realize a high quality, dry SiO 2 thin-film on

  9. Ab initio/GIAO-CCSD(T) (13)C NMR study of the rearrangement and dynamic aspects of rapidly equilibrating tertiary carbocations, C6H13(+) and C7H15(+).

    PubMed

    Olah, George A; Prakash, G K Surya; Rasul, Golam

    2016-01-05

    The rearrangement pathways of the equilibrating tertiary carbocations, 2,3-dimethyl-2-butyl cation (C6H13(+), 1), 2,3,3-trimethyl-2-butyl cation (C7H15(+), 5) and 2,3-dimethyl-2-pentyl cation (C7H15(+), 8 and 9) were investigated using the ab initio/GIAO-CCSD(T) (13)C NMR method. Comparing the calculated and experimental (13)C NMR chemical shifts of a series of carbocations indicates that excellent prediction of δ(13)C could be achieved through scaling. In the case of symmetrical equilibrating cations (1 and 5) the Wagner-Meerwein 1,2-hydride and 1,2-methide shifts, respectively, produce the same structure. This indicates that the overall (13)C NMR chemical shifts are conserved and independent of temperature. However, in the case of unsymmetrical equilibrating cations (8 and 9) the Wagner-Meerwein shift produces different tertiary structures, which have slightly different thermodynamic stabilities and, thus, different spectra. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level structure 8 is only 90 calories/mol more stable than structure 9. Based on computed (13)C NMR chemical shift calculations, mole fractions of these isomers were determined by assuming the observed chemical shifts are due to the weighted average of the chemical shifts of the static ions. © 2015 Wiley Periodicals, Inc.

  10. Transient rheology of crystallizing andesitic magmas

    NASA Astrophysics Data System (ADS)

    de Biasi, L. J.; Chevrel, M. O.; Hanson, J. B.; Cimarelli, C.; Lavallée, Y.; Dingwell, D. B.

    2012-04-01

    The viscosity of magma strongly influences its rheological behaviour, which is a key determinant of magma transport processes and volcanic eruptions. Understanding the factors controlling the viscosity of magma is important to our assessment of hazards posed by active volcanoes. In nature, magmas span a very wide range in viscosity (10-1 to 1014 Pa s), depending on chemical composition (including volatile content), temperature, and importantly, crystal fraction, which further induces a complex strain rate dependence (i.e. non-Newtonian rheology). Here, we present results of transient viscosities of a crystallizing andesitic melt (57 wt.% SiO2) from Tungurahua volcano (Ecuador). We followed the experimental method developed by Vona et al. (2011) for the concentric cylinder apparatus, but optimized its implementation by leaving the spindle in situ before quenching the experimental products, to preserve the complete developed texture of the sample. The viscosity is investigated under super-liquidus (1400 ° C) and sub-liquidus temperatures (1162 and 1167 ° C). For each temperature increment, thermal equilibrium is achieved over a period of days while the spindle constantly stirs the magma. Simultaneous monitoring of the torque is used to calculate the apparent viscosity of the transient suspension. To get a better understanding of the nucleation and crystal growth processes that are involved at sub-liquidus conditions, further time-step experiments were carried out, where the samples were quenched at various equilibration stages. The mineralogical assemblage, as well as the crystal fraction, distribution and preferential alignment were then quantitatively analyzed. At temperatures below the liquidus, the suspension shows a progressive, but irregular increase of the relative shear viscosity. First, the viscosity slightly increases, possibly due to the crystallization of small, equant oxides and the formation of plagioclase nuclei. After some time (1.5-2.5 days), crystallization of large, tabular plagioclase begins, inducing a significantly stronger increase in apparent viscosity until thermo-chemical equilibration is achieved. After continued stirring the apparent viscosity slightly decreases, likely due to increasing crystal alignment. The analysis of pre-equilibrium quenched samples indicates that crystals nucleate and grow preferentially in proximity to both the spindle and the crucible wall. Furthermore, decreasing the stirring rate (aka strain rate) results in an increase in the apparent viscosity, which evidences the non-Newtonian characteristics of the magmatic suspension. In conclusion, these experiments indicate that natural andesitic magmas undergo significant rheological changes at the onset of crystallization. The observed thermo-chemical variations elucidate a transient viscosity, which deserves consideration into all problems of magma transport. Reference: Vona, A., Romano, C., Dingwell, D.B., Giordano, D. 2011. The rheology of crystal-bearing basaltic magmas from Stromboli and Etna. Geochim. Cosmochim. Acta, 75, 3214-3236.

  11. Effect of controlled and uncontrolled rate of cooling, prior to controlled rate of freezing, on motion characteristics and acrosomal integrity of cryopreserved ram spermatozoa.

    PubMed

    Joshi, Anil; Kumar, Davendra; Naqvi, S M K; Maurya, V P

    2008-12-01

    A programmable cell freezer provides ideal cryobiological conditions for controlled-rate cooling and freezing of ram spermatozoa. The purpose of this study was to investigate the effects of controlled (Group 1) and uncontrolled (Group 2) cooling conditions prior to programmable freezing of ram semen on post-thaw sperm motion characteristics and acrosomal integrity of ram spermatozoa. Semen samples of good initial motility obtained from adult Malpura rams were pooled, diluted to 1 × 10(9) spermatozoa per milliliter with Egg yolk-TEST-glycerol extender, and packaged in 0.25 mL straws. Straws representing Group 1 were cooled in a programmable cell freezer from 25°C to 5°C at the rate of -0.15°C per minute followed by a holding time of 2 h for equilibration, while straws of Group 2 were allowed to cool slowly up to 5°C and equilibrate for 2 h in the cold cabinet. After equilibration, straws of Group 2 were also loaded in the cell freezer for freezing straws of both the treatment groups simultaneously from 5°C to -125°C at the rate of -25°C per minute. Thawing of straws was done at 50°C for 10 s and the quality of frozen-thawed spermatozoa was objectively assessed by using sperm motility analyzer. Thawed samples were also evaluated for acrosomal integrity after staining the dried semen smears with Giemsa stain. The average post-thaw motility of straws was significantly higher (P < 0.05) in samples frozen after controlled cooling, compared with samples frozen after uncontrolled rate of cooling. The percent of spermatozoa with normal acrosome was also significantly (P < 0.05) higher in Group 1, compared to Group 2. The results indicate that controlled-rate cooling has a significant effect on post-thaw motility and acrosomal integrity of frozen-thawed ram spermatozoa, compared to uncontrolled-rate cooling prior to programmable freezing.

  12. Demonstration of Temperature Dependent Energy Migration in Dual-Mode YVO4: Ho3+/Yb3+ Nanocrystals for Low Temperature Thermometry

    PubMed Central

    Kumar Mahata, Manoj; Koppe, Tristan; Kumar, Kaushal; Hofsäss, Hans; Vetter, Ulrich

    2016-01-01

    A dual mode rare-earth based vanadate material (YVO4: Ho3+/Yb3+), prepared through ethylene glycol assisted hydrothermal method, demonstrating both downconversion and upconversion, along with systematic investigation of the luminescence spectroscopy within 12–300 K is presented herein. The energy transfer processes have been explored via steady-state and time-resolved spectroscopic measurements and explained in terms of rate equation description and temporal evolution below room temperature. The maximum time for energy migration from host to rare earth (Ho3+) increases (0.157 μs to 0.514 μs) with the material’s temperature decreasing from 300 K to 12 K. The mechanism responsible for variation of the transients’ character is discussed through thermalization and non-radiative transitions in the system. More significantly, the temperature of the nanocrystals was determined using not only the thermally equilibrated radiative intra-4f transitions of Ho3+ but also the decay time and rise time of vanadate and Ho3+ energy levels. Our studies show that the material is highly suitable for temperature sensing below room temperature. The maximum relative sensor sensitivity using the rise time of Ho3+ energy level (5F4/5S2) is 1.35% K−1, which is the highest among the known sensitivities for luminescence based thermal probes. PMID:27805060

  13. The Cooling History and Structure of the Ordinary Chondrite Parent Bodies

    NASA Technical Reports Server (NTRS)

    Benoit, P. H.; Sears, D. W. G.

    1996-01-01

    Most major meteorite classes exhibit significant ranges of metamorphism. The effects of metamorphism have been extensively characterized, but the heat source(s) and the metamorphic environment are unknown. Proposed beat sources include Al-26, Fe-60, electromagnetic induction, and impact. It is typically assumed that metamorphism occurred in parent bodies of some sort, but it uncertain whether these bodies were highly structured ("onion skins") or were chaotic mixes of material ("rubble piles"). The lack of simple trends of metallographic cooling rates with petrologic type has been considered supportive of both concepts. In this study, we use induced thermoluminescence (TL) as an indicator of thermal history. The TL of ordinary chondrites is produced by sodic feldspar, and the induced TL peak temperature is related to its crystallographic order/disorder. Ordered feldspar has TL peak temperatures of approx. 120 C, and disordered feldspar has TL peak temperatures of approx. 220 C. While ordered feldspar can be easily disordered in the laboratory by heating above 650 C and is easily quenched in the disordered form, producing ordered feldspar requires cooling at geologic cooling rates. We have measured the induced TL properties of 101 equilibrated ordinary chondrites, including 49 H, 29 L, and 23 LL chondrites. For the H chondrites there is an apparent trend of decreasing induced TL peak temperature with increasing petrologic type. H4 chondrites exhibit a tight range of TL peak temperatures, 190 C - 200 C, while H6 chondrites exhibit TL peak temperatures between 180 C and 190 C. H5 chondrites cover the range between H4 and H6, and also extend up to 210 C. Similar results are obtained for LL chondfiles and most L6 chondrites have lower induced TL peak temperatures than L5 chondrites.

  14. Redox reactions with empirical potentials: atomistic battery discharge simulations.

    PubMed

    Dapp, Wolf B; Müser, Martin H

    2013-08-14

    Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each atom. Along with exchanging partial charges across bonds, atoms can swap integer charges. With redoxSQE we study the discharge behavior of a nano-battery, and demonstrate that this reproduces the generic properties of a macroscopic battery qualitatively. Examples are the dependence of the battery's capacity on temperature and discharge rate, as well as performance degradation upon recharge.

  15. Structural modeling of Ge6.25As32.5Se61.25 using a combination of reverse Monte Carlo and Ab initio molecular dynamics.

    PubMed

    Opletal, George; Drumm, Daniel W; Wang, Rong P; Russo, Salvy P

    2014-07-03

    Ternary glass structures are notoriously difficult to model accurately, and yet prevalent in several modern endeavors. Here, a novel combination of Reverse Monte Carlo (RMC) modeling and ab initio molecular dynamics (MD) is presented, rendering these complicated structures computationally tractable. A case study (Ge6.25As32.5Se61.25 glass) illustrates the effects of ab initio MD quench rates and equilibration temperatures, and the combined approach's efficacy over standard RMC or random insertion methods. Submelting point MD quenches achieve the most stable, realistic models, agreeing with both experimental and fully ab initio results. The simple approach of RMC followed by ab initio geometry optimization provides similar quality to the RMC-MD combination, for far fewer resources.

  16. Peak groundwater depletion in the High Plains Aquifer, projections from 1930 to 2110

    USDA-ARS?s Scientific Manuscript database

    Peak groundwater depletion from overtapping aquifers beyond recharge rates occurs as the depletion rate increases until a peak occurs followed by a decreasing trend as pumping equilibrates towards available recharge. The logistic equation of Hubbert’s study of peak oil is used to project measurement...

  17. The effect of natural organic matter on mercury methylation by Desulfobulbus propionicus 1pr3

    USGS Publications Warehouse

    Moreau, John W.; Gionfriddo, Caitlin M.; Krabbenhoft, David P.; Ogorek, Jacob M.; DeWild, John F.; Aiken, George R.; Roden, Eric E.

    2015-01-01

    Methylation of tracer and ambient mercury (200Hg and 202Hg, respectively) equilibrated with four different natural organic matter (NOM) isolates was investigated in vivo using the Hg-methylating sulfate-reducing bacterium Desulfobulbus propionicus 1pr3. Desulfobulbus cultures grown fermentatively with environmentally representative concentrations of dissolved NOM isolates, Hg[II], and HS− were assayed for absolute methylmercury (MeHg) concentration and conversion of Hg(II) to MeHg relative to total unfiltered Hg(II). Results showed the 200Hg tracer was methylated more efficiently in the presence of hydrophobic NOM isolates than in the presence of transphilic NOM, or in the absence of NOM. Different NOM isolates were associated with variable methylation efficiencies for either the 202Hg tracer or ambient 200Hg. One hydrophobic NOM, F1 HpoA derived from dissolved organic matter from the Florida Everglades, was equilibrated for different times with Hg tracer, which resulted in different methylation rates. A 5 day equilibration with F1 HpoA resulted in more MeHg production than either the 4 h or 30 day equilibration periods, suggesting a time dependence for NOM-enhanced Hg bioavailability for methylation.

  18. Development and Evaluation of an Online Air Quality Monitor (DIVEAIR2) for Diving Compressors

    DTIC Science & Technology

    2009-03-01

    nonextreme levels. However, our experience with field testing has shown that the temperatures of work spaces commonly used for instrument setup and...so far. Nevertheless, one strategy for field use might be to allow the monitor to equilibrate to the ambient temperature near the compressor before...limit be subject to change, depending on experience with actual field testing. 4. Before any monitors are delivered to the Fleet for field use, we

  19. Insights from fumarole gas geochemistry on the origin of hydrothermal fluids on the Yellowstone Plateau

    USGS Publications Warehouse

    Chiodini, Giovanni; Caliro, Stefano; Lowenstern, Jacob B.; Evans, William C.; Bergfeld, D.; Tassi, Franco; Tedesco, Dario

    2012-01-01

    The chemistry of Yellowstone fumarole gases shows the existence of two component waters, type MC, influenced by the addition of deep mantle fluid, and type CC, influenced by crustal interactions (CC). MC is high in 3He/4He (22 Ra) and low in 4He/40Ar (~1), reflecting input of deep mantle components. The other water is characterized by 4He concentrations 3-4 orders of magnitude higher than air-saturated meteoric water (ASW). These high He concentrations originate through circulation in Pleistocene volcanic rocks, as well as outgassing of Tertiary and older (including Archean) basement, some of which could be particularly rich in uranium, a major 4He source. Consideration of CO2-CH4-CO-H2O-H2 gas equilibrium reactions indicates equilibration temperatures from 170 °C to 310 °C. The estimated temperatures highly correlate with noble-gas variations, suggesting that the two waters differ in temperature. Type CC is ~170 °C whereas the MC is hotter, at 340 °C. This result is similar to models proposed by previous studies of thermal water chemistry. However, instead of mixing the deep hot component simply with cold, meteoric waters we argue that addition of a 4He-rich component, equilibrated at temperatures around 170 °C, is necessary to explain the range in fumarole gas chemistry.

  20. Variations in Melt Generation and Migration along the Aleutian Arc (Invited)

    NASA Astrophysics Data System (ADS)

    Plank, T. A.; Van Keken, P. E.

    2013-12-01

    The generation and ascent of mantle melt beneath volcanic arcs sets the course for how magmas differentiate to form the continental crust and erupt explosively from volcanoes. Although the basic framework of melting at subduction zones is understood to involve the convective influx of hot mantle (Tp ≥ 1300°C) and advective transport of water-rich fluids from the subducting slab, the P-T paths that melts follow during melt generation and migration are still not well known. The Aleutian Arc provides an opportunity to explore the conditions of mantle melting in the context of volcanoes that span an unusually large range in the depth to the slab, from Seguam island, with among the shallowest depths to the slab worldwide (~65 km, [1]) to Bogoslof island, behind the main volcanic front and twice the depth to the slab (~130 km). Here we combine thermal models tuned to Aleutian subduction parameters [after 2] with petrological estimates of the T and P of mantle-melt equilibration, using a major element geothermometer [3] and estimates of H2O and fO2 from olivine-hosted melt inclusion measurements [4] for basaltic magmas from 6 volcanoes in the central Aleutians (Korovin, Seguam, Bogoslof, Pakushin, Akutan, Shishaldin). We find mantle-melt equilibration conditions to vary systematically as a function of the depth to the slab, from 30 km and 1220°C (for Seguam) to 60 km and 1300°C (for Bogoslof). Such shallow depths, which extend up to the Moho, define a region perched well above the hot core of the mantle wedge predicted from thermal models, even considering the shallow depths of slab-mantle coupling (< 60 km) required to supply hot mantle beneath Seguam. Thus, even though the greatest melt production will occur in the hot core of the wedge (50-100 km depth), melts apparently ascend and re-equilibrate in the shallowest mantle. Volcanoes that overlie the greatest depth to the slab, and lie furthest from the wedge corner, stall at greater depths (~60 km), at the base of the conductive upper plate (i.e., lithosphere). The conductive lid and isotherms shallow toward the wedge corner. This leads to shallower depths of melt equilibration at shallower depths to the slab. A second effect is infiltration of melt into the thinning lithosphere, likely due to the increase in strain-rate toward the wedge corner, which favors melt segregation, migration, and shallow equilibration [5]. Such a process is developed most beneath Seguam, where melts collect at the Moho (~ 30km), but are still > 1200°C. Such equilibration depths in the uppermost mantle (30-60 km) and temperatures typical of the base of the conductive lid appear to characterize most modeled primary arc magmas [6], and point to a final re-setting point in the mantle that controls the composition of bulk arc crust. [1] Syracuse & Abers, 2006, G3. [2] Syracuse, van Keken, Abers, (2010) PEPI. [3] Lee, Luffi, Plank, Dalton, Leeman (2009) EPSL. [4] Zimmer et al. (2010) J.Pet. [5] Holzman & Kendall (2010). [6] Ruscitto et al. (2012) G3.

  1. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (-0.21 ± 0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (-0.11 to -0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

  2. Density Relaxation of Liquid-Vapor Critical Fluids Examined in Earth's Gravity

    NASA Technical Reports Server (NTRS)

    Wilkinson, R. Allen

    2000-01-01

    This work shows quantitatively the pronounced differences between the density equilibration of very compressible dense fluids in Earth's gravity and those in microgravity. The work was performed onsite at the NASA Glenn Research Center at Lewis Field and is complete. Full details are given in references 1 and 2. Liquid-vapor critical fluids (e.g., water) at their critical temperature and pressure, are very compressible. They collapse under their own weight in Earth's gravity, allowing only a thin meniscus-like layer with the critical pressure to survive. This critical layer, however, greatly slows down the equilibration process of the entire sample. A complicating feature is the buoyancy-driven slow flows of layers of heavier and lighter fluid. This work highlights the incomplete understanding of the hydrodynamics involved in these fluids.

  3. Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth's mantle

    NASA Astrophysics Data System (ADS)

    Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas

    2012-05-01

    The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal-silicate equilibration at a common set of P-T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35-50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5-3 orders of magnitude, metal-silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal-silicate partitioning as well as an overprint by late accretion.

  4. 40 CFR 92.119 - Hydrocarbon analyzer calibration.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... plot of the difference between the span and zero response versus fuel flow will be similar to the one... basic operating adjustment using the appropriate fuel (see § 92.112) and zero-grade air. (2) Optimize on.... Allow at least one-half hour after the oven has reached temperature for the system to equilibrate. (C...

  5. 40 CFR 86.331-79 - Hydrocarbon analyzer calibration.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... plot of the difference between the span and zero response versus fuel flow will be similar to the one... least one-half hour after the oven has reached temperature for the system to equilibrate. (c) Initial... difference between the span-gas response and the zero-gas response. Incrementally adjust the fuel flow above...

  6. Thermosensory perception regulates speed of movement in response to temperature changes in Drosophila melanogaster.

    PubMed

    Soto-Padilla, Andrea; Ruijsink, Rick; Sibon, Ody C M; van Rijn, Hedderik; Billeter, Jean-Christophe

    2018-04-12

    Temperature influences physiology and behavior of all organisms. For ectotherms, which lack central temperature regulation, temperature adaptation requires sheltering from or moving to a heat source. As temperature constrains the rate of metabolic reactions, it can directly affect ectotherm physiology and thus behavioral performance. This direct effect is particularly relevant for insects whose small body readily equilibrates with ambient temperature. In fact, models of enzyme kinetics applied to insect behavior predict performance at different temperatures, suggesting that thermal physiology governs behavior. However, insects also possess thermosensory neurons critical for locating preferred temperatures, showing cognitive control. This suggests that temperature-related behavior can emerge directly from a physiological effect, indirectly as consequence of thermosensory processing, or through both. To separate the roles of thermal physiology and cognitive control, we developed an arena that allows fast temperature changes in time and space, and in which animals' movements are automatically quantified. We exposed wild-type and thermosensory receptor mutants Drosophila melanogaster to a dynamic temperature environment and tracked their movements. The locomotor speed of wild-type flies closely matched models of enzyme kinetics, but the behavior of thermosensory mutants did not. Mutations in thermosensory receptor dTrpA1 ( Transient receptor potential ) expressed in the brain resulted in a complete lack of response to temperature changes, while mutation in peripheral thermosensory receptor Gr28b(D) resulted in diminished response. We conclude that flies react to temperature through cognitive control, informed by interactions between various thermosensory neurons, whose behavioral output resembles that of enzyme kinetics. © 2018. Published by The Company of Biologists Ltd.

  7. Long-ranged Fermi-Pasta-Ulam systems in thermal contact: Crossover from q-statistics to Boltzmann-Gibbs statistics

    NASA Astrophysics Data System (ADS)

    Bagchi, Debarshee; Tsallis, Constantino

    2017-04-01

    The relaxation to equilibrium of two long-range-interacting Fermi-Pasta-Ulam-like models (β type) in thermal contact is numerically studied. These systems, with different sizes and energy densities, are coupled to each other by a few thermal contacts which are short-range harmonic springs. By using the kinetic definition of temperature, we compute the time evolution of temperature and energy density of the two systems. Eventually, for some time t >teq, the temperature and energy density of the coupled system equilibrate to values consistent with standard Boltzmann-Gibbs thermostatistics. The equilibration time teq depends on the system size N as teq ∼Nγ where γ ≃ 1.8. We compute the velocity distribution P (v) of the oscillators of the two systems during the relaxation process. We find that P (v) is non-Gaussian and is remarkably close to a q-Gaussian distribution for all times before thermal equilibrium is reached. During the relaxation process we observe q > 1 while close to t =teq the value of q converges to unity and P (v) approaches a Gaussian. Thus the relaxation phenomenon in long-ranged systems connected by a thermal contact can be generically described as a crossover from q-statistics to Boltzmann-Gibbs statistics.

  8. Mineralogy and geothermometry of high-temperature rhyolites from the central and western Snake River Plain

    USGS Publications Warehouse

    Honjo, N.; Bonnichsen, B.; Leeman, W.P.; Stormer, J.C.

    1992-01-01

    Voluminous mid-Miocene rhyolitic ash-flow tuffs and lava flows are exposed along the northern and southern margins of the central and western Snake River Plain. These rhyolites are essentially anhydrous with the general mineral assemblage of plagioclase ??sanidine ?? quartz + augite + pigeonite ?? hypersthene ?? fayalitic olivine + Fe-Ti oxides + apatite + zircon which provides an opportunity to compare feldspar, pyroxene, and Fe-Ti oxide equilibration temperatures for the same rocks. Estimated pyroxene equilibration temperatures (based on the geothermometers of Lindsley and coworkers) range from 850 to 1000??C, and these are well correlated with whole-rock compositions. With the exception of one sample, agreement between the two-pyroxene thermometers tested is well within 50??C. Fe-Ti oxide geothermometers applied to fresh magnetite and ilmenite generally yield temperatures about 50 to 100??C lower than the pyroxene temperatures, and erratic results are obtained if these minerals exhibit effects of subsolidus oxidation and exsolution. Results of feldspar thermometry are more complicated, and reflect uncertainties in the thermometer calibrations as well as in the degree of attainment of equilibrium between plagioclase and sanidine. In general, temperatures obtained using the Ghiorso (1984) and Green and Usdansky (1986) feldspar thermometers agree with the pyroxene temperatures within the respective uncertainties. However, uncertainties in the feldspar temperatures are the larger of the two (and exceed ??60??C for many samples). The feldspar thermometer of Fuhrman and Lindsley (1988) produces systematically lower temperatures for many of the samples studied. The estimated pyroxene temperatures are considered most representative of actual magmatic temperatures for these rhyolites. This range of temperatures is significantly higher than those for rhyolites from many other suites, and is consistent with the hypothesis that the Snake River Plain rhyolitic magmas formed by partial fusion of relatively dry (e.g. granulitic) crustal lithologies. ?? 1992 Springer-Verlag.

  9. Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from far- east Russia: product of recent melt/fluid-rock reaction

    NASA Astrophysics Data System (ADS)

    Rudnick, R. L.; Ionov, D. A.

    2006-12-01

    Peridotite xenoliths from the Tok and Barhatny localities in far-east Russia are characterized by strong Li elemental and isotopic disequilibria caused by addition of Li to the rocks via diffusion from a small-volume grain boundary fluid or melt. Because Li diffuses rapidly at mantle temperatures, the disequilibrium is a transient feature and its preservation in these samples indicates that Li addition occurred shortly before or even during the entrainment of the xenoliths in the host basalts. δ&^{7}Licpx is consistently lower than that of coexisting olivines and Δ&^{7}Liol-cpx, which ranges from 2.8 to 22.9‰,correlates with bulk rock composition. The most refractory samples experienced the greatest overall Li addition and most closely approximate elemental and isotopic equilibrium due to longer equilibration times and probably also greater infiltration of the Li-bearing melt or fluid. The variable but often extreme isotopic compositions produced by this process (δ&^{7}Licpx down to -15 and δ&^{7}Liol up to +12) do not reflect the presence of an isotopically exotic recycled component, as has been previously inferred for xenoliths from this region. The best estimate for the δ&^{7}Li of the source of the Li in the Tok xenoliths is δ&^{7}Li = +1.4, which is identical to that of the host basalt. A single sample from the Koppy locality, which is situated closest to the paleo-Pacific subduction zone, shows both elemental and isotopic equilibration of Li and has a "normal" δ&^{7}Licpx of +3.5. The analytically identical δ&^{7}Li of olivine and cpx from this sample, coupled with its relatively low equilibration temperature of 990°C suggests that there is no discernible Li isotopic fractionation between coexisting minerals at mantle temperatures. This study highlights the very large isotopic effects that can be produced via kinetic fractionation in peridotite xenoliths at high temperatures and associated with host-rock xenolith interactions.

  10. Iron Isotope Constraints on Planetesimal Core Formation

    NASA Astrophysics Data System (ADS)

    Jordan, M.; Young, E. D.

    2016-12-01

    The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

  11. Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

    Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

  12. Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

    DOE PAGES

    Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; ...

    2017-05-16

    Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

  13. Dual stable isotopes of CH4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO2

    NASA Astrophysics Data System (ADS)

    Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

    2017-07-01

    Volcanism and post-magmatism contribute significant annual methane (CH4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH4 (as well as carbon dioxide (CO2) and other gases), but the ultimate sources of this CH4 flux have not been elucidated. Here we use dual stable isotope analysis (δ2H and δ13C) of CH4 sampled from ten high-temperature geothermal pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ13C and δ2H values of CH4 emitted from hot springs (26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ13CCH4 and δ13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH4, or with equilibration of CH4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ13CCH4 and δ13CCO2 ranged from 250-350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ2HH2O of the thermal springs and the measured δ2HCH4 values are consistent with equilibration between the source water and the CH4 at the formation temperatures. Though the ultimate origin of the CH4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C1/C2 + composition of the gases is more consistent with abiotic origins for most of the samples. Thus, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH4 flux from the Yellowstone National Park volcanic system.

  14. Chemical nonequilibrium Navier-Stokes solutions for hypersonic flow over an ablating graphite nosetip

    NASA Technical Reports Server (NTRS)

    Chen, Y. K.; Henline, W. D.

    1993-01-01

    The general boundary conditions including mass and energy balances of chemically equilibrated or nonequilibrated gas adjacent to ablating surfaces have been derived. A computer procedure based on these conditions was developed and interfaced with the Navier-Stokes solver for predictions of the flow field, surface temperature, and surface ablation rates over re-entry space vehicles with ablating Thermal Protection Systems (TPS). The Navier-Stokes solver with general surface thermochemistry boundary conditions can predict more realistic solutions and provide useful information for the design of TPS. A test case with a proposed hypersonic test vehicle configuration and associated free stream conditions was developed. Solutions with various surface boundary conditions were obtained, and the effect of nonequilibrium gas as well as surface chemistry on surface heating and ablation rate were examined. The solutions of the GASP code with complete ablating surface conditions were compared with those of the ASC code. The direction of future work is also discussed.

  15. Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

    NASA Astrophysics Data System (ADS)

    Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

    2018-06-01

    Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

  16. Assessment of structural, thermal, and mechanical properties of portlandite through molecular dynamics simulations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hajilar, Shahin, E-mail: shajilar@iastate.edu; Shafei, Behrouz, E-mail: shafei@iastate.edu

    The structural, thermal, and mechanical properties of portlandite, the primary solid phase of ordinary hydrated cement paste, are investigated using the molecular dynamics method. To understand the effects of temperature on the structural properties of portlandite, the coefficients of thermal expansion of portlandite are determined in the current study and validated with what reported from the experimental tests. The atomic structure of portlandite equilibrated at various temperatures is then subjected to uniaxial tensile strains in the three orthogonal directions and the stress-strain curves are developed. Based on the obtained results, the effect of the direction of straining on the mechanicalmore » properties of portlandite is investigated in detail. Structural damage analysis is performed to reveal the failure mechanisms in different directions. The energies of the fractured surfaces are calculated in different directions and compared to those of the ideal surfaces available in the literature. The key mechanical properties, including tensile strength, Young's modulus, and fracture strain, are extracted from the stress-strain curves. The sensitivity of the obtained mechanical properties to temperature and strain rate is then explored in a systematic way. This leads to valuable information on how the structural and mechanical properties of portlandite are affected under various exposure conditions and loading rates. - Graphical abstract: Fracture mechanism of portlandite under uniaxial strain in the z-direction. - Highlights: • The structural, thermal, and mechanical properties of portlandite are investigated. • The coefficients of thermal expansion are determined. • The stress-strain relationships are studied in three orthogonal directions. • The effects of temperature and strain rate on mechanical properties are examined. • The plastic energy required for fracture in the crystalline structure is reported.« less

  17. Transport in a field aligned magnetized plasma/neutral gas boundary: the end of the plasma

    NASA Astrophysics Data System (ADS)

    Cooper, Christopher Michael

    The objective of this dissertation is to characterize the physics of a boundary layer between a magnetized plasma and a neutral gas along the direction of a confining magnetic field. A series of experiments are performed at the Enormous Toroidal Plasma Device (ETPD) at UCLA to study this field aligned Neutral Boundary Layer (NBL) at the end of the plasma. A Lanthanum Hexaboride (LaB6) cathode and semi-transparent anode creates a magnetized, current-free helium plasma which terminates on a neutral helium gas without touching any walls. Probes are inserted into the plasma to measure the basic plasma parameters and study the transport in the NBL. The experiment is performed in the weakly ionized limit where the plasma density (ne) is much less than the neutral density (nn) such that ne/nn < 5%. The NBL is characterized by a field-aligned electric field which begins at the point where the plasma pressure equilibrates with the neutral gas pressure. Beyond the pressure equilibration point the electrons and ions lose their momentum by collisions with the neutral gas and come to rest. An electric field is established self consistently to maintain a current-free termination through equilibration of the different species' stopping rates in the neutral gas. The electric field resembles a collisional quasineutral sheath with a length 10 times the electron-ion collision length, 100 times the neutral collision length, and 10,000 times the Debye length. Collisions with the neutral gas dominate the losses in the system. The measured plasma density loss rates are above the classical cross-field current-free ambipolar rate, but below the anomalous Bohm diffusion rate. The electron temperature is below the ionization threshold of the gas, 2.2 eV in helium. The ions are in thermal equilibrium with the neutral gas. A generalized theory of plasma termination in a Neutral Boundary Layer is applied to this case using a two-fluid, current-free, weakly ionized transport model. The electron and ion momentum equations along the field are combined in a generalized Ohm's law which predicts the axial electric field required to maintain a current-free termination. The pressure balance criteria for termination and the predicted electric field are confirmed over a scaling of plasma parameters. The experiment and the model are relevant for studying NBLs in other systems, such as the atmospheric termination of the aurora or detached gaseous divertors. A steady state modified ambipolar system is measured in the ETPD NBL. The drift speeds associated with these currents are a small fraction of the plasma flow speeds and the problem is treated as a perturbation to the termination model. The current-free condition on the model is relaxed to explain the presence of the divergence free current.

  18. Comparison of nickel silicide and aluminium ohmic contact metallizations for low-temperature quantum transport measurements.

    PubMed

    Polley, Craig M; Clarke, Warrick R; Simmons, Michelle Y

    2011-10-03

    We examine nickel silicide as a viable ohmic contact metallization for low-temperature, low-magnetic-field transport measurements of atomic-scale devices in silicon. In particular, we compare a nickel silicide metallization with aluminium, a common ohmic contact for silicon devices. Nickel silicide can be formed at the low temperatures (<400°C) required for maintaining atomic precision placement in donor-based devices, and it avoids the complications found with aluminium contacts which become superconducting at cryogenic measurement temperatures. Importantly, we show that the use of nickel silicide as an ohmic contact at low temperatures does not affect the thermal equilibration of carriers nor contribute to hysteresis in a magnetic field.

  19. The effects of cooling rates and type of freezing extenders on cryosurvival of rat sperm

    PubMed Central

    Varisli, Omer; Scott, Hollie; Agca, Cansu; Agca, Yuksel

    2013-01-01

    Cryopreservation of rat sperm is very challenging due to its sensitivity to various stress factors. The objective of this study was to determine the optimal cooling rate and extender for epididymal sperm of outbred Sprague Dawley (SD) and inbred Fischer 344 (F344) rat strains. The epididymal sperm from 10–12 weeks old sexually mature SD and F344 strains were suspended in five different freezing extenders, namely HEPES buffered Tyrode’s lactate (TL-HEPES), modified Kreb’s Ringer bicarbonate (mKRB), 3% dehydrated skim milk (SM), Salamon’s Tris-citrate (TRIS), and tes/tris (TES). All extenders contained 20% egg yolk, 0.75% Equex Paste and 0.1 M raffinose or 0.1 M sucrose. The sperm samples in each extender were cooled to 4°C and held for 45 min for equilibration before freezing. The equilibrated sperm samples in each extender were placed onto a shallow quartz dish inserted into Linkam Cryostage (BCS 196). The samples were then cooled to a final temperature of −150 °C by using various cooling rates (10, 40, 70, and 100 °C/min). For thawing, the quartz dish containing the sperm samples were rapidly removed from the Linkam cryo-stage and placed on a 37 °C slide warmer and held for 1 min before motility analysis. Sperm membrane and acrosomal integrity and mitochondrial membrane potential (MMP) were assessed by SYBR-14/Propidium iodide, Alexa Fluor-488-PNA conjugate and JC-1, respectively. The total motility, acrosomal integrity, membrane integrity and MMP values were compared among cooling rates and extenders. Both cooling rate and type of extender had significant effect on cryosurvival (P<0.05). Sperm motility increased as cooling rate was increased for both strains (P<0.05). Highest cryosurvival was achieved when 100 °C/min cooling rate was used in combination with TES extender containing 20% egg yolk, 0.75% Equex paste and either 0.1 M sucrose or raffinose (P < 0.05). This study showed that TES extender containing 0.1 M raffinose or sucrose with 70 °C /min and 100 °C /min cooling rate improved post-thaw motility of rat sperm. PMID:23727068

  20. A Tale of Two Melt Rocks: Equilibration and Metal/Sulfide-Silicate Segregation in the L7 Chondrites PAT 91501 and LEW 88663

    NASA Astrophysics Data System (ADS)

    Harvey, R. P.

    1993-07-01

    Type 7 ordinary chondrites have experienced temperatures near or beyond those necessary for partial melting. Two recently collected Antarctic specimens, PAT91501 (PAT) and LEW88663 (LEW), have been tentatively identified as L7 chondrites based on mineral and oxygen isotope compositions [1,2]. The petrology and mineralogy of these meteorites suggests that they have undergone significant metal/sulfide-silicate segregation, with implications for meteorite parent bodies. PAT consists of an equigranular contact-framework of nearly euhedral olivine grains, with interstitial spaces filled by plagioclase, pyroxenes, and several minor phases. Ortho- and clinopyroxene occur in an exsolution relationship. Olivine and pyroxene are highly equilibrated, varying <<1% in Fe-endmember content. Pyroxene equilibration temperatures calculated for PAT using the methods of [3] are self-consistent at about 1180 degrees C. In thin section, PAT contains only traces of metal, as tiny isolated blebs in sulfide grains; large (>1 cm) globular sulfide inclusions are seen in hand-sample [1], but are not present in the section examined. LEW was originally classified as an achondrite with olivine and pyroxene compositions similar to those in L chondrites [2]. Metal is absent in LEW, although the specimen is small and heavily rusted, making it impossible to gauge the original metal content. Olivine grains are commonly rounded in shape and seldom in contact with more than a few other grains. LEW olivine and pyroxene are also highly equilibrated. Veins of Ni-bearing metal oxides and sulfides are common. Both low- and high-Ca pyroxene occur as discrete grains, orthopyroxene often poikilitically enclosing olivine. Pyroxene equilibration temperatures for LEW are more variable than those for PAT and consistently lower, with an average around 900 degrees C. The various textural and compositional characteristics of PAT and LEW suggest they have experienced partial melting to varying degrees. Both visually resemble charges from experimental melting of ordinary chondrites [4-6]. The cumulate-like framework of olivine crystals in PAT suggests a high degree of partial melting, at peak temperatures sufficient to melt all other phases (above 1400 degrees C) [6]. The spheroidal sulfide nodules in PAT and the occurrence of metal (when present) only in association with sulfide strongly suggest gravitational segregation of a metal/sulfide liquid from a partial melt of the original chondritic assemblage. LEW features suggest less partial melting. Veins and grain coatings of sulfides and Fe-Ni oxides (that were probably metal before weathering) infer exposure to temperatures of 900-1000 degrees C [5]. The non-uniform olivine grain size and presence of remnant clinopyroxene grains in LEW imply that peak temperatures reached by this meteorite were not higher than 1200 degrees C [6]. The partial melting observed in PAT and LEW is probably a result of shock heating during impacts, as proposed in studies of Shaw (L7) and other similar lithologies [7]. If significant metal/sulfide-silicate segregation can occur in the relatively small volumes and short heating times associated with impact melting, even small planetesimals might be differentiated. This implies that the timescale necessary for planetary differentiation might have been significantly shortened by the assembly of already differentiated planetesimals to form meteorite parent bodies [8]. References: [1] Mason B. et al. (1992) Ant. Met. News., 15(2), 30. [2] Mason B. and Marlow R. (1992) Ant. Met. News., 15(1), 16. [3] Fonarev V. I. and Graphchikov A. A. (1991) In Progress in Metamorphic and Magmatic Petrology (L. L. Perchuk, ed.), 65-92, Cambridge University. [4] Smith B. A. and Goldstein J. I. (1977) GCA, 41, 1061-1072. [5] McSween H. Y. Jr. et al. (1978) LPS IX, 1437-1447. [6] Takahashi E. (1983) NIPR Spec. Is., 30, 168-180. [7] Taylor G. J. et al. (1979) GCA, 43, 323-337. [8] Taylor G. J. JGR, 97, 14717-14726.

  1. Natural gas production and anomalous geothermal gradients of the deep Tuscaloosa Formation

    USGS Publications Warehouse

    Burke, Lauri

    2011-01-01

    For the largest producing natural gas fields in the onshore Gulf of Mexico Basin, the relation between temperature versus depth was investigated. Prolific natural gas reservoirs with the highest temperatures were found in the Upper Cretaceous downdip Tuscaloosa trend in Louisiana. Temperature and production trends from the deepest field, Judge Digby field, in Pointe Coupe Parish, Louisiana, were investigated to characterize the environment of natural gas in the downdip Tuscaloosa trend. The average production depth in the Judge Digby field is approximately 22,000 ft. Temperatures as high as 400 degrees F are typically found at depth in Judge Digby field and are anomalously low when compared to temperature trends extrapolated to similar depths regionally. At 22,000 ft, the minimum and maximum temperatures for all reservoirs in Gulf Coast producing gas fields are 330 and 550 degrees F, respectively; the average temperature is 430 degrees F. The relatively depressed geothermal gradients in the Judge Digby field may be due to high rates of sediment preservation, which may have delayed the thermal equilibration of the sediment package with respect to the surrounding rock. Analyzing burial history and thermal maturation indicates that the deep Tuscaloosa trend in the Judge Digby field is currently in the gas generation window. Using temperature trends as an exploration tool may have important implications for undiscovered hydrocarbons at greater depths in currently producing reservoirs, and for settings that are geologically analogous to the Judge Digby fiel

  2. Electronic excitation of ground state atoms by collision with heavy gas particles

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1993-01-01

    Most of the important chemical reactions which occur in the very high temperature air produced around space vehicles as they enter the atmosphere were investigated both experimentally and theoretically, to some extent at least. One remaining reaction about which little is known, and which could be quite important at the extremely high temperatures that will be produced by the class of space vehicles now contemplated - such as the AOTV - is the excitation of bound electron states due to collisions between heavy gas particles. Rates of electronic excitation due to free electron collisions are known to be very rapid, but because these collisions quickly equilibrate the free and bound electron energy, the approach to full equilibrium with the heavy particle kinetic energy will depend primarily on the much slower process of bound electron excitation in heavy particle collisions and the subsequent rapid transfer to free electron energy. This may be the dominant mechanism leading to full equilibrium in the gas once the dissociation process has depleted the molecular states so the transfer between molecular vibrational energy and free electron energy is no longer available as a channel for equilibration of free electron and heavy particle kinetic energies. Two mechanisms seem probable in electronic excitation by heavy particle impact. One of these is the collision excitation and deexcitation of higher electronic states which are Rydberg like. A report, entitled 'Semi-Classical Theory of Electronic Excitation Rates', was submitted previously. This presented analytic expressions for the transition probabilities, assuming that the interaction potential is an exponential repulsion with a perturbation ripple due to the dipole-induced dipole effect in the case of neutral-neutral collisions, and to the ion-dipole interaction in the case of ion-neutral collisions. However the above may be, there is little doubt that excitation of ground state species by collision occurs at the point where the initial and final potentials cross, or at least come very close. Therefore, this mechanism would be applicable to the case where a gas is initially at very low temperature suddenly subjected to high energy heavy particle bombardment. This situation would model the measurement of excitation cross section by molecular beam techniques, for example. The purpose is to report values of cross sections and rate coefficients for collision excitation of ground state atoms estimated with the Landau-Zener transition theory and to compare results with measurement of excitation cross sections for a beam of Hydrogen atoms impacting Argon atom targets. Some very dubious approximations are used, and the comparison with measurement is found less than ideal, but results are at least consistent within order of magnitude. The same model is then applied to the case of N-N atom collisions, even though the approximations then become even more doubtful. Still the rate coefficients obtained are at least plausible in both magnitude and functional form, and as far as I am aware these are the only estimates available for such rate coefficients.

  3. Theory of ion transport with fast acid-base equilibrations in bioelectrochemical systems.

    PubMed

    Dykstra, J E; Biesheuvel, P M; Bruning, H; Ter Heijne, A

    2014-07-01

    Bioelectrochemical systems recover valuable components and energy in the form of hydrogen or electricity from aqueous organic streams. We derive a one-dimensional steady-state model for ion transport in a bioelectrochemical system, with the ions subject to diffusional and electrical forces. Since most of the ionic species can undergo acid-base reactions, ion transport is combined in our model with infinitely fast ion acid-base equilibrations. The model describes the current-induced ammonia evaporation and recovery at the cathode side of a bioelectrochemical system that runs on an organic stream containing ammonium ions. We identify that the rate of ammonia evaporation depends not only on the current but also on the flow rate of gas in the cathode chamber, the diffusion of ammonia from the cathode back into the anode chamber, through the ion exchange membrane placed in between, and the membrane charge density.

  4. Etude des phenomenes dynamiques ultrarapides et des caracteristiques impulsionnelles d'emission terahertz du supraconducteur YBCO

    NASA Astrophysics Data System (ADS)

    Savard, Stephane

    Les premieres etudes d'antennes a base de supraconducteurs a haute temperature critique emettant une impulsion electromagnetique dont le contenu en frequence se situe dans le domaine terahertz remontent a 1996. Une antenne supraconductrice est formee d'un micro-pont d'une couche mince supraconductrice sur lequel un courant continu est applique. Un faisceau laser dans le visible est focalise sur le micro-pont et place le supraconducteur dans un etat hors-equilibre ou des paires sont brisees. Grace a la relaxation des quasiparticules en surplus et eventuellement de la reformation des paires supraconductrices, nous pouvons etudier la nature de la supraconductivite. L'analyse de la cinetique temporelle du champ electromagnetique emis par une telle antenne terahertz supraconductrice s'est averee utile pour decrire qualitativement les caracteristiques de celle-ci en fonction des parametres d'operation tels que le courant applique, la temperature et la puissance d'excitation. La comprehension de l'etat hors-equilibre est la cle pour comprendre le fonctionnement des antennes terahertz supraconductrices a haute temperature critique. Dans le but de comprendre ultimement cet etat hors-equilibre, nous avions besoin d'une methode et d'un modele pour extraire de facon plus systematique les proprietes intrinseques du materiau qui compose l'antenne terahertz a partir des caracteristiques d'emission de celle-ci. Nous avons developpe une procedure pour calibrer le spectrometre dans le domaine temporel en utilisant des antennes terahertz de GaAs bombarde aux protons H+ comme emetteur et detecteur. Une fois le montage calibre, nous y avons insere une antenne emettrice dipolaire de YBa 2Cu3O7-delta . Un modele avec des fonctions exponentielles de montee et de descente du signal est utilise pour lisser le spectre du champ electromagnetique de l'antenne de YBa 2Cu3O7-delta, ce qui nous permet d'extraire les proprietes intrinseques de ce dernier. Pour confirmer la validite du modele choisi, nous avons mesure les proprietes intrinseques du meme echantillon de YBa2Cu3O7- delta avec la technique pompe-visible et sonde-terahertz donnant, elle aussi, acces aux temps caracteristiques regissant l'evolution hors-equilibre de ce materiau. Dans le meilleur scenario, ces temps caracteristiques devraient correspondre a ceux evalues grace a la modelisation des antennes. Un bon controle des parametres de croissance des couches minces supraconductrices et de fabrication du dispositif nous a permis de realiser des antennes d'emission terahertz possedant d'excellentes caracteristiques en terme de largeur de bande d'emission (typiquement 3 THz) exploitables pour des applications de spectroscopie resolue dans le domaine temporel. Le modele developpe et retenu pour le lissage du spectre terahertz decrit bien les caracteristiques de l'antenne supraconductrice pour tous les parametres d'operation. Toutefois, le lien avec la technique pompe-sonde lors de la comparaison des proprietes intrinseques n'est pas direct malgre que les deux techniques montrent que le temps de relaxation des porteurs augmente pres de la temperature critique. Les donnees en pompe-sonde indiquent que la mesure du temps de relaxation depend de la frequence de la sonde, ce qui complique la correspondance des proprietes intrinseques entre les deux techniques. De meme, le temps de relaxation extrait a partir du spectre de l'antenne terahertz augmente en s'approchant de la temperature critique (T c) de YBa2Cu 3O7-delta. Le comportement en temperature du temps de relaxation correspond a une loi de puissance qui est fonction de l'inverse du gap supraconducteur avec un exposant 5 soit 1/Delta 5(T). Le travail presente dans cette these permet de mieux decrire les caracteristiques des antennes supraconductrices a haute temperature critique et de les relier aux proprietes intrinseques du materiau qui les compose. De plus, cette these presente les parametres a ajuster comme le courant applique, la puissance de la pompe, la temperature d'operation, etc, afin d'optimiser l'emission et les performances de ces antennes supraconductrices entre autres pour maximiser leur etendue en frequence dans une perspective d'application en spectroscopie terahertz. Cependant, plusieurs des resultats obtenus soulevent la difficulte de decrire l'etat hors-equilibre et la necessite de developper une theorie pour le supraconducteur YBa2 Cu3O7-delta

  5. Optimization of the secondary drying step in freeze drying using TDLAS technology.

    PubMed

    Schneid, Stefan C; Gieseler, Henning; Kessler, William J; Luthra, Suman A; Pikal, Michael J

    2011-03-01

    The secondary drying phase in freeze drying is mostly developed on a trial-and-error basis due to the lack of appropriate noninvasive process analyzers. This study describes for the first time the application of Tunable Diode Laser Absorption Spectroscopy, a spectroscopic and noninvasive sensor for monitoring secondary drying in laboratory-scale freeze drying with the overall purpose of targeting intermediate moisture contents in the product. Bovine serum albumin/sucrose mixtures were used as a model system to imitate high concentrated antibody formulations. First, the rate of water desorption during secondary drying at constant product temperatures (-22 °C, -10 °C, and 0 °C) was investigated for three different shelf temperatures. Residual moisture contents of sampled vials were determined by Karl Fischer titration. An equilibration step was implemented to ensure homogeneous distribution of moisture (within 1%) in all vials. The residual moisture revealed a linear relationship to the water desorption rate for different temperatures, allowing the evaluation of an anchor point from noninvasive flow rate measurements without removal of samples from the freeze dryer. The accuracy of mass flow integration from this anchor point was found to be about 0.5%. In a second step, the concept was successfully tested in a confirmation experiment. Here, good agreement was found for the initial moisture content (anchor point) and the subsequent monitoring and targeting of intermediate moisture contents. The present approach for monitoring secondary drying indicated great potential to find wider application in sterile operations on production scale in pharmaceutical freeze drying. © 2011 American Association of Pharmaceutical Scientists

  6. Weak and strong coupling equilibration in nonabelian gauge theories

    NASA Astrophysics Data System (ADS)

    Keegan, Liam; Kurkela, Aleksi; Romatschke, Paul; van der Schee, Wilke; Zhu, Yan

    2016-04-01

    We present a direct comparison studying equilibration through kinetic theory at weak coupling and through holography at strong coupling in the same set-up. The set-up starts with a homogeneous thermal state, which then smoothly transitions through an out-of-equilibrium phase to an expanding system undergoing boost-invariant flow. This first apples-to-apples comparison of equilibration provides a benchmark for similar equilibration processes in heavy-ion collisions, where the equilibration mechanism is still under debate. We find that results at weak and strong coupling can be smoothly connected by simple, empirical power-laws for the viscosity, equilibration time and entropy production of the system.

  7. Experimental and theoretical analysis of the rate of solvent equilibration in the hanging drop method of protein crystal growth

    NASA Technical Reports Server (NTRS)

    Fowlis, William W.; Delucas, Lawrence J.; Twigg, Pamela J.; Howard, Sandra B.; Meehan, Edward J.

    1988-01-01

    The principles of the hanging-drop method of crystal growth are discussed, and the rate of water evaporation in a water droplet (containing protein, buffer, and a precipitating agent) suspended above a well containing a double concentration of precipitating agent is investigated theoretically. It is shown that, on earth, the rate of evaporation may be determined from diffusion theory and the colligative properties of solutions. The parameters affecting the rate of evaporation include the temperature, the vapor pressure of water, the ionization constant of the salt, the volume of the drop, the contact angle between the droplet and the coverslip, the number of moles of salt in the droplet, the number of moles of water and salt in the well, the molar volumes of water and salt, the distance from the droplet to the well, and the coefficient of diffusion of water vapor through air. To test the theoretical equations, hanging-drop experiments were conducted using various reagent concentrations in 25-microliter droplets and measuring the evaporation times at 4 C and 25 C. The results showed good agreement with the theory.

  8. Micro-balance sensor integrated with atomic layer deposition chamber

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Martinson, Alex B. F.; Libera, Joseph A.; Elam, Jeffrey W.

    The invention is directed to QCM measurements in monitoring ALD processes. Previously, significant barriers remain in the ALD processes and accurate execution. To turn this exclusively dedicated in situ technique into a routine characterization method, an integral QCM fixture was developed. This new design is easily implemented on a variety of ALD tools, allows rapid sample exchange, prevents backside deposition, and minimizes both the footprint and flow disturbance. Unlike previous QCM designs, the fast thermal equilibration enables tasks such as temperature-dependent studies and ex situ sample exchange, further highlighting the feasibility of this QCM design for day-to-day use. Finally, themore » in situ mapping of thin film growth rates across the ALD reactor was demonstrated in a popular commercial tool operating in both continuous and quasi-static ALD modes.« less

  9. Investigation of thermal and temporal responses of ionization chambers in radiation dosimetry.

    PubMed

    AlMasri, Hussein; Funyu, Akira; Kakinohana, Yasumasa; Murayama, Sadayuki

    2012-07-01

    The ionization chamber is a primary dosimeter that is used in radiation dosimetry. Generally, the ion chamber response requires temperature/pressure correction according to the ideal gas law. However, this correction does not consider the thermal volume effect of chambers. The temporal and thermal volume effects of various chambers (CC01, CC13, NACP parallel-plate, PTW) with different wall and electrode materials have been studied in a water phantom. Measurements were done after heating the water with a suitable heating system, and chambers were submerged for a sufficient time to allow for temperature equilibrium. Temporal results show that all chambers equilibrate quickly in water. The equilibration time was between 3 and 5 min for all chambers. Thermal results show that all chambers expanded in response to heating except for the PTW, which contracted. This might be explained by the differences in the volumes of all chambers and also by the difference in wall material composition of PTW from the other chambers. It was found that the smallest chamber, CC01, showed the greatest expansion. The magnitude of the expansion was ~1, 0.8, and 0.9% for CC01, CC13, and parallel-plate chambers, respectively, in the temperature range of 295-320 K. The magnitude of the detected contraction was <0.3% for PTW in the same temperature range. For absolute dosimetry, it is necessary to make corrections for the ion chamber response, especially for small ion chambers like the CC01. Otherwise, room and water phantom temperatures should remain within a close range.

  10. Multivariate optimization of a headspace solid-phase microextraction method followed by gas chromatography with mass spectrometry for the determination of terpenes in Nicotiana langsdorffii.

    PubMed

    Ardini, Francisco; Carro, Marina Di; Abelmoschi, Maria Luisa; Grotti, Marco; Magi, Emanuele

    2014-07-01

    A simple and sensitive procedure based on headspace solid-phase microextraction and gas chromatography with mass spectrometry was developed for the determination of five terpenes (α-pinene, limonene, linalool, α-terpineol, and geraniol) in the leaves of Nicotiana langsdorffii. The microextraction conditions (extraction temperature, equilibration time, and extraction time) were optimized by means of a Doehlert design. The experimental design showed that, for α-pinene and limonene, a low temperature and a long extraction time were needed for optimal extraction, while linalool, α-terpineol, and geraniol required a high temperature and a long extraction time. The chosen compromise conditions were temperature 60°C, equilibration time 15 min and extraction time 50 min. The main analytical figures of the optimized method were evaluated; LODs ranged from 0.07 ng/g (α-pinene) to 8.0 ng/g (geraniol), while intraday and interday repeatability were in the range 10-17% and 9-13%, respectively. Finally, the procedure was applied to in vitro wild-type and transgenic specimens of N. langsdorffii subjected to abiotic stresses (chemical and heat stress). With the exception of geraniol (75-374 ng/g), low concentration levels of terpenes were measured (ng/g level or lower); some interesting variations in terpene concentration induced by abiotic stress were observed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Oxygen deficient Ti oxides (natural magnéli phases) from mudstone xenoliths with native iron from Disko, central West Greenland

    NASA Astrophysics Data System (ADS)

    Pedersen, A. K.; Rønsbo, J. G.

    1987-05-01

    Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron. The blue oxides are compositionally similar to magnéli phases TinO2n-1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al1Ti{1/3+}Ti{2/4+}O7 (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al2-x(Ti{0.5/4+}(Mg,Fe)0.5)xTi{n-2/4+}O2n-1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.

  12. The Thermal States of Accreting Planets: From Mars-like Embryos to a MAD Earth

    NASA Astrophysics Data System (ADS)

    Stewart, S. T.; Lock, S. J.

    2015-12-01

    The thermal states of rocky planets can vary widely during the process of accretion. The thermal structure affects several major processes on the growing planet, including the mechanics of core formation, pressure-temperature conditions for metal-silicate equilibration, mixing, and atmospheric erosion. Because impact energy is distributed heterogeneously, accretional energy is preferentially deposited in the gravitationally re-equilibrated outer layers of the planet for both small and giant impacts. The resulting stably stratified structure inhibits complete mixing within the mantle. Initially, the specific energy of giant impacts between Mars-mass embryos leads to melting of the mantle. However, as planet formation progresses, the specific energies of giant impacts increase and can drive the mantle into a transient supercritical state. In the hottest regions of the planet, metal and silicates are miscible, and metal exsolution occurs as the structure cools. The cooling time of the supercritical structure is typically longer than the timescale for metal segregation to the core. Thus, these high temperature excursions during planet formation are significant for understanding metal-silicate equilibration. Furthermore, when a supercritical planet is also rapidly rotating, the mantle, atmosphere and disk (MAD) form a continuous dynamic and thermodynamic structure. Lunar origin by condensation from a MAD Earth can explain the major characteristics of the Moon (Lock et al., this meeting). One of the greatest uncertainties in understanding the thermal states of planets during accretion is the changing composition and mass of the atmosphere. After the dispersal of the solar nebula, the thermal boundary condition imposed by the atmosphere can vary between silicate vapor and condensed ices. The coupled problem of atmospheric origin and planetary accretion can be used to constrain the many uncertainties in the growth and divergence of the terrestrial planets in our solar system.

  13. Equilibration and Sensory Overload in the Pre-School Child: Some Effects of Children's Television Programming.

    ERIC Educational Resources Information Center

    Miller, Thomas W.

    This paper reports an attempt to research sensory overstimulation in a variety of children's television programs by rating the level of visual sensory stimulation, auditory sensory stimulation, verbal response patterns and nonverbal response patterns in 45 television programs designed for pre-school children. The Television Rating Inventory (TVRI)…

  14. Comparative mineral chemistry and textures of SAFOD fault gouge and damage-zone rocks

    USGS Publications Warehouse

    Moore, Diane E.

    2014-01-01

    Creep in the San Andreas Fault Observatory at Depth (SAFOD) drillhole is localized to two foliated gouges, the central deforming zone (CDZ) and southwest deforming zone (SDZ). The gouges consist of porphyroclasts of serpentinite and sedimentary rock dispersed in a foliated matrix of Mg-smectite clays that formed as a result of shearing-enhanced reactions between the serpentinite and quartzofeldspathic rocks. The CDZ takes up most of the creep and exhibits differences in mineralogy and texture from the SDZ that are attributable to its higher shearing rate. In addition, a ∼0.2-m-wide sector of the CDZ at its northeastern margin (NE-CDZ) is identical to the SDZ and may represent a gradient in creep rate across the CDZ. The SDZ and NE-CDZ have lower clay contents and larger porphyroclasts than most of the CDZ, and they contain veinlets and strain fringes of calcite in the gouge matrix not seen elsewhere in the CDZ. Matrix clays in the SDZ and NE-CDZ are saponite and corrensite, whereas the rest of the CDZ lacks corrensite. Saponite is younger than corrensite, reflecting clay crystallization under declining temperatures, and clays in the more actively deforming portions of the CDZ have better equilibrated to the lower-temperature conditions.

  15. Petrologic evidence that most ocean islands derive from thermally driven mantle plumes

    NASA Astrophysics Data System (ADS)

    Putirka, K. D.

    2006-12-01

    Perhaps the most crucial test of the mantle plume hypothesis concerns whether hot spots are indeed hot. To conduct this test, olivine-liquid equilibria are used to estimate mantle potential temperatures (Tp) for 15 putative plume localities (using the GEOROC database). Ocean islands (OIB) were selected on the availability of rocks that attain olivine control (where olivine addition/removal alone controls rock composition) so that primitive FeO contents could be estimated. Several other variables in addition to FeO must also be known: Except at Iceland and Hawaii, where large numbers of olivine analyses allow individual estimates for the maximum forsterite contents (Fomax) of olivines, a single Fomax value, 91.5, is adopted for all OIB (and MORB; determined from a global database of olivine compositions); as a null hypothesis, MORB-like values for oxygen fugacity (QFM-1; Bezos and Humler, 2005) and the Fe-Mg exchange coefficient between olivine and liquid (0.31; calculated from Toplis, 2005, Herzberg and O'Hara, 1998) are adopted. Generalized differences in water contents between OIB and MORB (Dixon et al., 2002) are also accounted for. All temperatures are calculated at 1 GPa, using averages of existing (Beattie, 1993) and new (Putirka et al., 2006) olivine geothermometers. Except for Galapagos, primitive OIBs have nearly uniform FeO contents that are higher compared to MORB (at MgO>10 wt. %, mean OIB FeOt = 11.6 wt. %). These high FeO contents require higher mean temperatures of olivine-liquid equilibration for OIB, by an average of 150±20°C compared to MORB. Olivine equilibration temperatures do not depend on mantle source composition, so are independent of whether eclogite-type components occur in the mantle. If a peridotite bulk composition is assumed (to estimate melt fraction from partial melting experiments) olivine equilibration temperatures can be converted to Tp; OIB (Galapagos excepted) yield a mean Tp of 1583°C, compared to 1397°C for MORB. When inter- island compositional variation is accounted for, all OIB except Galapagos yield excess temperatures (Tp^{OIB} - Tp^{MORB}) of 133-280°C, with a mean of 186± 36°C. Galapagos lavas yield an excess temperature of 16°C; perhaps mixing has diluted its thermal signal, but in any event, its Tp is essentially identical to MORB. Nevertheless, most OIB (93% in this sample) exhibit large excess temperatures. Thermally driven mantle plumes, as proposed by Morgan (1971), thus appear to be common, not rare. A second implication, less certain than the first, involves the narrow standard deviation of ±36°C for Tp at OIB, which almost certainly reflects a lower limit to actual thermal variability. This narrow range indicates that all hot spots derive from a single thermal boundary layer.

  16. Weak and strong coupling equilibration in nonabelian gauge theories

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Keegan, Liam; Kurkela, Aleksi; Romatschke, Paul

    2016-04-06

    In this study, we present a direct comparison studying equilibration through kinetic theory at weak coupling and through holography at strong coupling in the same set-up. The set-up starts with a homogeneous thermal state, which then smoothly transitions through an out-of-equilibrium phase to an expanding system undergoing boost-invariant flow. This first apples-to-apples comparison of equilibration provides a benchmark for similar equilibration processes in heavy-ion collisions, where the equilibration mechanism is still under debate. We find that results at weak and strong coupling can be smoothly connected by simple, empirical power-laws for the viscosity, equilibration time and entropy production of themore » system.« less

  17. Shallow (2-meter) Temperature Surveys in Colorado

    DOE Data Explorer

    Richard E. Zehner

    2012-02-01

    Shallow temperature surveys are useful in early-stage geothermal exploration to delineate surface outflow zones, with the intent to identify the source of upwelling, usually a fault. Detailed descriptions of the 2-meter survey method and equipment design can be found in Coolbaugh et al. (2007) and Sladek et al. (2007), and are summarized here. The survey method was devised to measure temperature as far below the zone of solar influence as possible, have minimal equilibration time, and yet be portable enough to fit on the back of an all-terrain vehicle (ATV); Figure 2). This method utilizes a direct push technology (DPT) technique where 2.3 m long, 0.54" outer diameter hollow steel rods are pounded into the ground using a demolition hammer. Resistance temperature devices (RTD) are then inserted into the rods at 2-meter depths, and allowed to equilibrate for one hour. The temperatures are then measured and recorded, the rods pulled out of the ground, and re-used at future sites. Usually multiple rods are planted over the course of an hour, and then the sampler returns back to the first station, measures the temperatures, pulls the rods, and so on, to eliminate waiting time. At Wagon Wheel Gap, 32 rods were planted around the hot springs between June 20 and July 1, 2012. The purpose was to determine the direction of a possible upflow fault or other structure. Temperatures at 1.5m and 2m depths were measured and recorded in the attribute table of this point shapefile. Several anomalous temperatures suggest that outflow is coming from a ~N60W striking fault or shear zone that contains the quartz-fluorite-barite veins of the adjacent patented mining claims. It should be noted that temperatures at 2m depth vary according to the amount of solar heating from above, as well as possible geothermal heating from below.

  18. The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

    NASA Astrophysics Data System (ADS)

    Horita, Juske; Cole, David R.; Wesolowski, David J.

    1995-03-01

    The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

  19. Energy relaxation of intense laser pulse-produced plasmas

    NASA Astrophysics Data System (ADS)

    Shihab, M.; Abou-Koura, G. H.; El-Siragy, N. M.

    2016-05-01

    We describe a collisional radiative model (CRE) of homogeneously expanded nickel plasmas in vacuum. The CRE model is coupled with two separate electron and ion temperature magneto-hydrodynamic equations. On the output, the model provides the temporal variation of the electron temperature, ion temperature, and average charge state. We demonstrate the effect of three-body recombination ({∝}N_e T^{-9/2}_e) on plasma parameters, as it changes the time dependence of electron temperature from t^{-2} to t^{-1} and exhibits a pronounced effect leading to a freezing feature in the average charge state. In addition, the effect of the three-body recombination on the warm up of ions and delaying the equilibration is addressed.

  20. Comparison of nickel silicide and aluminium ohmic contact metallizations for low-temperature quantum transport measurements

    PubMed Central

    2011-01-01

    We examine nickel silicide as a viable ohmic contact metallization for low-temperature, low-magnetic-field transport measurements of atomic-scale devices in silicon. In particular, we compare a nickel silicide metallization with aluminium, a common ohmic contact for silicon devices. Nickel silicide can be formed at the low temperatures (<400°C) required for maintaining atomic precision placement in donor-based devices, and it avoids the complications found with aluminium contacts which become superconducting at cryogenic measurement temperatures. Importantly, we show that the use of nickel silicide as an ohmic contact at low temperatures does not affect the thermal equilibration of carriers nor contribute to hysteresis in a magnetic field. PMID:21968083

  1. Entanglement Dynamics in Miscible Polyisoprene / Poly(p-tert-butyl styrene) Blends

    NASA Astrophysics Data System (ADS)

    Watanabe, Hiroshi

    2011-03-01

    Viscoelastic and dielectric behavior was examined for well entangled, miscible blends of high- M cis-polyisoprene (PI) and poly(p-tert-butyl styrene) (PtBS). The dielectric data of the blends, reflecting the global motion of the PI chains having the type-A dipoles, indicated that PI and PtBS were the fast and slow components therein. At high temperatures T , the blends exhibited two-step entanglement plateau. The high frequency (ω) plateau height was well described by a simple mixing rule of the entanglement length based on the number fraction of the Kuhn segments. At low T , the blend exhibited the Rouse-like power-law behavior of storage and loss moduli, G ' = G ~ω0.5 , in the range of ω where the high- ω plateau was supposed to emerge. This lack of the high- ω plateau was attributed to retardation of the Rouse equilibration of the PI chain over the entanglement length due to the hindrance from the slow PtBS chains: The PI and PtBS chains were equilibrated cooperatively, and the retardation due to PtBS shortened the plateau for PI to a width not resolved experimentally. A simple model for this cooperative equilibration formulated on the basis of the dielectric data described the viscoelastic data surprisingly well.

  2. Effect of rapid addition and dilution of dimethyl sulfoxide and 37 degrees C equilibration on viability of rabbit morulae thawed rapidly.

    PubMed

    Kojima, T; Soma, T; Oguri, N

    1987-06-01

    The aim of the present study was to examine the effects of various conditions of addition and dilution of dimethyl sulfoxide (Me2SO) and 37 degrees C equilibration, and also the effects of freezing in the solution which was prepared in advance and stored in plastic straws at -20 degrees C on the viability of rabbit morulae thawed rapidly. The embryos were cooled from room temperature to -30 degrees C at 1 degree C/min in the presence of 1.5 M Me2SO using a programmable liquid nitrogen vapor freezing machine with an automatic seeding device, then cooled rapidly, and stored in liquid nitrogen. The frozen straws were thawed rapidly (greater than 1000 degrees C/min). When Me2SO was added in a single step, equilibrated with embryos at 37 degrees C for 15 min and diluted out in a single step, a very high survival was obtained: transferable/recovered, 90%: developed/recovered, 96%. When embryos were pipetted into 1.5 M Me2SO that was prepared in advance, stocked in straws at -20 degrees C, and cooled, the proportions of transferable and developed embryos were equivalent to those of embryos frozen in the solution that was prepared immediately before use.

  3. Antimisting kerosene: Base fuel effects, blending and quality control techniques

    NASA Technical Reports Server (NTRS)

    Yavrouian, A. H.; Ernest, J.; Sarohia, V.

    1984-01-01

    The problems associated with blending of the AMK additive with Jet A, and the base fuel effects on AMK properties are addressed. The results from the evaluation of some of the quality control techniques for AMK are presented. The principal conclusions of this investigation are: significant compositional differences for base fuel (Jet A) within the ASTM specification DI655; higher aromatic content of the base fuel was found to be beneficial for the polymer dissolution at ambient (20 C) temperature; using static mixer technology, the antimisting additive (FM-9) is in-line blended with Jet A, producing AMK which has adequate fire-protection properties 15 to 20 minutes after blending; degradability of freshly blended and equilibrated AMK indicated that maximum degradability is reached after adequate fire protection is obtained; the results of AMK degradability as measured by filter ratio, confirmed previous RAE data that power requirements to decade freshly blended AMK are significantly higher than equilibrated AMK; blending of the additive by using FM-9 concentrate in Jet A produces equilibrated AMK almost instantly; nephelometry offers a simple continuous monitoring capability and is used as a real time quality control device for AMK; and trajectory (jet thurst) and pressure drop tests are useful laboratory techniques for evaluating AMK quality.

  4. Oxygen potential of uranium--plutonium oxide as determined by controlled- atmosphere thermogravimetry

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Swanson, Gerald C.

    1975-10-01

    The oxygen-to-metal atom ratio, or O/M, of solid solution uranium- plutonium oxide reactor fuel is a measure of the concentration of crystal defects in the oxide which affect many fuel properties, particularly, fuel oxygen potential. Fabrication of a high-temperature oxygen electrode, employing an electro-active tip of oxygen-deficient solid-state electrolyte, intended to confirm gaseous oxygen potentials is described. Uranium oxide and plutonium oxide O/M reference materials were prepared by in situ oxidation of high purity metals in the thermobalance. A solid solution uranium-plutonium oxide O/M reference material was prepared by alloying the uranium and plutonium metals in a yttrium oxide cruciblemore » at 1200°C and oxidizing with moist He at 250°C. The individual and solid solution oxides were isothermally equilibrated with controlled oxygen potentials between 800 and 1300°C and the equilibrated O/ M ratios calculated with corrections for impurities and buoyancy effects. Use of a reference oxygen potential of -100 kcal/mol to produce an O/M of 2.000 is confirmed by these results. However, because of the lengthy equilibration times required for all oxides, use of the O/M reference materials rather than a reference oxygen potential is recommended for O/M analysis methods calibrations.« less

  5. Solubility of uranium oxide in molten salt electrolysis bath of LiF-BaF2 with LaF3 additive

    NASA Astrophysics Data System (ADS)

    Alangi, Nagaraj; Mukherjee, Jaya; Gantayet, L. M.

    2016-03-01

    The solubility of UO2 in the molten mixtures of equimolar LiF-BaF2(1:1) with LaF3 as additive was studied in the range of 1423 K-1523 K. The molten fluoride salt mixture LiF-BaF2 LaF3 was equilibrated with a sintered uranium oxide pellet at 1423 K, 1473 K, 1523 K and the salt samples were collected after equilibration. Studies were conducted in the range of 10%-50% by weight additions of LaF3 in the equimolar LiF-BaF2(1:1) base fluoride salt bath. Solubility of UO2 increased with rise in LaF3 concentration in the molten fluoride in the temperature range of 1423 K-1523 K. At a given concentration of LaF3, the UO2 solubility increased monotonously with temperature. With mixed solvent, when UF4 was added as a replacement of part of LaF3 in LiF-BaF2(1:1)-10 wt% LaF3 and LiF-BaF2(1:1)-30 wt% LaF3, there was an enhancement of solubility of UO2.

  6. Controlled precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3

    NASA Astrophysics Data System (ADS)

    Wang, Yong; Li, Zhibao; Demopoulos, George P.

    2008-03-01

    In this study, homogeneous (unseeded) precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3 in supersaturated solutions was investigated. Factors that influence the precipitation of MgCO 3·3H 2O, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied. SEM images and particle size distribution show that the temperature, initial concentration and titration speed have significant effect on nesquehonite's crystal morphology and particle size. In addition, stirring speed and equilibration time also have some influence on its properties. X-ray powder diffraction (XRD) results show that the obtained crystals compositions are greatly affected by the reaction temperature. With the morphological transformation, their corresponding composition also change from MgCO 3· xH 2O to Mg 5(CO 3) 4(OH) 2·4H 2O in the interval of 288-333 K. With the optimization of operating conditions, the crystals can grow up to a length of about 40 μm and a width of 5 μm, indicating good filtration properties. High-purity nesquehonite obtained in this study was calcined to produce highly pure MgO at 1073 K as shown by XRD results.

  7. Excitation transfer and trapping kinetics in plant photosystem I probed by two-dimensional electronic spectroscopy.

    PubMed

    Akhtar, Parveen; Zhang, Cheng; Liu, Zhengtang; Tan, Howe-Siang; Lambrev, Petar H

    2018-03-01

    Photosystem I is a robust and highly efficient biological solar engine. Its capacity to utilize virtually every absorbed photon's energy in a photochemical reaction generates great interest in the kinetics and mechanisms of excitation energy transfer and charge separation. In this work, we have employed room-temperature coherent two-dimensional electronic spectroscopy and time-resolved fluorescence spectroscopy to follow exciton equilibration and excitation trapping in intact Photosystem I complexes as well as core complexes isolated from Pisum sativum. We performed two-dimensional electronic spectroscopy measurements with low excitation pulse energies to record excited-state kinetics free from singlet-singlet annihilation. Global lifetime analysis resolved energy transfer and trapping lifetimes closely matches the time-correlated single-photon counting data. Exciton energy equilibration in the core antenna occurred on a timescale of 0.5 ps. We further observed spectral equilibration component in the core complex with a 3-4 ps lifetime between the bulk Chl states and a state absorbing at 700 nm. Trapping in the core complex occurred with a 20 ps lifetime, which in the supercomplex split into two lifetimes, 16 ps and 67-75 ps. The experimental data could be modelled with two alternative models resulting in equally good fits-a transfer-to-trap-limited model and a trap-limited model. However, the former model is only possible if the 3-4 ps component is ascribed to equilibration with a "red" core antenna pool absorbing at 700 nm. Conversely, if these low-energy states are identified with the P 700 reaction centre, the transfer-to-trap-model is ruled out in favour of a trap-limited model.

  8. Stable isotope analyses of the peralkaline volcanics Gregory Rift Valley, Kenya

    NASA Technical Reports Server (NTRS)

    Black, S.; Macdonald, R.; Fallick, A. E.; Kelly, M.

    1993-01-01

    Delta O-18 analyses of the Naivasha rhyolites, basalts, Menengai trachytes and the Yatta phonolite are presented together with D/H analyses of the Naivasha rhyolites. Delta O-18 results vary from 5.7 to 8.9 per mill which is within the reported range of delta O-18 analyses for continental volcanics. Closure temperatures calulated from the basalts and rhyolites show equilibration to be at magmatic temperatures. D/H values range from -40 to -148 per mill indicating that the rhyolites have undergone large scale degasssing.

  9. Temperature Profile of a Stoichiometric CH4/N2O Flame from Laser Excited Fluorescence Measurements on OH,

    DTIC Science & Technology

    1982-07-01

    19 6. Burner Body Temperature at Several Points Below the Edge of the Burner Head............................ 20 7. An Example of Data Used...effects almost certainly influenced the results of Wang and Davis1 who attributed a plot with two straight-line portions to nonequilibrium distributions of...ground state is equilibrated, one has N, Ja (2J"+l)exp(- EN ,, j,,/kT) (2) where EN ,J1 is the ground state energy, k is Boltzmann’s constant and T is the

  10. A Recipe for implementing the Arrhenius-Shock-Temperature State Sensitive WSD (AWSD) model, with parameters for PBX 9502

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aslam, Tariq Dennis

    2017-10-03

    A reactive ow model for the tri-amino-tri-nitro-benzene (TATB) based plastic bonded explosive PBX 9502 is presented. This newly devised model is based primarily on the shock temperature of the material, along with local pressure, and accurately models a broader range of detonation and initiation scenarios. The equation of state for the reactants and products, as well as the thermodynamic closure of pressure and temperature equilibration are carried over from the Wescott-Stewart-Davis (WSD) model7,8. Thus, modifying an existing WSD model in a hydrocode should be rather straightforward.

  11. Quench of non-Markovian coherence in the deep sub-Ohmic spin–boson model: A unitary equilibration scheme

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yao, Yao, E-mail: yaoyao@fudan.edu.cn

    The deep sub-Ohmic spin–boson model shows a longstanding non-Markovian coherence at low temperature. Motivating to quench this robust coherence, the thermal effect is unitarily incorporated into the time evolution of the model, which is calculated by the adaptive time-dependent density matrix renormalization group algorithm combined with the orthogonal polynomials theory. Via introducing a unitary heating operator to the bosonic bath, the bath is heated up so that a majority portion of the bosonic excited states is occupied. It is found in this situation the coherence of the spin is quickly quenched even in the coherent regime, in which the non-Markovianmore » feature dominates. With this finding we come up with a novel way to implement the unitary equilibration, the essential term of the eigenstate-thermalization hypothesis, through a short-time evolution of the model.« less

  12. Geochemical evaluation of the geothermal resources in the San Marcos region, Guatemala

    USGS Publications Warehouse

    Fournier, R.O.; Hanshaw, B.B.

    1986-01-01

    The chemical and isotopic compositions of hot springs in the San Marcos region of Guatemala are internally consistent with a hydrologic model in which a deep 240??C reservoir and one or more shallow 195-200??C reservoirs are present. Variations in hot-spring water compositions results from a combination of boiling, mixing with cold, dilute water, and chemical re-equilibration with decreasing temperature. The recharge water for the deep 240??C reservoir is isotopically heavier than the local meteoric water and probably comes from many kilometers to the west or southwest. The water in the shallow reservoir is a mixture of the 240??C water with about 20 ?? 5% of cold, locally derived meteoric water. After mixing, the water in the shallow reservoir re-equilibrates with reservoir rock at 195-200??C. In some places additional mixing with cold water occurs after water leaves the shallow reservoir. ?? 1986.

  13. The granulite suite: Impact melts and metamorphic breccias of the early lunar crust

    NASA Astrophysics Data System (ADS)

    Cushing, J. A.; Taylor, G. J.; Norman, M. D.; Keil, K.

    1993-03-01

    The granulite suite consists of two major types of rocks. One is coarse-grained and poikilitic with many euhedral crystals of olivine and plagioclase. These characteristics indicate crystallization from a melt; the poikilitic granulites are impact melt breccias. The other group is finer-grained and granoblastic, with numerous triple junctions; the granoblastic granulites are metamorphic rocks. Compositional groups identified by Lindstrom and Lindstrom contain both textural types. Two pyroxene thermometry indicates that both groups equilibrated at 1000 to 1150 C. Calculations suggest that the granoblastic group, which has an average grain size of about 80 microns, was annealed for less than 6 x 10 exp 4 y at 1000 C, and for less than 2500 y at 1150 C. Similar equilibration temperatures suggest that both groups were physically associated after impact events produced the poikilitic melts. Granulitic impactites hold important information about the pre-Nectarian bombardment history of the Moon, and the composition and thermal evolution of the early lunar crust. Granulitic impactites are widely considered to be an important rock type in the lunar crust, but how they formed is poorly understood. Metal compositions and elevated concentrations of meteoritic siderophile elements suggest that most lunar granulites are impact breccias. Their occurrence as clasts in approximately 3.9 Ga breccias, and Ar-(40-39) ages greater than or = 4.2 Ga for some granulites show that they represent a component of the lunar crust which formed prior to the Nectarian cataclysm. Petrographic characteristics of lunar granulites indicate at least two endmember textural variants which apparently formed in fundamentally different ways. One type has granoblastic textures consisting of equant, polygonal to rounded grains, and abundant triple junctions with small dispersions around 120 degrees indicating a close approach to textural equilibrium. As suggested by many authors, granoblastic granulites probably formed by subsolidus annealing and recrystallization of fragmental or glassy protoliths. Examples of this type include 15418, 78155, and 79215. The other textural type consists of poikilitic to poikiloblastic rocks with euhedral to subhedral plagioclase and olivine enclosed by interstitial pyroxene. In some cases, the texture resembles that of an orthocumulate. Examples of this type include 60035, 67955, and 77017. Rounding of grain edges is common in poikilitic granulites, but the regular crystal shapes and widely dispersed dihedral angles show they are far from textural equilibrium.

  14. The granulite suite: Impact melts and metamorphic breccias of the early lunar crust

    NASA Technical Reports Server (NTRS)

    Cushing, J. A.; Taylor, G. J.; Norman, M. D.; Keil, K.

    1993-01-01

    The granulite suite consists of two major types of rocks. One is coarse-grained and poikilitic with many euhedral crystals of olivine and plagioclase. These characteristics indicate crystallization from a melt; the poikilitic granulites are impact melt breccias. The other group is finer-grained and granoblastic, with numerous triple junctions; the granoblastic granulites are metamorphic rocks. Compositional groups identified by Lindstrom and Lindstrom contain both textural types. Two pyroxene thermometry indicates that both groups equilibrated at 1000 to 1150 C. Calculations suggest that the granoblastic group, which has an average grain size of about 80 microns, was annealed for less than 6 x 10 exp 4 y at 1000 C, and for less than 2500 y at 1150 C. Similar equilibration temperatures suggest that both groups were physically associated after impact events produced the poikilitic melts. Granulitic impactites hold important information about the pre-Nectarian bombardment history of the Moon, and the composition and thermal evolution of the early lunar crust. Granulitic impactites are widely considered to be an important rock type in the lunar crust, but how they formed is poorly understood. Metal compositions and elevated concentrations of meteoritic siderophile elements suggest that most lunar granulites are impact breccias. Their occurrence as clasts in approximately 3.9 Ga breccias, and Ar-(40-39) ages greater than or = 4.2 Ga for some granulites show that they represent a component of the lunar crust which formed prior to the Nectarian cataclysm. Petrographic characteristics of lunar granulites indicate at least two endmember textural variants which apparently formed in fundamentally different ways. One type has granoblastic textures consisting of equant, polygonal to rounded grains, and abundant triple junctions with small dispersions around 120 degrees indicating a close approach to textural equilibrium. As suggested by many authors, granoblastic granulites probably formed by subsolidus annealing and recrystallization of fragmental or glassy protoliths. Examples of this type include 15418, 78155, and 79215. The other textural type consists of poikilitic to poikiloblastic rocks with euhedral to subhedral plagioclase and olivine enclosed by interstitial pyroxene. In some cases, the texture resembles that of an orthocumulate. Examples of this type include 60035, 67955, and 77017. Rounding of grain edges is common in poikilitic granulites, but the regular crystal shapes and widely dispersed dihedral angles show they are far from textural equilibrium. The textures of poikilitic granulites are more consistent with the formation of these rocks by crystallization from a melt than by subsolidus metamorphism. A few samples have been recognized with textural characteristics transitional between those of the granoblastic and poikiloblastic endmembers (e.g., 72559, 78527). Pyroxene compositions taken from the literature and determined for this study by electron microprobe were used to calculate equilibration temperatures. The Kretz Ca transfer (solvus) thermometer and the Lindsley and Anderson graphical method both give similar temperatures, which range from approximately 1000 to 1150 C. There is no apparent temperature difference between granoblastic and poikilitic varieties, but there is a hint in these data that the more ferroan varieties equilibrated to lower temperatures. Additional studies are in progress to test this possibility.

  15. Determination of the delta(18O/16O)of Water: RSIL Lab Code 489

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler

    2008-01-01

    The purpose of the technique described by the Reston Stable Isotope Laboratory (RSIL) lab code 489 is to present a method to determine the delta(180/160), abbreviated as delta-180, of water. This delta-18O measurement of water also is a component of National Water Quality Laboratory (NWQL in USGS) schedules 1142 and 1172. Water samples are loaded into glass sample containers on a vacuum manifold to equilibrate gaseous CO2 at constant temperature (25 deg C) with water samples. After loading water samples on the vacuum manifold, air is evacuated through capillary to avoid evaporation, and CO2 is added. The samples are shaken to increase the equilibration rate of water and CO2. When isotopic equilibrium has been attained, an aliquot of CO2 is extracted sequentially from each sample container, separated from water vapor by means of a dry ice trap, and introduced into a dual-inlet isotope-ratio mass spectrometer (DI-IRMS) for determination of the delta-18O value. There is oxygen isotopic fractionation between water and CO2, but it is constant at constant temperature. The DI-IRMS is a DuPont double-focusing mass spectrometer. It has a double collector. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other ion beams are collected in the front collector. The instrument is capable of measuring mass/charge (m/z) 44 and 45 or 44 and 46 by changing the ion-accelerating voltage under computer control. The ion beams from these m/z values are as follows: m/z 44=CO2=12C16O16O, m/z 45=CO2=13C16O16O primarily, and m/z 46 = CO2=12C16O18O primarily. The data acquisition and control software calculates delta-18O values.

  16. Interstitial distribution of charged macromolecules in the dog lung: a kinetic model.

    PubMed

    Parker, J C; Miniati, M; Pitt, R; Taylor, A E

    1987-01-01

    A mathematic model was constructed to investigate conflicting physiologic data concerning the charge effect of continuous capillaries to macromolecules in the lung. We simulated the equilibration kinetics of lactate dehydrogenase (MR 4.2 nM) isozymes LDH 1 (pI = 5.0) and LDH 5 (pI = 7.9) between plasma and lymph using previously measured permeability coefficients, lung tissue distribution volumes (VA) and plasma concentrations (CP) in lung tissue. Our hypothesis is that the fixed anionic charges in interstitium, basement membrane, and cell surfaces determine equilibration rather than charged membrane effects at the capillary barrier, so the same capillary permeability coefficients were used for both isozymes. Capillary filtration rates and protein fluxes were calculated using conventional flux equations. Initial conditions at baseline and increased left atrial pressures (PLA) were those measured in animal studies. Simulated equilibration of isozymes over 30 h in the model at baseline capillary pressures accurately predicted the observed differences in lymph/plasma concentration ratios (CL/CP) between isotopes at 4 h and equilibration of these ratios at 24 h. Quantitative prediction of isozyme CL/CP ratios was also obtained at increased PLA. However, an additional cation selective compartment representing the surface glycocalyx was required to accurately simulate the initial higher transcapillary clearances of cationic LDH 5. Thus experimental data supporting the negative barrier, positive barrier, and no charge barrier hypotheses were accurately reproduced by the model using only the observed differences in interstitial partitioning of isozymes without differences in capillary selectivity.

  17. Comparison of an in-helmet temperature monitor system to rectal temperature during exercise.

    PubMed

    Wickwire, P Jason; Buresh, Robert J; Tis, Laurie L; Collins, Mitchell A; Jacobs, Robert D; Bell, Marla M

    2012-01-01

    Body temperature monitoring is crucial in helping to decrease the amount and severity of heat illnesses; however, a practical method of monitoring temperature is lacking. In response to the lack of a practical method of monitoring the temperature of athletes, Hothead Technologies developed a device (HOT), which continuously monitors an athlete's fluctuations in body temperature. HOT measures forehead temperature inside helmets. The purpose of this study was to compare HOT against rectal temperature (Trec). Male volunteers (n = 29, age = 23.5 ± 4.5 years, weight = 83.8 ± 10.4 kg, height = 180.1 ± 5.8 cm, body fat = 12.3 ± 4.5%) exercised on a treadmill at an intensity of 60-75% heart rate reserve (HRR) (wet bulb globe temperature [WBGT] = 28.7° C) until Trec reached 38.7° C. The correlation between Trec and HOT was 0.801 (R = 0.64, standard error of the estimate (SEE) = 0.25, p = 0.00). One reason for this relatively high correlation is the microclimate that HOT is monitoring. HOT is not affected by the external climate greatly because of its location in the helmet. Therefore, factors such as evaporation do not alter HOT temperature to a great degree. HOT was compared with Trec in a controlled setting, and the exercise used in this study was moderate aerobic exercise, very unlike that used in football. In a controlled laboratory setting, the relationship between HOT and Trec showed favorable correlations. However, in applied settings, helmets are repeatedly removed and replaced forcing HOT to equilibrate to forehead temperature every time the helmet is replaced. Therefore, future studies are needed to mimic how HOT will be used in field situations.

  18. Thermochemistry and Kinetics of the Cl+O2 Association Reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Kreutter, K. D.; Shackelford, C. J.; Wine, P. H.

    1997-01-01

    Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).

  19. Changes in apple liquid phase concentration throughout equilibrium in osmotic dehydration.

    PubMed

    Barat, J M; Barrera, C; Frías, J M; Fito, P

    2007-03-01

    Previous results on apple tissue equilibration during osmotic dehydration showed that, at very long processing times, the solute concentrations of the fruit liquid phase and the osmotic solution were the same. In the present study, changes in apple liquid phase composition throughout equilibrium in osmotic dehydration were analyzed and modeled. Results showed that, by the time osmosed samples reached the maximum weight and volume loss, solute concentration of the fruit liquid phase was higher than that of the osmotic solution. The reported overconcentration could be explained in terms of the apple structure shrinkage that occurred during the osmotic dehydration with highly concentrated osmotic solutions due to the elastic response of the food structure to the loss of water and intake of solutes. The fruit liquid phase overconcentration rate was observed to depend on the concentration of the osmotic solution, the processing temperature, the sample size, and shape of the cellular tissue.

  20. Micelle Morphology and Mechanical Response of Triblock Gels

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.

    2010-01-12

    The effect of polymer concentration on mechanical response and micelle morphology of ABA and AB copolymers in B-selective solvents has been systematically studied. Micelle morphology was determined using a combination of small-angle X-ray scattering, shear, and birefringence while mechanical response at low and high strains was determined using indentation techniques. Self-consistent field theory calculations were used to determine micelle volume fraction profiles and to construct an equilibrium phase map. The transition from spherical to cylindrical micelles increases the triblock gel modulus and energy dissipation. Combining knowledge of gel relaxation time, which determines the rate at which the gel can equilibratemore » its micelle structure, with the equilibrium phase map allows estimation of the experimental temperatures and time scales over which kinetic trapping will arrest micelle structure evolution. Kinetic trapping enables cylindrical morphologies to be obtained at significantly lower polymer fractions than is possible in equilibrated systems.« less

  1. Observations of potassium in the tenuous lunar atmosphere

    NASA Technical Reports Server (NTRS)

    Kozlowski, Richard W. H.; Sprague, Ann L.; Hunten, Donald M.

    1990-01-01

    Observations of neutral potassium (K) in the tenuous lunar atmosphere are described. An echelle spectrograph, CCD, and data acquisition system are used to obtain emission spectra of neutral K atoms in the lunar atmosphere as observed by the 1.54 telescope at the Catalina Observatory at first quarter the night of April 29, 1989. A table of relevant lunar atmosphere parameters summarizes the results of the investigation. It is found that the number density at the surface is 9.5 + or - 1 atoms per cu cm and that there is a large nonthermal component and a deficiency of atoms equilibrated to the surface temperature. The calculated thermalization rate of the nonthermal component through encounters with the lunar surface gives a source of strength for the thermal component factor of 7 greater than loss by photoionization. Possible explanations for the low thermalized population observed are considered.

  2. NMR analyses of complex d-glucose anomerization.

    PubMed

    Kaufmann, Martin; Mügge, Clemens; Kroh, Lothar W

    2018-11-01

    Analyzing the 1 H NMR spectrum of d-glucose, the resonance frequencies of the anomeric protons of five d-glucose anomers could be determined in dependence on temperature. Besides, the relative concentrations of all cyclic d-glucose anomers could be quantified. Based on that, thermodynamic parameters were calculated. In addition, ring opening rate constants of all cyclic d-glucose anomers were measured for the first time using 1 H selective blind saturation transfer NMR spectroscopy. The results presented here give rise to the assumption that furanoid anomers highly influence the reactivity of total d-glucose. Finally, the complex anomeric equilibration curves for a freshly prepared solution of crystalline α-d-glucopyranose are presented. Based on that, it is hypothesized that the reactivity of a solution of a reducing sugar in general and d-glucose in particular depends on time until the thermodynamic equilibrium state is reached. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Constraining the Timescales of Rehydration in Nominally Anhydrous Minerals Using 3D Numerical Diffusion Models

    NASA Astrophysics Data System (ADS)

    Lynn, K. J.; Warren, J. M.

    2017-12-01

    Nominally anhydrous minerals (NAMs) are important for characterizing deep-Earth water reservoirs, but the water contents of olivine (ol), orthopyroxene (opx), and clinopyroxene (cpx) in peridotites generally do not reflect mantle equilibrium conditions. Ol is typically "dry" and decoupled from H in cpx and opx, which is inconsistent with models of partial melting and/or diffusive loss of H during upwelling beneath mid-ocean ridges. The rehydration of mantle pyroxenes via late-stage re-fertilization has been invoked to explain their relatively high water contents. Here, we use sophisticated 3D diffusion models (after Shea et al., 2015, Am Min) of H in ol, opx, and cpx to investigate the timescales of rehydration across a range of conditions relevant for melt-rock interaction and serpentinization of peridotites. Numerical crystals with 1 mm c-axis lengths and realistic crystal morphologies are modeled using recent H diffusivities that account for compositional variation and diffusion anisotropy. Models were run over timescales of minutes to millions of years and temperatures from 300 to 1200°C. Our 3D models show that, at the high-T end of the range, H concentrations in the cores of NAMs are partially re-equilibrated in as little as a few minutes, and completely re-equilibrated within hours to weeks. At low-T (300°C), serpentinization can induce considerable diffusion in cpx and opx. H contents are 30% re-equilibrated after continuous exposure to hydrothermal fluids for 102 and 105 years, respectively, which is inconsistent with previous interpretations that there is no effect on H in opx under similar conditions. Ol is unaffected after 1 Myr due to the slower diffusivity of the proton-vacancy mechanism at 300°C (2-4 log units lower than for opx). In the middle of the T range (700-1000°C), rehydration of opx and cpx occurs over hours to days, while ol is somewhat slower to respond (days to weeks), potentially allowing the decoupling observed in natural samples to occur via melt re-fertilization. Finally, off-center and oblique sections are common in natural samples and measurements likely reflect at least partially re-equilibrated compositions. Thus, the high water contents in peridotites may reflect variable NAM rehydration over a range of temperatures and timescales relevant for mid ocean ridge processes.

  4. A direct CO2 control system for ocean acidification experiments: testing effects on the coralline red algae Phymatolithon lusitanicum.

    PubMed

    Sordo, Laura; Santos, Rui; Reis, Joao; Shulika, Alona; Silva, Joao

    2016-01-01

    Most ocean acidification (OA) experimental systems rely on pH as an indirect way to control CO 2 . However, accurate pH measurements are difficult to obtain and shifts in temperature and/or salinity alter the relationship between pH and p CO 2 . Here we describe a system in which the target p CO 2 is controlled via direct analysis of p CO 2 in seawater. This direct type of control accommodates potential temperature and salinity shifts, as the target variable is directly measured instead of being estimated. Water in a header tank is permanently re-circulated through an air-water equilibrator. The equilibrated air is then routed to an infrared gas analyzer (IRGA) that measures p CO 2 and conveys this value to a Proportional-Integral-Derivative (PID) controller. The controller commands a solenoid valve that opens and closes the CO 2 flush that is bubbled into the header tank. This low-cost control system allows the maintenance of stabilized levels of p CO 2 for extended periods of time ensuring accurate experimental conditions. This system was used to study the long term effect of OA on the coralline red algae Phymatolithon lusitanicum . We found that after 11 months of high CO 2 exposure, photosynthesis increased with CO 2 as opposed to respiration, which was positively affected by temperature. Results showed that this system is adequate to run long-term OA experiments and can be easily adapted to test other relevant variables simultaneously with CO 2 , such as temperature, irradiance and nutrients.

  5. A direct CO2 control system for ocean acidification experiments: testing effects on the coralline red algae Phymatolithon lusitanicum

    PubMed Central

    Santos, Rui; Reis, Joao; Shulika, Alona

    2016-01-01

    Most ocean acidification (OA) experimental systems rely on pH as an indirect way to control CO2. However, accurate pH measurements are difficult to obtain and shifts in temperature and/or salinity alter the relationship between pH and pCO2. Here we describe a system in which the target pCO2 is controlled via direct analysis of pCO2 in seawater. This direct type of control accommodates potential temperature and salinity shifts, as the target variable is directly measured instead of being estimated. Water in a header tank is permanently re-circulated through an air-water equilibrator. The equilibrated air is then routed to an infrared gas analyzer (IRGA) that measures pCO2 and conveys this value to a Proportional-Integral-Derivative (PID) controller. The controller commands a solenoid valve that opens and closes the CO2 flush that is bubbled into the header tank. This low-cost control system allows the maintenance of stabilized levels of pCO2 for extended periods of time ensuring accurate experimental conditions. This system was used to study the long term effect of OA on the coralline red algae Phymatolithon lusitanicum. We found that after 11 months of high CO2 exposure, photosynthesis increased with CO2 as opposed to respiration, which was positively affected by temperature. Results showed that this system is adequate to run long-term OA experiments and can be easily adapted to test other relevant variables simultaneously with CO2, such as temperature, irradiance and nutrients. PMID:27703853

  6. The classification and complex thermal history of the enstatite chondrites

    NASA Technical Reports Server (NTRS)

    Zhang, Yanhong; Benoit, Paul H.; Sears, Derek W. G.

    1995-01-01

    We have carried out instrumental neutron activation analysis of 11 enstatite chondrites and electron microprobe analyses of 17 enstatite chondrites, most of which were previously little described. We report here the third known EH5 chondrite (LEW 88180) and an unusual EL6 chondrite (LEW 87119), new data on four EL3 chondrites (ALH 85119, EET 90299, PCA 91020, and MAC 88136, which is paired with MAC 88180 and MAC 88184), the second EL5 chondrite (TIL 91714), and an unusual metal-rich and sulfide-poor EL3 chondrite (LEW 87223). The often discussed differences in mineral composition displayed by the EH and EL chondrites are not as marked after the inclusion of the new samples in the database, and the two classes apparently experienced a similar range of equilibrium temperatures. However, texturally the EL chondrites appear to have experienced much higher levels of metamorphic alteration than EH chondrites of similar equilibration temperatures. Most of the petrologic type criteria are not applicable to enstatite chondrites and, unlike the ordinary chondrites, texture and mineralogy reflect different aspects of the meteorite history. We therefore propose that the existing petrologic type scheme not be used for enstatite chondrites. We suggest that while 'textural type' reflects peak metamorphic temperatures, the 'mineralogical type' reflects equilibration during postmetamorphic (probably regolith) processes. Unlike the ordinary chondrites and EH chondrites, EL chondrites experienced an extensive low-temperature metamorphic episode. There are now a large number of enstatite meteorite breccias and impact melts, and apparently surface processes were important in determining the present nature of the enstatite chondrites.

  7. High temperature normal phase liquid chromatography of aromatic hydrocarbons on bare zirconia.

    PubMed

    Paproski, Richard E; Liang, Chen; Lucy, Charles A

    2011-11-04

    The normal phase HPLC behavior of a bare zirconia column was studied at temperatures up to 200 °C using a hexane mobile phase. The use of elevated column temperatures significantly decreased the retention of twenty five aromatic model compounds according to the van't Hoff equation (>30-fold decrease for some compounds). Large improvements in peak shape, efficiency (>2.2-fold), aromatic group-type selectivity, and column re-equilibration times (>5-fold) were obtained at elevated temperatures. The thermal decomposition of two polar nitrogen compounds (indole and carbazole) was observed in a hexane/dichloromethane mobile phase at temperatures greater than 100 °C. The first order decomposition of carbazole was studied in further detail. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. A Particle X-ray Temporal Diagnostic (PXTD) for studies of kinetic, multi-ion effects, and ion-electron equilibration rates in Inertial Confinement Fusion plasmas at OMEGA (invited)

    NASA Astrophysics Data System (ADS)

    Sio, H.; Frenje, J. A.; Katz, J.; Stoeckl, C.; Weiner, D.; Bedzyk, M.; Glebov, V.; Sorce, C.; Gatu Johnson, M.; Rinderknecht, H. G.; Zylstra, A. B.; Sangster, T. C.; Regan, S. P.; Kwan, T.; Le, A.; Simakov, A. N.; Taitano, W. T.; Chacòn, L.; Keenan, B.; Shah, R.; Sutcliffe, G.; Petrasso, R. D.

    2016-11-01

    A Particle X-ray Temporal Diagnostic (PXTD) has been implemented on OMEGA for simultaneous time-resolved measurements of several nuclear products as well as the x-ray continuum produced in High Energy Density Plasmas and Inertial Confinement Fusion implosions. The PXTD removes systematic timing uncertainties typically introduced by using multiple instruments, and it has been used to measure DD, DT, D3He, and T3He reaction histories and the emission history of the x-ray core continuum with relative timing uncertainties within ±10-20 ps. This enables, for the first time, accurate and simultaneous measurements of the x-ray emission histories, nuclear reaction histories, their time differences, and measurements of Ti(t) and Te(t) from which an assessment of multiple-ion-fluid effects, kinetic effects during the shock-burn phase, and ion-electron equilibration rates can be made.

  9. A Particle X-ray Temporal Diagnostic (PXTD) for studies of kinetic, multi-ion effects, and ion-electron equilibration rates in Inertial Confinement Fusion plasmas at OMEGA (invited)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sio, H.; Frenje, J. A.; Katz, J.

    Here, a Particle X-ray Temporal Diagnostic (PXTD) has been implemented on OMEGA for simultaneous time-resolved measurements of several nuclear products as well as the x-ray continuum produced in High Energy Density Plasmas and Inertial Confinement Fusion implosions. The PXTD removes systematic timing uncertainties typically introduced by using multiple instruments, and it has been used to measure DD, DT, D 3He, and T 3He reaction histories and the emission history of the x-ray core continuum with relative timing uncertainties within ±10-20 ps. This enables, for the first time, accurate and simultaneous measurements of the x-ray emission histories, nuclear reaction histories, theirmore » time differences, and measurements of T i(t) and T e(t) from which an assessment of multiple-ion-fluid effects, kinetic effects during the shock-burn phase, and ion-electron equilibration rates can be made.« less

  10. A Particle X-ray Temporal Diagnostic (PXTD) for studies of kinetic, multi-ion effects, and ion-electron equilibration rates in Inertial Confinement Fusion plasmas at OMEGA (invited)

    DOE PAGES

    Sio, H.; Frenje, J. A.; Katz, J.; ...

    2016-09-14

    Here, a Particle X-ray Temporal Diagnostic (PXTD) has been implemented on OMEGA for simultaneous time-resolved measurements of several nuclear products as well as the x-ray continuum produced in High Energy Density Plasmas and Inertial Confinement Fusion implosions. The PXTD removes systematic timing uncertainties typically introduced by using multiple instruments, and it has been used to measure DD, DT, D 3He, and T 3He reaction histories and the emission history of the x-ray core continuum with relative timing uncertainties within ±10-20 ps. This enables, for the first time, accurate and simultaneous measurements of the x-ray emission histories, nuclear reaction histories, theirmore » time differences, and measurements of T i(t) and T e(t) from which an assessment of multiple-ion-fluid effects, kinetic effects during the shock-burn phase, and ion-electron equilibration rates can be made.« less

  11. Pork loin quality is not indicative of fresh belly or fresh and cured ham quality.

    PubMed

    Arkfeld, E K; Wilson, K B; Overholt, M F; Harsh, B N; Lowell, J E; Hogan, E K; Klehm, B J; Bohrer, B M; Mohrhauser, D A; King, D A; Wheeler, T L; Dilger, A C; Shackelford, S D; Boler, D D

    2016-12-01

    The objective was to characterize the relationship between fresh loin quality with fresh belly or fresh and cured ham quality. Pigs raised in 8 barns representing 2 seasons [cold ( = 4,290) and hot ( = 3,394)] and 2 production focuses [lean ( = 3,627) and quality ( = 4,057)] were used. Carcass characteristics and other meat quality data were collected on 7,684 carcasses. All of the carcasses were evaluated for HCW, LM depth, tenth rib fat depth, leg (ham primal) weight, instrumental color on the gluteus medius and gluteus profundus of the ham face, and subjective loin quality. Instrumental loin color and ultimate pH (≥ 22 h postmortem) were collected on the ventral side of loins along with dimensions and firmness scores of fresh bellies from 50% of the carcasses. Ten percent of the boneless loins and fresh hams were evaluated for slice shear force (SSF) or cured ham characteristics. Correlation coefficients between traits were computed using the CORR procedure of SAS and considered significantly different from 0 at ≤ 0.05. Temperature decline, beginning at 31 min postmortem and concluding at 22 h postmortem, for the longissimus dorsi and semimembranosus muscles were evaluated on 10% of the carcasses. Ultimate loin pH was correlated with dimensional belly characteristics ( ≥ |0.07|; < 0.0001) fresh ham instrumental color ( ≥ |0.03|; ≤ 0.05), and semimembranosus ultimate pH ( = 0.33; < 0.0001). Further, ultimate loin pH was correlated ( ≤ 0.01) with pump retention ( = 0.087) and cooked yield ( = 0.156) of cured hams. Instrumental L*on the ventral surface of the loin was related to L* on both muscles of the ham face ( ≤ 0.0001). Even though significant relationships between the loin, belly, and ham were detected, the variability in belly and ham quality explained by variability in loin quality was poor (≤ 22.09%). Compositional differences between the loin and belly may have contributed to those poor relationships. Additionally, differences in temperature declines during chilling between the loin and ham likely contributed to the weak nature of relationships. Equilibration of longissimus dorsi temperature to ambient cooler temperature occurred at 14 h postmortem ( = 0.0005), yet the semimembranosus had not equilibrated with ambient (equilibration bay) temperature ( < 0.0001) at 22 h postmortem. Using loin quality to draw conclusions about fresh belly and fresh and cured ham quality may be misleading.

  12. Clumped isotope thermometry in deeply buried sedimentary carbonates: The effects of C-O bond reordering and recrystallization

    NASA Astrophysics Data System (ADS)

    Passey, B. H.; Shenton, B.; Grossman, E. L.; Henkes, G. A.; Laya, J. C.; Perez-Huerta, A.

    2014-12-01

    Constraining the thermal histories of sedimentary basins is fundamental to a range of geologic applications including tectonics, petroleum system analysis, and the genesis of ore deposits. Carbonate rocks can serve as archives of basin thermal histories through solid-state reordering of their 13C-18O, or 'clumped isotope', bonds at elevated burial temperatures. Here we present one of the first applied studies of carbonate clumped isotope reordering to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Permian Palmarito Formation, Venezuela and the Carboniferous Bird Spring Formation, Nevada, USA. Carbonate components in the Palmarito Formation, buried to ~4 km depth, yield statistically indistinguishable clumped isotope temperatures (T(Δ47)) ranging from 86 to 122 °C. Clumped isotope temperatures of components in the more deeply buried Bird Spring Formation (>5 km), range from ~100 to 165 °C and differ by component type, with brachiopods and pore-filling cements yielding the highest T(Δ47) (mean = 153 and 141 °C, respectively) and crinoids and host rock yielding significantly cooler T(Δ47) (mean = 103 and 114 °C). New high-resolution thermal histories are coupled with kinetic models to predict the extent of solid-state C-O bond reordering during burial and exhumation for both sites. Application of these models suggests that brachiopods in the Palmarito Formation experienced partial bond reordering without complete equilibration of clumped isotopes at maximum burial temperature. In contrast, clumped isotope bonds of brachiopods from the Bird Spring Formation appear to have completely equilibrated at maximum burial temperature, and now reflect blocking temperatures 'locked-in' during cooling. The 40-50 °C cooler clumped isotope temperatures measured in Bird Spring Formation crinoids and host rock can be explained by both recrystallization and cementation during shallow burial and a greater inherent resistance to solid-state reordering than brachiopods.

  13. Magma storage prior to the 1912 eruption at Novarupta, Alaska

    USGS Publications Warehouse

    Hammer, J.E.; Rutherford, M.J.; Hildreth, W.

    2002-01-01

    New analytical and experimental data constrain the storage and equilibration conditions of the magmas erupted in 1912 from Novarupta in the 20th century's largest volcanic event. Phase relations at H2O+CO2 fluid saturation were determined for an andesite (58.7 wt% SiO2) and a dacite (67.7 wt%) from the compositional extremes of intermediate magmas erupted. The phase assemblages, matrix melt composition and modes of natural andesite were reproduced experimentally under H2O-saturated conditions (i.e., PH2O=PTOT) in a negatively sloping region in T-P space from 930 ??C/100 MPa to 960 ??C/75 MPa with fO2???N NO + 1. The H2O-saturated equilibration conditions of the dacite are constrained to a T-P region from 850 ??C/ 50 MPa to 880 ??C/25 MPa. If H2O-saturated, these magmas equilibrated at (and above) the level where coerupted rhyolite equilibrated (???100 MPa), suggesting that the andesite-dacite magma reservoir was displaced laterally rather than vertically from the rhyolite magma body. Natural mineral and melt compositions of intermediate magmas were also reproduced experimentally under saturation conditions with a mixed (H2O + CO2) fluid for the same range in PH2O. Thus, a storage model in which vertically stratified mafic to silicic intermediate magmas underlay H2O-saturated rhyolite is consistent with experimental findings only if the intermediates have XH2Ofl=0.7 and 0.9 for the extreme compositions, respectively. Disequilibrium features in natural pumice and scoria include pristine minerals existing outside their stability fields, and compositional zoning of titanomagnetite in contact with ilmenite. Variable rates of chemical equilibration which would eliminate these features constrain the apparent thermal excursion and re-distribution of minerals to the time scale of days.

  14. Toxicity Minimized Cryoprotectant Addition and Removal Procedures for Adherent Endothelial Cells

    PubMed Central

    Davidson, Allyson Fry; Glasscock, Cameron; McClanahan, Danielle R.; Benson, James D.; Higgins, Adam Z.

    2015-01-01

    Ice-free cryopreservation, known as vitrification, is an appealing approach for banking of adherent cells and tissues because it prevents dissociation and morphological damage that may result from ice crystal formation. However, current vitrification methods are often limited by the cytotoxicity of the concentrated cryoprotective agent (CPA) solutions that are required to suppress ice formation. Recently, we described a mathematical strategy for identifying minimally toxic CPA equilibration procedures based on the minimization of a toxicity cost function. Here we provide direct experimental support for the feasibility of these methods when applied to adherent endothelial cells. We first developed a concentration- and temperature-dependent toxicity cost function by exposing the cells to a range of glycerol concentrations at 21°C and 37°C, and fitting the resulting viability data to a first order cell death model. This cost function was then numerically minimized in our state constrained optimization routine to determine addition and removal procedures for 17 molal (mol/kg water) glycerol solutions. Using these predicted optimal procedures, we obtained 81% recovery after exposure to vitrification solutions, as well as successful vitrification with the relatively slow cooling and warming rates of 50°C/min and 130°C/min. In comparison, conventional multistep CPA equilibration procedures resulted in much lower cell yields of about 10%. Our results demonstrate the potential for rational design of minimally toxic vitrification procedures and pave the way for extension of our optimization approach to other adherent cell types as well as more complex systems such as tissues and organs. PMID:26605546

  15. Detection of haemoglobins with abnormal oxygen affinity by single blood gas analysis and 2,3-diphosphoglycerate measurement.

    PubMed

    Guerrini, G; Morabito, A; Samaja, M

    2000-10-01

    The aim is to determine if a single measurement of blood 2,3-diphosphoglycerate combined with gas analysis (pH, PCO2, PO2 and saturation) can identify the cause of an altered blood-oxygen affinity: the presence of an abnormal haemoglobin or a red cell disorder. The population (n=94) was divided into healthy controls (A, n=14), carriers of red cell disorders (B, n=72) and carriers of high oxygen affinity haemoglobins (C, n=8). Those variables were measured both in samples equilibrated at selected PCO2 and PO2 and in venous blood. In the univariable approach applied to equilibrated samples, we correctly identified C subjects in 93.6% or 96.8% of the cases depending on the selected variable, the standard P50 (PO2 at which 50% of haemoglobin is oxygenated) or a composite variable calculated from the above measurements. After introducing the haemoglobin concentration as a further discriminating variable, the A and B subjects were correctly identified in 91.9% or 94.2% of the cases, respectively. These figures become 93.0% or 86.1%, and 93.7% or 94.9% of the cases when using direct readings from venous blood, thereby avoiding the blood equilibration step. This test is feasible also in blood samples stored at 4 degrees C for 48 h, or at room temperature for 8 h.

  16. A simple headspace equilibration method for measuring dissolved methane

    USGS Publications Warehouse

    Magen, C; Lapham, L.L.; Pohlman, John W.; Marshall, Kristin N.; Bosman, S.; Casso, Michael; Chanton, J.P.

    2014-01-01

    Dissolved methane concentrations in the ocean are close to equilibrium with the atmosphere. Because methane is only sparingly soluble in seawater, measuring it without contamination is challenging for samples collected and processed in the presence of air. Several methods for analyzing dissolved methane are described in the literature, yet none has conducted a thorough assessment of the method yield, contamination issues during collection, transport and storage, and the effect of temperature changes and preservative. Previous extraction methods transfer methane from water to gas by either a "sparge and trap" or a "headspace equilibration" technique. The gas is then analyzed for methane by gas chromatography. Here, we revisit the headspace equilibration technique and describe a simple, inexpensive, and reliable method to measure methane in fresh and seawater, regardless of concentration. Within the range of concentrations typically found in surface seawaters (2-1000 nmol L-1), the yield of the method nears 100% of what is expected from solubility calculation following the addition of known amount of methane. In addition to being sensitive (detection limit of 0.1 ppmv, or 0.74 nmol L-1), this method requires less than 10 min per sample, and does not use highly toxic chemicals. It can be conducted with minimum materials and does not require the use of a gas chromatograph at the collection site. It can therefore be used in various remote working environments and conditions.

  17. Importance of equilibration time in the partitioning and toxicity of zinc in spiked sediment bioassays

    USGS Publications Warehouse

    Lee, J.-S.; Lee, B.-G.; Luoma, S.N.; Yoo, H.

    2004-01-01

    The influences of spiked Zn concentrations (1-40 ??mol/g) and equilibration time (???95 d) on the partitioning of Zn between pore water (PW) and sediment were evaluated with estuarine sediments containing two levels (5 and 15 ??mol/g) of acid volatile sulfides (AVS). Their influence on Zn bioavailability was also evaluated by a parallel, 10-d amphipod (Leptocheirus plumulosus) mortality test at 5, 20, and 85 d of equilibration. During the equilibration, AVS increased (up to twofold) with spiked Zn concentration ([Zn]), whereas Zn-simultaneously extracted metals ([SEM]; Zn with AVS) remained relatively constant. Concentrations of Zn in PW decreased most rapidly during the initial 30 d and by 11- to 23-fold during the whole 95-d equilibration period. The apparent partitioning coefficient (Kpw, ratio of [Zn] in SEM to PW) increased by 10- to 20-fold with time and decreased with spiked [Zn] in sediments. The decrease of PW [Zn] could be explained by a combination of changes in AVS and redistribution of Zn into more insoluble phases as the sediment aged. Amphipod mortality decreased significantly with the equilibration time, consistent with decrease in dissolved [Zn]. The median lethal concentration (LC50) value (33 ??M) in the second bioassay, conducted after 20 d of equilibration, was twofold the LC50 in the initial bioassay at 5 d of equilibration, probably because of the change of dissolved Zn speciation. Sediment bioassay protocols employing a short equilibration time and high spiked metal concentrations could accentuate partitioning of metals to the dissolved phase and shift the pathway for metal exposure toward the dissolved phase.

  18. The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Barnes, S. J.

    1986-01-01

    The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

  19. Assessment of geothermal resources at Newcastle, Utah

    USGS Publications Warehouse

    Blackett, Robert E.; Shubat, Michael A.; Chapman, David S.; Forster, Craig B.; Schlinger, Charles M.

    1989-01-01

    Integrated geology, geophysics, and geochemistry studies in the Newcastle area of southwest Utah are used to develop a conceptual geologic model of a blind, moderate-temperature hydrothermal system. Studies using 12 existing and 12 new, thermal gradient test holes, in addition to geologic mapping, gravity surveys, and other investigations have helped define the thermal regime. Preliminary results indicate that the up-flow region is located near the west-facing escarpment of an adjacent mountain range, probably related to the bounding range-front fault. Chemical geothermometers suggest equilibration temperatures ranging from 140??C to 170??C. The highest temperature recorded in the system is 130??C from an exploration well drilled by the Unocal Corporation.

  20. Exploring the dynamics of kinetic/multi-ion effects and ion-electron equilibration rates in ICF plasmas at OMEGA

    NASA Astrophysics Data System (ADS)

    Sio, H.

    2017-10-01

    During the last few years, an increasing number of experiments have shown that kinetic and multi-ion-fluid effects do impact the performance of an ICF implosion. Observations include: increasing yield degradation as the implosion becomes more kinetic; thermal decoupling between ion species; anomalous yield scaling for different fuel mixtures; ion diffusion; and fuel stratification. The common theme in these experiments is that the results are based on time-integrated nuclear observables that are affected by an accumulation of effects throughout the implosion, which complicate interpretation of the data. A natural extension of these studies is therefore to conduct time-resolved measurements of multiple nuclear-burn histories to explore the dynamics of kinetic/multi-ion effects in the fuel and their impact on the implosion performance. This was accomplished through simultaneous, high-precision measurements of the relative timing of the onset, bang time and duration of DD, D3He, DT and T3He burn from T3He (with trace D) or D3He gas-filled implosions using the new Particle X-ray Temporal Diagnostic (PXTD) on OMEGA. As the different reactions have different temperature sensitivities, Ti(t) was determined from the data. Uniquely to the PXTD, several x-ray emission histories (in different energy bands) were also measured, from which a spatially averaged Te(t) was also determined. The inferred Ti(t) and Te(t) data have been used to experimentally explore ion-electron equilibration rates and the Coulomb Logarithm for various plasma conditions. Finally, the implementation and use of PXTD, which represents a significant advance at OMEGA, have laid the foundation for implementing a Te(t) measurement in support of the main cryogenic DT programs at OMEGA and the NIF. This work was supported in part by the US DOE, LLE, LLNL, and DOE NNSA SSGF.

  1. Phase and vortex correlations in superconducting Josephson-junction arrays at irrational magnetic frustration.

    PubMed

    Granato, Enzo

    2008-07-11

    Phase coherence and vortex order in a Josephson-junction array at irrational frustration are studied by extensive Monte Carlo simulations using the parallel-tempering method. A scaling analysis of the correlation length of phase variables in the full equilibrated system shows that the critical temperature vanishes with a power-law divergent correlation length and critical exponent nuph, in agreement with recent results from resistivity scaling analysis. A similar scaling analysis for vortex variables reveals a different critical exponent nuv, suggesting that there are two distinct correlation lengths associated with a decoupled zero-temperature phase transition.

  2. Phase transitions and dynamics of bulk and interfacial water.

    PubMed

    Franzese, G; Hernando-Martínez, A; Kumar, P; Mazza, M G; Stokely, K; Strekalova, E G; de los Santos, F; Stanley, H E

    2010-07-21

    New experiments on water at the surface of proteins at very low temperature display intriguing dynamic behaviors. The extreme conditions of these experiments make it difficult to explore the wide range of thermodynamic state points needed to offer a suitable interpretation. Detailed simulations suffer from the same problem, where equilibration times at low temperature become extremely long. We show how Monte Carlo simulations and mean field calculations using a tractable model of water help interpret the experimental results. Here we summarize the results for bulk water and investigate the thermodynamic and dynamic properties of supercooled water at an interface.

  3. Equilibration in finite Bose systems

    NASA Astrophysics Data System (ADS)

    Wolschin, Georg

    2018-06-01

    The equilibration of a finite Bose system is modeled using a gradient expansion of the collision integral that leads to a nonlinear transport equation. For constant transport coefficients, it is solved in closed form through a nonlinear transformation. Using schematic initial conditions, the exact solution and the equilibration time are derived and compared to the corresponding case for fermions. Applications to the fast equilibration of the gluon system created initially in relativistic heavy-ion collisions, and to cold quantum gases are envisaged.

  4. Equilibration of experimentally determined protein structures for molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Walton, Emily B.; Vanvliet, Krystyn J.

    2006-12-01

    Preceding molecular dynamics simulations of biomolecular interactions, the molecule of interest is often equilibrated with respect to an initial configuration. This so-called equilibration stage is required because the input structure is typically not within the equilibrium phase space of the simulation conditions, particularly in systems as complex as proteins, which can lead to artifactual trajectories of protein dynamics. The time at which nonequilibrium effects from the initial configuration are minimized—what we will call the equilibration time—marks the beginning of equilibrium phase-space exploration. Note that the identification of this time does not imply exploration of the entire equilibrium phase space. We have found that current equilibration methodologies contain ambiguities that lead to uncertainty in determining the end of the equilibration stage of the trajectory. This results in equilibration times that are either too long, resulting in wasted computational resources, or too short, resulting in the simulation of molecular trajectories that do not accurately represent the physical system. We outline and demonstrate a protocol for identifying the equilibration time that is based on the physical model of Normal Mode Analysis. We attain the computational efficiency required of large-protein simulations via a stretched exponential approximation that enables an analytically tractable and physically meaningful form of the root-mean-square deviation of atoms comprising the protein. We find that the fitting parameters (which correspond to physical properties of the protein) fluctuate initially but then stabilize for increased simulation time, independently of the simulation duration or sampling frequency. We define the end of the equilibration stage—and thus the equilibration time—as the point in the simulation when these parameters attain constant values. Compared to existing methods, our approach provides the objective identification of the time at which the simulated biomolecule has entered an energetic basin. For the representative protein considered, bovine pancreatic trypsin inhibitor, existing methods indicate a range of 0.2-10ns of simulation until a local minimum is attained. Our approach identifies a substantially narrower range of 4.5-5.5ns , which will lead to a much more objective choice of equilibration time.

  5. Effect of human milk fortifiers on bacterial growth in human milk.

    PubMed

    Santiago, Myla S; Codipilly, Champa N; Potak, Debra C; Schanler, Richard J

    2005-10-01

    As a component in human milk fortifiers (HMF), iron may equilibrate with human milk for as long as 24 hours, bind important bacteriostatic proteins, and potentially affect the host defense properties of human milk. We compared bacterial growth in human milk prepared with each of two HMF differing in their content of iron. Samples of human milk obtained from mothers of premature infants were divided and mixed with one of two HMF and maintained at refrigerator temperature. Refrigerated milk samples were removed at 0, 24, and 72 hours for determination of total bacterial colony counts (TBCC). TBCC did not differ between groups but declined from 0 to 72 hours, p<0.001. These data suggest that differences in iron content, or other nutrients in HMF, do not affect bacterial growth in human milk. Storage of fortified human milk at refrigerator temperature for 72 hours results in decreased bacterial growth. As a component in human milk fortifiers (HMF), iron may equilibrate with human milk for as long as 24 hours, bind important bacteriostatic proteins, and potentially affect the host defense properties of human milk. We compared bacterial growth in human milk prepared with each of two HMF differing in their content of iron. Samples of human milk obtained from mothers of premature infants were divided and mixed with one of two HMF and maintained at refrigerator temperature. Refrigerated milk samples were removed at 0, 24, and 72 hours for determination of total bacterial colony counts (TBCC).

  6. Microstructural evidence of melting in crustal rocks (Invited)

    NASA Astrophysics Data System (ADS)

    Holness, M. B.; Cesare, B.; Sawyer, E. W.

    2010-12-01

    The signature of the former presence of melt on a microscopic scale is highly variable, subject to modification both during the melting event and during its subsequent history. Static pyrometamorphism results in melt films on grain boundaries between reactant phases. If a volume increase is involved, melting results in hydrofracture. On a longer timescale, as demonstrated by fragments of the crustal source in lava flows at El Hoyazo (SE Spain), melt occurs throughout the rock. These examples are highly unusual: the great majority of rocks that underwent melting cooled more slowly, permitting microstructural modification driven by a combination of textural equilibration, reaction and deformation. In the absence of deformation, and at constant temperature, melt-bearing rocks approach textural equilibrium, characterised by uniform grain size, smoothly curved grain boundaries and the establishment at all three-grain junctions of the equilibrium dihedral angle. The dihedral angle controls melt connectivity, with consequences for melt mobility and rock rheology. However, deformation is the rule rather than the exception in regional metamorphic terrains with profound effects on melt distribution. If deformation occurs predominantly by diffusive processes, textural equilibration can keep pace. At higher deformation rates melt is squeezed into planar pockets aligned parallel to the shearing direction or perpendicular to the extensional stress. Microstructures formed during solidification are controlled by cooling rate, H2O, and the size of the melt pockets. Large pockets solidify to look like igneous rocks. In small pores the supersaturation required for crystal growth is high and melt persist to lower temperatures, even being preserved as tiny glassy inclusions (“nanogranites”) in regional terranes. The pore size effect changes crystallization order, resulting in small, highly cuspate grains on grain boundaries with low dihedral angles. Crystallisation microstructures of poly-component liquids are highly dependent on diffusion rates, and therefore H2O content. Dry conditions result in diffusion-limited crystallisation to form intergrowths and symplectites (e.g. granophyre). The cooling rate must be slow in order to nucleate and grow individual grains from the melt. If the melt was primarily concentrated in thick films on grain boundaries this results in the “string of beads” texture. If there is sufficient water, and the rocks stay sufficiently hot, the microstructures will move towards a granular texture, driven by the reduction in interfacial energy. Highly cuspate pseudomorphs of melt at three-grain junctions will become rounded as the dihedral angle increases (generally towards the range 110-140°). Melt-related microstructures are more likely to be retained in dry rocks: in migmatite terranes in which melting was driven by infiltration of aqueous fluids and where melt extraction wasn’t pervasive, microstructures are likely to have been significantly modified by sub-solidus recrystallisation, especially likely if the rock underwent intense deformation on the retrograde path.

  7. Theorie de la Levitation Radiative a L'equilibre dans les Etoiles Naines Blanches Chaudes

    NASA Astrophysics Data System (ADS)

    Chayer, Pierre

    1995-01-01

    Les resultats de nouveaux calculs detailles de levitation radiative dans des naines blanches chaudes utilisant la base de donnees atomiques TOPBASE sont presentes. Des accelerations radiatives et des abondances d'equilibre ont ete calculees pour C, N, O, Ne, Na, Mg, Al, Si, S, Ar, Ca, et Fe, sur des grilles de modeles d'enveloppes stellaires riches en hydrogene et riches en helium. La grille des modeles de DA a des gravites telles que log g = 7.0, 7.5, 8.0, et 8.5, et couvre les temperatures effectives pour lesquelles 100,000K >= T_ {rm eff} >= 20,000K par sauts de 2,500K. La grille des modeles de DO/DB est similaire mais se prolonge a T_{rm eff } = 130,000K. Les resultats d'abondances d'equilibre de Ni dans des DA utilisant la base de donnees de Kurucz sont aussi presentes. Nous discutons dans les moindres details de la physique incluse dans les calculs afin de fournir une bonne comprehension physique de la levitation radiative sous les conditions rencontrees dans les naines blanches. Nous discutons aussi de la forme et de la dependance en fonction de la profondeur des reservoirs des elements, crees par un equilibre entre l'acceleration radiative et la gravite locale effective dans differentes enveloppes stellaires. Nous soulignons le role important joue dans la morphologie de ces reserviors par les etats d'ionisation dominants se trouvant dans la configuration gaz noble. Nos resultats centraux sont presentes sous forme de figures montrant le comportement de l'abondance photospherique estimee pour chaque element en fonction de la temperature effective et de la gravite de surface. Nous apportons egalement des ameliorations aux calculs de levitation radiative en utilisant une approche de modeles d'atmospheres pour les etoiles riches en hydrogene. Nous mettons l'emphase, en particulier, sur le role des traces d'elements lourds qui peuvent etre presents dans le plasma. Nous utilisons une table d'opacite monochromatique detaillee calculee pour un plasma compose de H contenant de faibles quantites de C, N, O, et Fe pour illustrer comment les abondances d'equilibre des elements supportes reagissent a la redistribution du flux causee par l'addition de ces traces de matiere opaque. Nous traitons ce probleme, en premier lieu, selon une approche basee sur des modeles d'enveloppes et, en second lieu, selon une approche basee sur des modeles d'atmospheres. Nous considerons aussi deux autres ameliorations concernant, premierement, un traitement plus sophistique de la redistribution de la quantite de mouvement d'un ion suite a l'absorption d'un photon, et deuxiemement, l'utilisation d'une meilleure valeur de la largeur du profil de raie associee a l'elargissement par pression. Bien qu'une poignee d'abondances soient disponibles a partir de l'analyse des observations qui ont ete faites jusqu'a maintenant, nous sommes neanmoins capables de conclure, a l'aide de comparaisons detaillees, que la theorie de la levitation radiative a l'equilibre ne reussit pas a expliquer quantitativement les patrons d'abondances des elements lourds observes dans les naines blanches chaudes. Au moins un autre mecanisme doit competionner avec la levitation radiative et le triage gravitationnel dans les atmospheres/enveloppes des naines blanches chaudes. Nous suggerons la possibilite d'un vent stellaire ou encore la possibilite d'accretion.

  8. Simultaneous Determination of Benzene and Toluene in Pesticide Emulsifiable Concentrate by Headspace GC-MS

    PubMed Central

    Jiang, Hua; Yang, Jing; Fan, Li; Li, Fengmin; Huang, Qiliang

    2013-01-01

    The toxic inert ingredients in pesticide formulations are strictly regulated in many countries. In this paper, a simple and efficient headspace-gas chromatography-mass spectrometry (HSGC-MS) method using fluorobenzene as an internal standard (IS) for rapid simultaneous determination of benzene and toluene in pesticide emulsifiable concentrate (EC) was established. The headspace and GC-MS conditions were investigated and developed. A nonpolar fused silica Rtx-5 capillary column (30 m × 0.20 mm i.d. and 0.25 μm film thickness) with temperature programming was used. Under optimized headspace conditions, equilibration temperature of 120°C, equilibration time of 5 min, and sample size of 50 μL, the regression of the peak area ratios of benzene and toluene to IS on the concentrations of analytes fitted a linear relationship well at the concentration levels ranging from 3.2 g/L to 16.0 g/L. Standard additions of benzene and toluene to blank different matrix solutions 1ead to recoveries of 100.1%–109.5% with a relative standard deviation (RSD) of 0.3%–8.1%. The method presented here stands out as simple and easily applicable, which provides a way for the determination of toxic volatile adjuvant in liquid pesticide formulations. PMID:23607048

  9. Selection Experiments in the Penna Model for Biological Aging

    NASA Astrophysics Data System (ADS)

    Medeiros, G.; Idiart, M. A.; de Almeida, R. M. C.

    We consider the Penna model for biological aging to investigate correlations between early fertility and late life survival rates in populations at equilibrium. We consider inherited initial reproduction ages together with a reproduction cost translated in a probability that mother and offspring die at birth, depending on the mother age. For convenient sets of parameters, the equilibrated populations present genetic variability in what regards both genetically programmed death age and initial reproduction age. In the asexual Penna model, a negative correlation between early life fertility and late life survival rates naturally emerges in the stationary solutions. In the sexual Penna model, selection experiments are performed where individuals are sorted by initial reproduction age from the equilibrated populations and the separated populations are evolved independently. After a transient, a negative correlation between early fertility and late age survival rates also emerges in the sense that populations that start reproducing earlier present smaller average genetically programmed death age. These effects appear due to the age structure of populations in the steady state solution of the evolution equations. We claim that the same demographic effects may be playing an important role in selection experiments in the laboratory.

  10. Corresponding state-based correlations for the temperature-dependent surface tension of saturated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Tian, Jianxiang; Zhang, Cuihua; Zhang, Laibin; Zheng, Mengmeng; Liu, Shuzhen

    2017-10-01

    Based on the recent progresses on the corresponding state-based correlations for the temperature-dependent surface tension of saturated fluids [I. Cachadiña, A. Mulero and J. X. Tian, Fluid Phase Equilibr. 442 (2017) 68; J. X. Tian, M. M. Zheng, H. L. Yi, L. B. Zhang and S. Z. Liu, Mod. Phys. Lett. B 31 (2017) 1750110], we proposed a new correlation for saturated hydrocarbons. This correlation includes three fluid-independent parameters and inquires the critical temperature, the triple-point temperature and the surface tension at the triple-point temperature as inputs for each hydrocarbon. Results show that this correlation can reproduce NIST data with absolute average deviation (AAD) less than 1% for 10 out of 19 hydrocarbons and AAD less than 5% for 17 out of 19 hydrocarbons, clearly better than other correlations.

  11. Effect of equilibration on primitive path analyses of entangled polymers.

    PubMed

    Hoy, Robert S; Robbins, Mark O

    2005-12-01

    We use recently developed primitive path analysis (PPA) methods to study the effect of equilibration on entanglement density in model polymeric systems. Values of Ne for two commonly used equilibration methods differ by a factor of 2-4 even though the methods produce similar large-scale chain statistics. We find that local chain stretching in poorly equilibrated samples increases entanglement density. The evolution of Ne with time shows that many entanglements are lost through fast processes such as chain retraction as the local stretching relaxes. Quenching a melt state into a glass has little effect on Ne. Equilibration-dependent differences in short-scale structure affect the craze extension ratio much less than expected from the differences in PPA values of Ne.

  12. Effect of ambient temperature on the thermal profile of the human forearm, hand, and fingers

    NASA Technical Reports Server (NTRS)

    Montgomery, L. D.; Williams, B. A.

    1976-01-01

    Forearm, hand, and finger skin temperatures were measured on the right and left sides of seven resting men. The purpose was to determine the bilateral symmetry of these segmental temperature profiles at ambient temperatures from 10 to 45 C. Thermistors placed on the right and left forearms, hands, and index fingers were used to monitor the subjects until equilibration was reached at each ambient temperature. Additionally, thermal profiles of both hands were measured with copper-constantan thermocouples. During one experimental condition (23 C ambient), rectal, ear canal, and 24 skin temperatures were measured on each subject. Average body and average skin temperatures are given for each subject at the 23 C ambient condition. Detailed thermal profiles are also presented for the dorsal, ventral, and circumferential left forearm, hand, and finger skin temperatures at 23 C ambient. No significant differences were found between the mean skin temperatures of the right and left contralateral segments at any of the selected ambient temperatures.

  13. Subcritical Water Extraction of Amino Acids from Atacama Desert Soils

    NASA Technical Reports Server (NTRS)

    Amashukeli, Xenia; Pelletier, Christine C.; Kirby, James P.; Grunthaner, Frank J.

    2007-01-01

    Amino acids are considered organic molecular indicators in the search for extant and extinct life in the Solar System. Extraction of these molecules from a particulate solid matrix, such as Martian regolith, will be critical to their in situ detection and analysis. The goals of this study were to optimize a laboratory amino acid extraction protocol by quantitatively measuring the yields of extracted amino acids as a function of liquid water temperature and sample extraction time and to compare the results to the standard HCl vapor- phase hydrolysis yields for the same soil samples. Soil samples from the Yungay region of the Atacama Desert ( Martian regolith analog) were collected during a field study in the summer of 2005. The amino acids ( alanine, aspartic acid, glutamic acid, glycine, serine, and valine) chosen for analysis were present in the samples at concentrations of 1 - 70 parts- per- billion. Subcritical water extraction efficiency was examined over the temperature range of 30 - 325 degrees C, at pressures of 17.2 or 20.0 MPa, and for water- sample contact equilibration times of 0 - 30 min. None of the amino acids were extracted in detectable amounts at 30 degrees C ( at 17.2 MPa), suggesting that amino acids are too strongly bound by the soil matrix to be extracted at such a low temperature. Between 150 degrees C and 250 degrees C ( at 17.2 MPa), the extraction efficiencies of glycine, alanine, and valine were observed to increase with increasing water temperature, consistent with higher solubility at higher temperatures, perhaps due to the decreasing dielectric constant of water. Amino acids were not detected in extracts collected at 325 degrees C ( at 20.0 MPa), probably due to amino acid decomposition at this temperature. The optimal subcritical water extraction conditions for these amino acids from Atacama Desert soils were achieved at 200 degrees C, 17.2 MPa, and a water- sample contact equilibration time of 10 min.

  14. Two-stage ordering processes under annealing of Sr submonolayers on Mo(1 1 2)

    NASA Astrophysics Data System (ADS)

    Fedorus, A.; Godzik, G.; Naumovets, A.; Pfnür, H.

    2004-09-01

    Using LEED as technique of investigation, the evolution of geometrical order in the system Sr/Mo(1 1 2) was studied after annealing at temperatures between 100 and 900 K. Two stages of ordering were found for the chain-like structures p(8 × 1) and p(5 × 1). Partial ordering occurred already at the base adsorption temperature (90 K) with slight improvement after annealing to temperatures around 200 K. The full equilibration of the layers, however, was found to happen only at high annealing temperatures (ranging between 500 and 600 K, depending on coverage). Correlating these data with the highly anisotropic diffusivity known for Sr overlayers on Mo(1 1 2), we assume that the low-temperature ordering sets in via a kink-like diffusion of adsorbate chains essentially along the substrate troughs, whereas in the high-temperature step, diffusion across the troughs is most important.

  15. How long does it take to equilibrate the unfolded state of a protein?

    PubMed Central

    Levy, Ronald M; Dai, Wei; Deng, Nan-Jie; Makarov, Dmitrii E

    2013-01-01

    How long does it take to equilibrate the unfolded state of a protein? The answer to this question has important implications for our understanding of why many small proteins fold with two state kinetics. When the equilibration within the unfolded state U is much faster than the folding, the folding kinetics will be two state even if there are many folding pathways with different barriers. Yet the mean first passage times (MFPTs) between different regions of the unfolded state can be much longer than the folding time. This seems to imply that the equilibration within U is much slower than the folding. In this communication we resolve this paradox. We present a formula for estimating the time to equilibrate the unfolded state of a protein. We also present a formula for the MFPT to any state within U, which is proportional to the average lifetime of that state divided by the state population. This relation is valid when the equilibration within U is very fast as compared with folding as it often is for small proteins. To illustrate the concepts, we apply the formulas to estimate the time to equilibrate the unfolded state of Trp-cage and MFPTs within the unfolded state based on a Markov State Model using an ultra-long 208 microsecond trajectory of the miniprotein to parameterize the model. The time to equilibrate the unfolded state of Trp-cage is ∼100 ns while the typical MFPTs within U are tens of microseconds or longer. PMID:23963761

  16. Real-time radiative divertor feedback control development for the NSTX-U tokamak using a vacuum ultraviolet spectrometer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Soukhanovskii, V. A., E-mail: vlad@llnl.gov; Kaita, R.; Stratton, B.

    2016-11-15

    A radiative divertor technique is planned for the NSTX-U tokamak to prevent excessive erosion and thermal damage of divertor plasma-facing components in H-mode plasma discharges with auxiliary heating up to 12 MW. In the radiative (partially detached) divertor, extrinsically seeded deuterium or impurity gases are used to increase plasma volumetric power and momentum losses. A real-time feedback control of the gas seeding rate is planned for discharges of up to 5 s duration. The outer divertor leg plasma electron temperature T{sub e} estimated spectroscopically in real time will be used as a control parameter. A vacuum ultraviolet spectrometer McPherson Modelmore » 251 with a fast charged-coupled device detector is developed for temperature monitoring between 5 and 30 eV, based on the Δn = 0, 1 line intensity ratios of carbon, nitrogen, or neon ion lines in the spectral range 300–1600 Å. A collisional-radiative model-based line intensity ratio will be used for relative calibration. A real-time T{sub e}-dependent signal within a characteristic divertor detachment equilibration time of ∼10–15 ms is expected.« less

  17. Real-time radiative divertor feedback control development for the NSTX-U tokamak using a vacuum ultraviolet spectrometer

    DOE PAGES

    Soukhanovskii, V. A.; Kaita, R.; Stratton, B.

    2016-08-04

    Here, a radiative divertor technique is planned for the NSTX-U tokamak to prevent excessive erosion and thermal damage of divertor plasma-facing components in H-mode plasma discharges with auxiliary heating up to 12 MW. In the radiative (partially detached) divertor, extrinsically seeded deuterium or impurity gases are used to increase plasma volumetric power and momentum losses. A real-time feedback control of the gas seeding rate is planned for discharges of up to 5 s duration. The outer divertor leg plasma electron temperature T e estimated spectroscopically in real time will be used as a control parameter. A vacuum ultraviolet spectrometer McPhersonmore » Model 251 with a fast charged-coupled device detector is developed for temperature monitoring between 5 and 30 eV, based on the Δn = 0, 1 line intensity ratios of carbon, nitrogen, or neon ion lines in the spectral range 300–1600 Å. A collisional-radiative model-based line intensity ratio will be used for relative calibration. A real-time T e-dependent signal within a characteristic divertor detachment equilibration time of ~10–15 ms is expected.« less

  18. Protein crystal growth results from shuttle flight 51-F

    NASA Technical Reports Server (NTRS)

    Bugg, C. E.

    1985-01-01

    The protein crystal growth (PCG) experiments run on 51-F were analyzed. It was found that: (1) sample stability is increased over that observed during the experiments on flight 51-D; (2) the dialysis experiments produced lysozyme crystals that were significantly larger than those obtained in our identical ground-based studies; (3) temperature fluctuations apparently caused problems during the crystallization experiments on 51-F; (4) it is indicated that teflon tape stabilizes droplets on the syringe tips; (5) samples survived during the reentry and landing in glass tips that were not stoppered with plungers; (6) from the ground-based studies, it was expected that equilibration should be complete within 2 to 4 days for all of these vapor-diffusion experiments, thus it appears that the vapor diffusion rates are somewhat slower under microgravity conditions; (7) drop tethering was highly successful, all four of the tethered drops were stable, even though they contained MPD solutions; (8) the PCG experiments on 51-F were done to assess the hardware and experimental procedures that are developed for future flights, when temperature control will be available. Lysozyme crystals obtained by microdialysis are considerably larger than those obtained on the ground, using the identical apparatus and procedures.

  19. What can the Hf–W System tell Us About the Mechanism and Timing of Earth's Core Formation?

    NASA Astrophysics Data System (ADS)

    Fischer, R. A.; Nimmo, F.; O'Brien, D. P.

    2018-05-01

    Strong tradeoff between effects of depth and extent of metal-silicate equilibration and formation timescale on the Hf-W system. Whole mantle equilibration requires k = 0.4. Later formation times require less equilibration to match Earth's anomaly.

  20. Twin defects in thick stoichiometric lithium tantalate crystals prepared by a vapor transport equilibration method

    NASA Astrophysics Data System (ADS)

    Yang, Jinfeng; Sun, Jun; Xu, Jingjun; Li, Qinglian; Shang, Jifang; Zhang, Ling; Liu, Shiguo; Huang, Cunxin

    2016-01-01

    The twins were observed and investigated in vapor transport equilibration (VTE) treated lithium tantalate crystals by burying congruent lithium tantalate crystals (CLT) in a Li-rich polycrystalline powder. Twins and their etched patterns were observed under an optical polarizing microscope, and the geometry of the twins was discussed. Twin composition planes were the { 01 1 bar 2 } planes. The cause of twinning was analyzed and verified by experiment. The results indicate that the emergence of twins is due to sintering stress, which arises from sintered Li-rich polycrystalline powders at high temperature. 3.2 mm thick stoichiometric lithium tantalate (SLT) crystals without twins were obtained by setting corundum crucibles over the top of the crystals to make crystals free from the sintering stress. In addition, cracks were observed at the intersection of twin bands, and the stress caused by the dislocation pile-up was considered to be the reason for the formation of cracks.

  1. Equilibration: Developing the Hard Core of the Piagetian Research Program.

    ERIC Educational Resources Information Center

    Rowell, J.A.

    1983-01-01

    Argues that the status of the concept of equilibration is classified by considering Piagetian theory as a research program in the sense elaborated in 1974 by Lakatos. A pilot study was made to examine the precision and testability of equilibration in Piaget's 1977 model.(Author/RH)

  2. Rapid spatial equilibration of a particle in a box.

    PubMed

    Malabarba, Artur S L; Linden, Noah; Short, Anthony J

    2015-12-01

    We study the equilibration behavior of a quantum particle in a one-dimensional box, with respect to a coarse-grained position measurement (whether it lies in a certain spatial window or not). We show that equilibration in this context indeed takes place and does so very rapidly, in a time comparable to the time for the initial wave packet to reach the edges of the box. We also show that, for this situation, the equilibration behavior is relatively insensitive to the precise choice of position measurements or initial condition.

  3. Climate dominated topography in a tectonically active mountain range

    NASA Astrophysics Data System (ADS)

    Adams, B. A.; Ehlers, T. A.

    2015-12-01

    Tests of the interactions between tectonic and climate forcing on Earth's topography often focus on the concept of steady-state whereby processes of rock deformation and erosion are opposing and equal. However, when conditions change such as the climate or tectonic rock uplift, then surface processes act to restore the balance between rock deformation and erosion by adjusting topography. Most examples of canonical steady-state mountain ranges lie within the northern hemisphere, which underwent a radical change in the Quaternary due to the onset of widespread glaciation. The activity of glaciers changed erosion rates and topography in many of these mountain ranges, which likely violates steady-state assumptions. With new topographic analysis, and existing patterns of climate and rock uplift, we explore a mountain range previously considered to be in steady-state, the Olympic Mountains, USA. The broad spatial trend in channel steepness values suggests that the locus of high rock uplift rates is coincident with the rugged range core, in a similar position as high temperature and pressure lithologies, but not in the low lying foothills as has been previously suggested by low-temperature thermochronometry. The details of our analysis suggest the dominant topographic signal in the Olympic Mountains is a spatial, and likely temporal, variation in erosional efficiency dictated by orographic precipitation, and Pleistocene glacier ELA patterns. We demonstrate the same topographic effects are recorded in the basin hypsometries of other Cenozoic mountain ranges around the world. The significant glacial overprint on topography makes the argument of mountain range steadiness untenable in significantly glaciated settings. Furthermore, our results suggest that most glaciated Cenozoic ranges are likely still in a mode of readjustment as fluvial systems change topography and erosion rates to equilibrate with rock uplift rates.

  4. Mineral chemistry of Pangidi basalt flows from Andhra Pradesh

    NASA Astrophysics Data System (ADS)

    Nageswara Rao, P. V.; Swaroop, P. C.; Karimulla, Syed

    2012-04-01

    This paper elucidates the compositional studies on clinopyroxene, plagioclase, titaniferous magnetite and ilmenite of basalts of Pangidi area to understand the geothermometry and oxybarometry conditions. Petrographic evidence and anorthite content (up to 85%) of plagioclase and temperature estimates of clinopyroxene indicate that the clinopyroxene is crystallized later than or together with plagioclase. The higher An content indicates that the parent magma is tholeiitic composition. The equilibration temperatures of clinopyroxene (1110-1190°C) and titaniferous magnetite and ilmenite coexisting mineral phases (1063-1103°C) are almost similar in lower basalt flow and it is higher for clinopyroxene (900-1110°C) when compared to titaniferous magnetite and ilmenite coexisting mineral phases (748-898°C) in middle and upper basalt flows. From this it can be inferred that the clinopyroxene is crystallized earlier than Fe-Ti oxide phases reequilibration, which indicates that the clinopyroxene temperature is the approximate eruption temperature of the present lava flows. The wide range of temperatures (900-1190°C) attained by clinopyroxene may point out that the equilibration of clinopyroxene crystals initiated from depth till closer to the surface before the melt erupted. Pangidi basalts follow the QFM buffer curve which indicates the more evolved tholeiitic composition. This suggests the parent tholeiitic magma suffered limited fractionation at high temperature under increasing oxygen fugacity in lower basalt flow and more fractionation at medium to lower temperatures under decreasing oxygen fugacity conditions during cooling of middle and upper basalt flows. The variation of oxygen fugacity indicates the oxidizing conditions for lower basalt flow (9.48-10.3) and extremely reducing conditions for middle (12.1-15.5) and upper basalt (12.4-15.54) flows prevailed at the time of cooling. Temperature vs. (FeO+Fe2O3)/(FeO+Fe2O3 +MgO) data plots for present basalts suggested the lower basaltic flow is formed at higher temperatures while the middle and upper basalt flows at medium to lower temperatures. The lower basalt flow is represented by higher temperatures which shows high modal values of opaques and glass whereas the medium to lower temperatures of middle and upper flow are caused by vesicular nature which contain larger content of gases and humid to semi-arid conditions during cooling.

  5. Carbide-metal assemblages in a sample returned from asteroid 25143 Itokawa: Evidence for methane-rich fluids during metamorphism

    NASA Astrophysics Data System (ADS)

    Harries, Dennis; Langenhorst, Falko

    2018-02-01

    We found that the particle RA-QD02-0115 returned by the Hayabusa spacecraft from near-Earth asteroid 25143 Itokawa contains the iron carbide haxonite (Fe21.9-22.7Co0.2-0.3Ni0.2-0.8)C6 and several Fe,Ni alloys, including multi-domain tetrataenite and spinodally decomposed taenite. Ellipsoidal to nearly spherical voids occur throughout the particle and suggest the presence of a fluid phase during textural and chemical equilibration of the host rock within the parent asteroid of 25143 Itokawa. The calculated solubility of carbon in Fe,Ni metal indicates that the carbide formed at temperatures larger than 600 °C during thermal metamorphism of the LL-chondritic mineral assemblage. Haxonite formed metastably with respect to graphite and cohenite, probably due to its high degree of lattice match with neighboring taenite, a low cooling rate at peak metamorphic temperatures, and the hindered nucleation of graphite. Thermodynamic equilibrium calculations indicate that the fluid present was dry (H2O-poor) and dominated by methane. The reactive fluid most plausibly had an atomic H/C ratio of 4-5 and was derived from the reduction of macromolecular, insoluble organic matter (IOM) that initially co-accreted with water ice. The initial presence of water is a necessary assumption to provide sufficient hydrogen for the formation of methane from hydrolyzed IOM. Metallic iron was in turn partially oxidized and incorporated into the ferromagnesian silicates during the high-temperature stage of metamorphism. An exemplary bulk reaction from unequilibrated material on the left to an equilibrated assemblage on the right may be written as: 330 CH0.8O0.2(IOM) + 500 H2O(ice/g) + 681 Fe(in alloy) + 566 FeSiO3(in Opx) → 300 CH4(g) + 32 H2(g) + 5 Fe23C6(in Hx) + 566 Fe2SiO4(in Ol) (Opx = orthopyroxene, Hx = haxonite, Ol = olivine, g = fluid species). The best estimate of the fluid/rock ratio in the region of the LL parent body where RA-QD02-0115 formed is about 3 × 10-3 and corresponds to an initial ice/rock ratio of about 7 × 10-3 (both by mass).

  6. Heat transfer from Atlantic waters to sea ice in the Arctic Ocean: Evidence from dissolved argon

    NASA Astrophysics Data System (ADS)

    Moore, R. M.; Spitzer, W.

    1990-11-01

    In an attempt to determine whether the temperature and salinity properties of Arctic Ocean waters above the Atlantic water temperature maximum are the result of heat transfer to sea-ice, dissolved Ar has been measured as a temperature tracer. Consistent with such a hypothesis, it is found that there is a transition from supersaturation of Ar in the upper waters to undersaturation below a depth of 275m. Using the known dependence of the solubility of Ar on T and S, and assuming that the water was originally equilibrated with the atmosphere at 760mm Hg, it has been calculated that ca. 0.6° C of cooling can be attributed to transfer of heat to sea-ice.

  7. Note: A dual temperature closed loop batch reactor for determining the partitioning of trace gases within CO2-water systems.

    PubMed

    Warr, Oliver; Rochelle, Christopher A; Masters, Andrew J; Ballentine, Christopher J

    2016-01-01

    An experimental approach is presented which can be used to determine partitioning of trace gases within CO2-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magnetic stirrer and high-pressure liquid chromatography pump, respectively.

  8. Characterizing the Chemical Stability of High Temperature Materials for Application in Extreme Environments

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth

    2005-01-01

    The chemical stability of high temperature materials must be known for use in the extreme environments of combustion applications. The characterization techniques available at NASA Glenn Research Center vary from fundamental thermodynamic property determination to material durability testing in actual engine environments. In this paper some of the unique techniques and facilities available at NASA Glenn will be reviewed. Multiple cell Knudsen effusion mass spectrometry is used to determine thermodynamic data by sampling gas species formed by reaction or equilibration in a Knudsen cell held in a vacuum. The transpiration technique can also be used to determine thermodynamic data of volatile species but at atmospheric pressures. Thermodynamic data in the Si-O-H(g) system were determined with this technique. Free Jet Sampling Mass Spectrometry can be used to study gas-solid interactions at a pressure of one atmosphere. Volatile Si(OH)4(g) was identified by this mass spectrometry technique. A High Pressure Burner Rig is used to expose high temperature materials in hydrocarbon-fueled combustion environments. Silicon carbide (SiC) volatility rates were measured in the burner rig as a function of total pressure, gas velocity and temperature. Finally, the Research Combustion Lab Rocket Test Cell is used to expose high temperature materials in hydrogen/oxygen rocket engine environments to assess material durability. SiC recession due to rocket engine exposures was measured as a function of oxidant/fuel ratio, temperature, and total pressure. The emphasis of the discussion for all techniques will be placed on experimental factors that must be controlled for accurate acquisition of results and reliable prediction of high temperature material chemical stability.

  9. Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

    USGS Publications Warehouse

    Stoffregen, R.E.; Rye, R.O.; Wasserman, M.D.

    1994-01-01

    Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400??C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from -6.25 moles alkali m-2s-1 at 400??C to - 11.7 moles alkali m-2s-1 at 200??C. The variation in these rates with temperature is given by the equation log k* = -8.17(1000/T(K)) + 5.54 (r2 = 0.987) which yields an activation energy of 37.4 ?? 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ?? 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100??C. Computed hydrogen diffusion coefficients range from -15.7 to -17.3 cm2s-1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause alteration of their radiometric ages. Furthermore, the rapid rate of hydrogen diffusion observed at 100-150??C suggests that fine-grained alunites are susceptible to rapid D-H re-equilibration even at surficial conditions. ?? 1994.

  10. Multicomponent Diffusion in Experimentally Cooled Melt Inclusions

    NASA Astrophysics Data System (ADS)

    Saper, L.; Stolper, E.

    2017-12-01

    Glassy olivine-hosted melt inclusions are compositionally zoned, characterized by a boundary layer depleted in olivine-compatible components that extends into the melt inclusion from its wall. The boundary layer forms in response to crystallization of olivine and relaxes with time due to diffusive exchange with the interior of the inclusion. At magmatic temperatures, the time scale for homogenization of inclusions is minutes to hours. Preservation of compositional gradients in natural inclusions results from rapid cooling upon eruption. A model of MgO concentration profiles that couples crystal growth and diffusive relaxation of a boundary layer can be used to solve for eruptive cooling rates [1]. Controlled cooling-rate experiments were conducted to test the accuracy of the model. Mauna Loa olivine containing >80 µm melt inclusions were equilibrated at 1225°C in a 1-atm furnace for 24 hours, followed by linear cooling at rates of 102 - 105 °C/hr. High-resolution concentration profiles of 40 inclusions were obtained using an electron microprobe. The model of [1] fits the experimental data with low residuals and the best-fit cooling rates are within 30% of experimental values. The initial temperature of 1225 °C is underestimated by 65°C. The model was modified using (i) MELTS to calculate the interface melt composition as a function of temperature, and (ii) a concentration-dependent MgO diffusion coefficient using the functional form of [2]. With this calibration the best-fit starting temperatures are within 5°C of the experimental values and the best-fit cooling rates are within 20% of experimental rates. The evolution of the CaO profile during cooling is evidence for strong diffusive coupling between melt components. Because CaO is incompatible in olivine, CaO concentrations are expected to be elevated in the boundary layer adjacent to the growing olivine. Although this is observed at short time scales, as the profile evolves the CaO concentration near the crystal interface becomes increasingly depleted. The drawdown in CaO can be explained by non-ideal mixing that leads to increases in the CaO activity coefficient in the melt. A regular solution model [3] can be used to describe the evolution of the CaO profiles. [1]Newcombe et al (2014) CMP 168 [2] Zhang (2010) RevMineralGeochem 72 [3] Ghiorso & Sack (1995) CMP 119

  11. Characterization of air temperature in modern ion chambers due to phantom geometry and ambient temperature changes.

    PubMed

    Saenz, Daniel L; Kirby, Neil; Gutiérrez, Alonso N

    2016-07-01

    Temperature and pressure corrections are necessary to account for the varying mass of air in the sensitive volume of a vented ionization chamber (IC) when performing absolute dose measurements. Locations commonly used to measure the presumed IC air temperature may not accurately represent the chamber cavity air temperature, and phantoms undergoing temperature changes further compound the problem. Prior studies have characterized thermal equilibrium in separate phantoms for Farmer chambers alone. However, the purpose of this study was to characterize the cavity air temperature dependence on changes in the ambient temperature and phantom geometry configuration for a wider and more modern variety of chambers to determine if previously published wait times apply to these chambers as well. Thermal conduction properties were experimentally investigated by modifying a PTW 0.3 cm(3) Semiflex IC with a thermocouple replacing the central electrode. Air cavity temperature versus time was recorded in three phantom geometries characteristic of common absolute dose measurements. The phantoms were (15 ± 1) °C before measurement with an IC at the treatment vault temperature of (21 ± 1) °C. Simulations were conducted to provide a theoretical basis for the measurements and to simulate temperature response of a PTW PinPoint® and Farmer chamber. The simulation methods were first validated by comparison with measured Semiflex chamber thermal response curves before extension to the other chambers. Two thermal equilibria curves were recorded on different time scales. IC temperature initially dropped to the colder phantom temperature but subsequently increased as the phantom itself equilibrated with the warmer room temperature. In a large phantom of dimensions (25.5 × 25.5 × 23.4) cm(3), 3 min was required before the IC temperature reached within 0.5 °C of its equilibrium within the phantom. Similarly, wait times of 2 min were needed for 7.5 and 2 cm slab phantoms. Recording of temperature in the phantom was deemed far more accurate than measurement in ambient air due to the air cavity thermally equilibrating with phantom temperature instead of the vented ambient air. Wait times of 3 and 2 min are needed for a cube and 7.5 cm slab phantom, respectively, to achieve 0.2% dosimetric accuracy (temperature accuracy of 0.5 °C). Chamber volume alone did not determine wait times, as a 0.3 cm(3) IC required a longer wait time than a Farmer chamber, suggesting wall thickness as an important variable as well.

  12. The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Beckett, J. R.; Stolper, E.

    1994-01-01

    Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

  13. Igneous fractionation and subsolidus equilibration of diogenite meteorites

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.

    1993-01-01

    Diogenites are coarse-grained orthopyroxenite breccias of remarkably uniform major element composition. Most diogenites contain homogeneous pyroxene fragments up to 5 cm across of Wo2En74Fs24 composition. Common minor constituents are chromite, olivine, trolite and metal, while silica, plagioclase, merrillite and diopside are trace phases. Diogenites are generally believed to be cumulates from the eucrite parent body, although their relationship with eucrites remains obscure. It has been suggested that some diogenites are residues after partial melting. I have performed EMPA and INAA for major, minor and trace elements on most diogenites, concentrating on coarse-grained mineral and lithic clasts in order to elucidate their igneous formation and subsequent metamorphic history. Major element compositions of diogenites are decoupled from minor and trace element compositions; the latter record an igneous fractionation sequence that is not preserved in the former. Low equilibration temperatures indicate that major element diffusion continued long after crystallization. Diffusion coefficients for trivalent and tetravalent elements in pyroxene are lower than those of divalent elements. Therefore, major element compositions of diogenites may represent means of unknown portions of a cumulate homogenized by diffusion, while minor and trace elements still yield information on their igneous history. The scale of major element equilibration is unknown, but is likely to be on the order of a few cm. Therefore, the diogenite precursors may have consisted largely of cm-sized, igneously zoned orthopyroxene grains, which were subsequently annealed during slow cooling, obliterating major element zoning but preserving minor and trace incompatible element zoning.

  14. Universality in the Equilibration of Quenched Yukawa One Component Plasmas

    NASA Astrophysics Data System (ADS)

    Langin, Thomas; McQuillen, Patrick; Strickler, Trevor; Maksimovic, Nikola; Pohl, Thomas; Killian, Thomas

    2015-11-01

    We study the equilibration of a Yukawa One Component Plasma (OCP) after a rapid change in the screening parameter from κ0 = ∞ to κf (n ,Te) , which is realized by photoionizing a laser cooled (T ~ 10 mK), uncorrelated gas of 88Sr atoms with density n between 1014 m-3 and 3 ×1016 m-3 using a two photon process in which the energy of one of the photons is adjustable. The excess photon energy above the ionization threshold sets the electron temperature, Te, and thus gives us control of κf. The resultant plasma is a classical plasma with strongly coupled ions, and is therefore described by the Yukawa OCP model with the electrons treated as a screening background. After photoionization, the ions develop spatial correlations to minimize their interaction energy, thus heating the ions. Since the dynamics of a Yukawa OCP depend solely on κ, we expect the heating process to be uniquely determined by κf. We verify this behavior by measuring the ion heating curve and comparing it to molecular dynamics simulations. We also report on how this behavior can be used to accurately measure n given a measured equilibration curve at a known Te. This work was supported by the United States National Science Foundation and the Department of Energy (PHY-0714603), the Air Force Office of Scientific Research (FA9550- 12-1-0267), and the Department of Defense (DoD) through the NDSEG Program.

  15. Conversion of para and ortho hydrogen in the Jovian planets

    NASA Technical Reports Server (NTRS)

    Massie, S. T.; Hunten, D. M.

    1982-01-01

    A mechanism is proposed which partially equilibrates the para and ortho rotational levels of molecular hydrogen in the atmospheres of Jupiter, Saturn, and Uranus. Catalytic reactions between the free-radical surface sites of aerosol particles and hydrogen modecules yield significant equilibration near 1 bar pressure, if the efficiency of conversion per collision is between 10 to the -8th and 10 to the -10th and the effective eddy mixing coefficient is 10,000 sq cm/sec. At lower pressures the ortho-para ratio retains the value at the top of the cloud layer, except for a very small effect from conversion in the thermosphere. The influence of conversion on the specific heat and adiabatic lapse rate is also investigated. The effect is found to be generally small, though is can rise to 10% inside the aerosol layer.

  16. Simulation study on the structural properties of colloidal particles with offset dipoles.

    PubMed

    Rutkowski, David M; Velev, Orlin D; Klapp, Sabine H L; Hall, Carol K

    2017-05-03

    A major research theme in materials science is determining how the self-assembly of new generations of colloidal particles of complex shape and surface charge is guided by their interparticle interactions. In this paper, we describe results from quasi-2D Monte Carlo simulations of systems of colloidal particles with offset transversely-oriented extended dipole-like charge distributions interacting via an intermediate-ranged Yukawa potential. The systems are cooled slowly through an annealing procedure during which the temperature is lowered in discrete steps, allowing the system to equilibrate. We perform ground state calculations for two, three and four particles at several shifts of the dipole vector from the particle center. We create state diagrams in the plane spanned by the temperature and the area fraction outlining the boundaries between fluid, string-fluid and percolated states at various values of the shift. Remarkably we find that the effective cooling rate in our simulations has an impact on the structures formed, with chains being more prevalent if the system is cooled quickly and cyclic structures more prevalent if the system is cooled slowly. As the dipole is further shifted from the center, there is an increased tendency to assemble into small cyclic structures at intermediate temperatures. These systems further self-assemble into open lattice-like arrangements at very low temperatures. The novel structures identified might be useful for photonic applications, new types of porous media for filtration and catalysis, and gel matrices with unusual properties.

  17. Temperature change rate actuated bubble mixing for homogeneous rehydration of dry pre-stored reagents in centrifugal microfluidics.

    PubMed

    Hin, S; Paust, N; Keller, M; Rombach, M; Strohmeier, O; Zengerle, R; Mitsakakis, K

    2018-01-16

    In centrifugal microfluidics, dead volumes in valves downstream of mixing chambers can hardly be avoided. These dead volumes are excluded from mixing processes and hence cause a concentration gradient. Here we present a new bubble mixing concept which avoids such dead volumes. The mixing concept employs heating to create a temperature change rate (TCR) induced overpressure in the air volume downstream of mixing chambers. The main feature is an air vent with a high fluidic resistance, representing a low pass filter with respect to pressure changes. Fast temperature increase causes rapid pressure increase in downstream structures pushing the liquid from downstream channels into the mixing chamber. As air further penetrates into the mixing chamber, bubbles form, ascend due to buoyancy and mix the liquid. Slow temperature/pressure changes equilibrate through the high fluidic resistance air vent enabling sequential heating/cooling cycles to repeat the mixing process. After mixing, a complete transfer of the reaction volume into the downstream fluidic structure is possible by a rapid cooling step triggering TCR actuated valving. The new mixing concept is applied to rehydrate reagents for loop-mediated isothermal amplification (LAMP). After mixing, the reaction mix is aliquoted into several reaction chambers for geometric multiplexing. As a measure for mixing efficiency, the mean coefficient of variation (C[combining macron]V[combining macron], n = 4 LabDisks) of the time to positivity (t p ) of the LAMP reactions (n = 11 replicates per LabDisk) is taken. The C[combining macron]V[combining macron] of the t p is reduced from 18.5% (when using standard shake mode mixing) to 3.3% (when applying TCR actuated bubble mixing). The bubble mixer has been implemented in a monolithic fashion without the need for any additional actuation besides rotation and temperature control, which are needed anyhow for the assay workflow.

  18. Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

    NASA Astrophysics Data System (ADS)

    Morozov, Mikhail; Brinkmann, Christian; Grodzicki, Michael; Lottermoser, Werner; Tippelt, Gerold; Amthauer, Georg; Kroll, Herbert

    2005-11-01

    The high-temperature partitioning of Fe2+ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa50) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe2+ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].

  19. Effect of shortening the prefreezing equilibration time with glycerol on the quality of chamois (Rupicapra pyrenaica), ibex (Capra pyrenaica), mouflon (Ovis musimon) and aoudad (Ammotragus lervia) ejaculates.

    PubMed

    Pradiee, J; O'Brien, E; Esteso, M C; Castaño, C; Toledano-Díaz, A; Lopez-Sebastián, A; Marcos-Beltrán, J L; Vega, R S; Guillamón, F G; Martínez-Nevado, E; Guerra, R; Santiago-Moreno, J

    2016-08-01

    The present study reports the effect of shortening the prefreezing equilibration time with glycerol on the quality of frozen-thawed ejaculated sperm from four Mediterranean mountain ungulates: Cantabrian chamois (Rupicapra pyrenaica), Iberian ibex (Capra pyrenaica), mouflon (Ovis musimon) and aoudad (Ammotragus lervia). Ejaculated sperm from these species were divided into two aliquots. One was diluted with either a Tris-citric acid-glucose based medium (TCG-glycerol; for chamois and ibex sperm) or a Tris-TES-glucose-based medium (TTG-glycerol; for mouflon and aoudad sperm), and maintained at 5°C for 3h prior to freezing. The other aliquot was diluted with either TCG (chamois and ibex sperm) or TTG (mouflon and aoudad sperm) and maintained at 5°C for 1h before adding glycerol (final concentration 5%). After a 15min equilibration period in the presence of glycerol, the samples were frozen. For the ibex, there was enhanced (P<0.05) sperm viability and acrosome integrity after the 3h as compared with the 15min equilibration time. For the chamois, subjective sperm motility and cell membrane functional integrity were less (P<0.05) following 15min of equilibration. In the mouflon, progressive sperm motility and acrosome integrity was less (P<0.05) when the equilibration time was reduced to 15min. For the aoudad, the majority of sperm variables measured were more desirable after the 3h equilibration time. The freezing-thawing processes reduced the sperm head size in all the species studied; however, the equilibration time further affected the frozen-thawed sperm head variables in a species-dependent fashion. While the equilibration time for chamois sperm might be shortened, this appears not to be the case for all ungulates. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Water in orthopyroxene from abyssal spinel peridotites of the East Pacific Rise (ODP Leg 147: Hess Deep)

    NASA Astrophysics Data System (ADS)

    Hesse, Kirsten T.; Gose, Jürgen; Stalder, Roland; Schmädicke, Esther

    2015-09-01

    Abyssal spinel peridotites from Hess Deep, East Pacific Rise (ODP Leg 147) were investigated concerning their major, minor, and trace element mineral chemistry and the incorporation of structural water in orthopyroxene. The rocks are partially serpentinized harzburgites containing primary minerals of olivine, orthopyroxene, clinopyroxene, and spinel. Orthopyroxene is enstatitic with Mg# (Mg/(Mg + Fe)) between 0.90 and 0.92 and Al2O3 from 0.5 to 2.9 wt.%. The residual harzburgite experienced high degrees of melt removal in the spinel peridotite stability field. The average degree of partial melting was calculated to be 17.5% (range: 16.4-17.8%). Trace element data of ortho- and clinopyroxenes reflect this strong depletion, characteristic for the restitic nature of abyssal peridotites. Mantle re-equilibration temperatures around 1000 °C indicate that, after melt extraction and before exhumation to the ocean floor, the rocks experienced significant cooling in the spinel peridotite facies. Water contents of orthopyroxene range from 86 to 233 wt. ppm H2O with an average concentration of 142 wt. ppm H2O. These results represent the first data on water contents in the sub-pacific mantle obtained by direct measurements of sub-oceanic peridotite. The water contents are not related to mineral chemistry, stratigraphy, melting degree, mantle equilibrium conditions or oxidation state. Calculated post-melt peridotite water contents vary between 40 and 100 wt. ppm H2O. Compared to Mid-Atlantic Ridge peridotites, the East Pacific Rise samples of Leg 147 contain somewhat lower water concentrations than samples from Leg 153 and considerably higher contents than those of Leg 209 (Gose et al., 2009; Schmädicke et al., 2011). In Leg 147, the strongest OH absorbtion band occurs at 3420 cm- 1, wheras orthopyroxene from MAR peridotite (Legs 153 and 209) has its strongest absorbtion band at 3566 and 3522 cm- 1. The mantle equilibrium temperature of Leg 147 peridotites is lower than that of Leg 209 ( 1250 °C) but close to that of Leg 153 samples (950-1000 °C). The high degree of partial melting of Leg 147 peridotite samples overlaps with the Leg 209 samples. In accordance to this data we conclude that in order to obtain relatively high water contents of up to 233 wt. ppm in depleted peridotite, after melt removal water must have re-entered the orthopyroxene structure. We suggest that re-equilibration of water contents took place under spinel-facies conditions before exhumation of the tectonite, since elevated temperatures enhance diffusion and elevated pressures facilitate hydrogen uptake. The extended time span between melt removal and uplift inferred from significant isobaric cooling of at least 200 K at spinel-facies depth facilitates re-equilibration of water contents and may explain the high concentrations. Exhumation from spinel-facies depth was fast and accompanied by further cooling such that re-equilibration to lower pressure assemblages and decompression-induced water loss were prevented.

  1. Electron transfer between cytochrome. alpha. and copper A in cytochrome c oxidase: A perturbed equilibrium study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Morgan, J.E.; Li, P.M.; Jang, D.J.

    1989-08-22

    Intramolecular electron transfer in partially reduced cytochrome c oxidase has been studied by the perturbed equilibrium method. The authors have prepared a three-electron-reduced, CO-inhibited form of the enzyme in which cytochrome a and copper A are partially reduced and in an intramolecular redox equilibrium. When these samples were irradiated with a nitrogen laser to photodissociate the bound CO, changes in absorbance at 598 and 830 nm were observed which were consistent with a fast electron transfer from cytochrome a to copper A. The absorbance changes at 598 nm gave an apparent rate of 17,000 {plus minus} 2,000 s{sup {minus}1} (1more » {sigma}), at pH 7.0 and 25.5{degree}C. These changes were not observed in either the CO mixed-valence or the CO-inhibited fully reduced forms of the enzyme. The rate was fastest at about pH 8.0, falling off toward both lower and higher pHs. There was a small but clear temperature dependence. The process was also observed in the cytochrome c-cytochrome c oxidase high-affinity complex. The electron equilibration measured between cytochrome {alpha} and copper A is far faster than any rate measured or inferred previously for this process.« less

  2. Factors influencing detection of eDNA from a stream-dwelling amphibian

    USGS Publications Warehouse

    Pilliod, David S.; Goldberg, Caren S.; Arkle, Robert S.; Waits, Lisette P.

    2013-01-01

    Environmental DNA (eDNA) methods for detecting and estimating abundance of aquatic species are emerging rapidly, but little is known about how processes such as secretion rate, environmental degradation, and time since colonization or extirpation from a given site affect eDNA measurements. Using stream-dwelling salamanders and quantitative PCR (qPCR) analysis, we conducted three experiments to assess eDNA: (i) production rate; (ii) persistence time under different temperature and light conditions; and (iii) detectability and concentration through time following experimental introduction and removal of salamanders into previously unoccupied streams. We found that 44–50 g individuals held in aquaria produced 77 ng eDNA/h for 2 h, after which production either slowed considerably or began to equilibrate with degradation. eDNA in both full-sun and shaded treatments degraded exponentially to 2) and when samples were collected within 5 m of the animals. Concentrations of eDNA detected were very low and increased steadily from 6–24 h after introduction, reaching 0.0022 ng/L. Within 1 h of removing salamanders from the stream, eDNA was no longer detectable. These results suggest that eDNA detectability and concentration depend on production rates of individuals, environmental conditions, density of animals, and their residence time.

  3. Kinetics of bacterial potentiometric titrations: the effect of equilibration time on buffering capacity of Pantoea agglomerans suspensions.

    PubMed

    Kapetas, Leon; Ngwenya, Bryne T; Macdonald, Alan M; Elphick, Stephen C

    2011-07-15

    Several recent studies have made use of continuous acid-base titration data to describe the surface chemistry of bacterial cells as a basis for accurately modelling metal adsorption to bacteria and other biomaterials of potential industrial importance. These studies do not share a common protocol; rather they titrate in different pH ranges and they use different stability criteria to define equilibration time during titration. In the present study we investigate the kinetics of bacterial titrations and test the effect they have on the derivation of functional group concentrations and acidity constants. We titrated suspensions of Pantoea agglomerans by varying the equilibration time between successive titrant additions until stability of 0.1 or 0.001 mV s(-1) was attained. We show that under longer equilibration times, titration results are less reproducible and suspensions exhibit marginally higher buffering. Fluorescence images suggest that cell lysis is not responsible for these effects. Rather, high DOC values and titration reversibility hysterisis after long equilibration times suggest that variability in buffering is due to the presence of bacterial exudates, as demonstrated by titrating supernatants separated from suspensions of different equilibration times. It is recommended that an optimal equilibration time is always determined with variable stability control and preliminary reversibility titration experiments. Copyright © 2011 Elsevier Inc. All rights reserved.

  4. High-throughput analysis of bergamot essential oil by fast solid-phase microextraction-capillary gas chromatography-flame ionization detection.

    PubMed

    Tranchida, Peter Quinto; Presti, Maria Lo; Costa, Rosaria; Dugo, Paola; Dugo, Giovanni; Mondello, Luigi

    2006-01-20

    The advantages of using a narrow-bore column in headspace solid-phase microextraction-gas chromatographic (HS-SPME-GC) analysis are investigated. An automated rapid HS-SPME-GC method for the determination of volatile compounds in a complex sample (bergamot essential oil) was developed. A low-capacity (7 microm) SPME fibre was employed, enabling a short equilibration time (15 min). The absorbed volatile compounds were then separated in 12.5 min on a 10 m x 0.1 mm I.D. capillary. The fast GC method was characterized by relatively moderate GC parameters (head pressure: 173 kPa; temperature program rate: 12 degrees C/min). The employment of the low-capacity fibre also suited the reduced sample capacity of the capillary employed, hence column overloading was avoided. Analytical repeatibility was determined in terms of retention times (maximum RSD: 0.32%) and peak areas (maximum RSD: 9.80%). The results obtained were compared to those derived from a conventional HS-SPME-GC (a 30 microm SPME fibre and 0.25 mm I.D. capillary were used) application on the same sample. In this respect, a great reduction of analytical time was obtained both with regard to the conventional SPME equilibration and GC run times, which both required 50 min. Peak resolution was altogether comparable in both applications. Although a slight loss in terms of sensitivity was observed in the rapid approach (generally within the 25-50% range), this did not impair the detection of all peaks of interest. Finally, the selectivities of the 30 and 7 microm fibres were evaluated and, as expected, these were in good agreement.

  5. Effect of Galacto-Oligosaccharides: Maltodextrin Matrices on the Recovery of Lactobacillus plantarum after Spray-Drying

    PubMed Central

    Sosa, Natalia; Gerbino, Esteban; Golowczyc, Marina A.; Schebor, Carolina; Gómez-Zavaglia, Andrea; Tymczyszyn, E. Elizabeth

    2016-01-01

    In this work maltodextrins were added to commercial galacto-oligosaccharides (GOS) in a 1:1 ratio and their thermophysical characteristics were analyzed. GOS:MD solutions were then used as matrices during spray-drying of Lactobacillus plantarum CIDCA 83114. The obtained powders were equilibrated at different relative humidities (RH) and stored at 5 and 20°C for 12 weeks, or at 30°C for 6 weeks. The Tgs of GOS:MD matrices were about 20–30°C higher than those of GOS at RH within 11 and 52%. A linear relation between the spin-spin relaxation time (T2) and T-Tg parameter was observed for GOS:MD matrices equilibrated at 11, 22, 33, and 44% RH at 5, 20, and 30°C. Spray-drying of L. plantarum CIDCA 83114 in GOS:MD matrices allowed the recovery of 93% microorganisms. In contrast, only 64% microorganisms were recovered when no GOS were included in the dehydration medium. Survival of L. plantarum CIDCA 83114 during storage showed the best performance for bacteria stored at 5°C. In a further step, the slopes of the linear regressions provided information about the rate of microbial inactivation for each storage condition (k values). This information can be useful to calculate the shelf-life of spray-dried starters stored at different temperatures and RH. Using GOS:MD matrices as a dehydration medium enhanced the recovery of L. plantarum CIDCA 83114 after spray-drying. This strategy allowed for the first time the spray-drying stabilization of a potentially probiotic strain in the presence of GOS. PMID:27199918

  6. Structural Characterization of Vapor-deposited Organic Glasses

    NASA Astrophysics Data System (ADS)

    Gujral, Ankit

    Physical vapor deposition, a common route of thin film fabrication for organic electronic devices, has recently been shown to produce organic glassy films with enhanced kinetic stability and anisotropic structure. Anisotropic structures are of interest in the organic electronics community as it has been shown that certain structures lead to enhanced device performance, such as higher carrier mobility and better light outcoupling. A mechanism proposed to explain the origin of the stability and anisotropy of vapor-deposited glasses relies on two parameters: 1) enhanced molecular mobility at the free surface (vacuum interface) of a glass, and 2) anisotropic molecular packing at the free surface of the supercooled liquid of the glass-forming system. By vapor-depositing onto a substrate maintained at Tsubstrate < Tg (where Tg is the glass transition temperature), the enhanced molecular mobility at the free surface allows every molecule that lands on the surface to at least partially equilibrate to the preferred anisotropic molecular packing motifs before being buried by further deposition. The extent of equilibration depends on the mobility at the surface, controlled by Tsubstrate, and the residence time on the free surface, controlled by the rate of deposition. This body of work deals with the optimization of deposition conditions and system chemistry to prepare and characterize films with functional anisotropic structures. Here, we show that structural anisotropy can be attained for a variety of molecular systems including a rod-shaped non-mesogen, TPD, a rod-shaped smectic mesogen, itraconazole, two discotic mesogens, phenanthroperylene-ester and triphenylene-ester, and a disc-shaped non-mesogen, m-MTDATA. Experimental evidence is also provided of the anisotropic molecular packing at the free surface (vacuum interface) for the disc-shaped systems that are consistent with the expectations of the proposed mechanism and the final bulk state of the vapor-deposited glasses.

  7. Slow Organic-to-Inorganic Sub-Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chang, Angela Y.; Cho, Yi-Ju; Chen, Kuan-Chen

    2016-05-31

    Carrier dynamics in methylammonium lead halide (CH3NH3PbI3-xClx) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long-lived (> nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%-60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band-edge photoluminescence (PL) decay only appears for excitation >= 2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon-energy excitationmore » yields slow dynamics consistent with negligible carrier trapping. Further, sub-bandgap two-photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub-lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic-to-inorganic sub-lattice equilibration timescale at optoelectronic-relevant excitation energies.« less

  8. Isotopic and chemical composition of parbati valley geothermal discharges, North-West Himalaya, India

    USGS Publications Warehouse

    Giggenbach, W.F.; Gonfiantini, R.; Jangi, B.L.; Truesdell, A.H.

    1983-01-01

    The isotopic compositions of the waters discharged from Parbati Valley geothermal areas indicate a higher altitude meteoric origin, with discharge temperatures reflecting variations in the depth of penetration of the waters to levels heated by the existence of a 'normal' geothermal gradient. On the basis of mixing models involving silica, tritium, discharge temperatures and chloride contents, deep equilibration temperatures of 120-140??C were obtained for Manikaran, possibly reaching 160??C at even greater depth. Geothermometers based on sulfate-water 18O exchange and gas reactions point to similar temperatures. Exceptionally high helium contents of the discharges correspond to apparent crustal residence times of the waters in the order of 10-100 Ma; relative nitrogen-argon contents support a largely meteoric origin of the waters with a possible fossil brine, but no detectable magmatic component. ?? 1983.

  9. Timing of pyroxenite formation in supra-subduction Josephine Ophiolite, Oregon.

    NASA Astrophysics Data System (ADS)

    Hough, T.; Le Roux, V.; Kurz, M. D.

    2017-12-01

    The Josephine ophiolite is a partly dismembered ophiolite located in southern Oregon and northwestern California (USA). It displays a large ( 640 km2) mantle section that is mostly composed of depleted spinel harzburgite and lherzolite re-equilibrated at temperatures of 900 °C. In addition, the peridotite section of the ophiolite contains minor dunites and pyroxenite veins ranging from orthopyroxenites to clinopyroxenites. Using field, petrological and geochemical data, previous studies have shown that the peridotite experienced 10-20% of hydrous flux melting. In addition, clinopyroxene and orthopyroxene in harzburgites show variable degrees of light rare-earth element (LREE) enrichment, which suggests percolation and re-equilibration with small fractions of boninite melt. Overall, the trace element concentrations of pyroxenes indicate that the harzburgites experienced particularly high degrees of melting in the mantle wedge. We collected a number of orthopyroxenite and clinopyroxenite veins in the mantle section of the Josephine Ophiolite. Here we present the major and rare-earth element (REE) contents of pyroxene in 4 orthopyroxenites and 2 clinopyroxenites and calculate the major element and REE closure temperatures for individual veins. We show that individual pyroxenites record drastic variations in their degree of REE depletion, indicating that multiple generations of melts percolated the peridotite. The pyroxenite veins also record higher REE closure temperatures (>1200 ºC) compared to the surrounding peridotite, potentially indicating rapid cooling after emplacement. REE closure temperatures are also higher than major element closure temperatures. In parallel, we analyzed Sr isotopes by MC-ICPMS in pyroxene separates from 4 veins. Results indicate that the maximum age of emplacement of orthopyroxenite veins corresponds to the age of exhumation. Some clinopyroxenites may have formed during earlier melt percolation events. This study supports the idea that the composition of melts that percolate the mantle wedge can be highly variable and that orthopyroxenites may be the last type of veins to form in those environments.

  10. Effectiveness of glucose-methanol extender for cryopreservation of Huso huso spermatozoa.

    PubMed

    Aramli, Mohammad Sadegh; Golshahi, Karim; Nazari, Rajab Mohammad; Aramli, Salim; Banan, Ashkan

    2015-11-01

    The present approach was designed to evaluate the methanol-glucose extender effects on sperm cryopreservation in beluga sturgeon, Huso huso. Sperm quality was examined by measuring post-thaw sperm motility and fertilizing rate at hatching stage. We first tested the effect of glucose concentration (0, 0.10, 0.15, 0.20 and 0.30M) in a methanol extender on post-thaw sperm motility. The optimal cryopreservation conditions were found to be 0.2M glucose in the extender. Then, motility and fertilization rates of sperm cryopreserved with 0.2M glucose and 10% methanol (GM) were compared to Tris-sucrose-KCl in 10% methanol extender (TSKM). Additionally, sperm motility and fertilizing ability in relation to 15 and 30min equilibration in GM extender before and after cryopreservation were measured. Higher post-thaw sperm motility duration and percentage as well as fertilization rate were obtained with the GM extender when compared to TSKM extender. Equilibration of sperm in extender did not affect the motility quality of either fresh-diluted or frozen/thawed sperm, while fertilization rate showed a significant decline alone after 30min of post-thaw storage. Our results indicated that the use of a simple extender consisting of 0.2M glucose in 10% methanol can be an alternative cryopreservation method to those previously described for sturgeons. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Experimental Determination of η/s for Finite Nuclear Matter.

    PubMed

    Mondal, Debasish; Pandit, Deepak; Mukhopadhyay, S; Pal, Surajit; Dey, Balaram; Bhattacharya, Srijit; De, A; Bhattacharya, Soumik; Bhattacharyya, S; Roy, Pratap; Banerjee, K; Banerjee, S R

    2017-05-12

    We present, for the first time, simultaneous determination of shear viscosity (η) and entropy density (s) and thus, η/s for equilibrated nuclear systems from A∼30 to A∼208 at different temperatures. At finite temperature, η is estimated by utilizing the γ decay of the isovector giant dipole resonance populated via fusion evaporation reaction, while s is evaluated from the nuclear level density parameter (a) and nuclear temperature (T), determined precisely by the simultaneous measurements of the evaporated neutron energy spectra and the compound nuclear angular momenta. The transport parameter η and the thermodynamic parameter s both increase with temperature, resulting in a mild decrease of η/s with temperature. The extracted η/s is also found to be independent of the neutron-proton asymmetry at a given temperature. Interestingly, the measured η/s values are comparable to that of the high-temperature quark-gluon plasma, pointing towards the fact that strong fluidity may be the universal feature of the strong interaction of many-body quantum systems.

  12. Heterogeneous photocatalytic oxidation of atmospheric trace contaminants

    NASA Technical Reports Server (NTRS)

    Ollis, David F.; Peral, Jose

    1991-01-01

    The following subject areas are covered: (1) design and construction of continuous flow photoreactor for study of oxidation of trace atmospheric contaminants; (2) establishment of kinetics of acetone oxidation including adsorption equilibration, variation of oxidation rate with acetone concentration and water (inhibitor), and variation of rate and apparent quantum yield with light intensity; (3) exploration of kinetics of butanol oxidation, including rate variation with concentration of butanol, and lack of inhibition by water; and (4) exploration of kinetics of catalyst deactivation during oxidation of butanol, including deactivation rate, influence of dark conditions, and establishment of photocatalytic regeneration of activity in alcohol-free air.

  13. Size Exclusion Chromatography Studies of the Initial Self-Association Steps of Chicken Egg White Lysozyme Nucleation

    NASA Technical Reports Server (NTRS)

    Ewing, Felecia; Donovan, David; Pusey, Marc

    2000-01-01

    Nucleation is one of the least understood aspects of crystallogenesis. In the case of macromolecule nucleation, this understanding is further hampered by uncertainty over what precisely is being discussed. We define the process of solute self-association (aggregation, oligomerization, interaction, clustering, etc.) whereby n-mers (n > or = 2) having a crystallographic or nascent crystallographic arrangement leading to the critical nucleus reversibly form in the solution, to be part of the nucleation process. This reversible self-association process is a fundamental part of the nucleation process, and occurs as a function of the solute concentration. In the case of chicken egg white lysozyme, a considerable body of experimental evidence leads us to the conclusion that it also forms the crystal growth units. Size exclusion chromatography is a simple and direct method for determining the equilibrium constants for the self-association process. A Pharmacia FPLC system was used to provide accurate solution flow rates. The column, injection valve, and sample loop were all mounted within a temperature-controlled chamber. Chromatographically re-purified lysozyme was first dialyzed against the column equilibration buffer, with injection onto the column after several hours pre-incubation at the running temperature. Preliminary experiments, were carried out using a Toyopearl HW-50F column (1 x 50cm), equilibrated with 0.1 M sodium acetate, 5% sodium chloride, pH 4.6, at 15C. Protein concentrations from 0.1 to 4 mg/ml were employed (C(sub sat) = 1.2 mg/ml). The data from several different protein preparations consistently shows a progressively decreasing elution volume with increasing protein concentration, indicating that reversible self-association is occurring. The dotted line indicates the monomeric lysozyme elution volume. However, lysozyme interacts with the column matrix in these experiments, which complicates data analysis.Accordingly, we are testing silica-based HPLC columns in an effort to eliminate this problem and substantially reduce the column volume and experimental run time. The results and data analysis from these and subsequent experiments will be presented.

  14. Diffusive Transport and Structural Properties of Liquid Iron Alloys at High Pressure

    NASA Astrophysics Data System (ADS)

    Posner, E.; Rubie, D. C.; Steinle-Neumann, G.; Frost, D. J.

    2017-12-01

    Diffusive transport properties of liquid iron alloys at high pressures (P) and temperatures (T) place important kinetic constraints on processes related to the origin and evolution of planetary cores. Earth's core composition is largely controlled by the extent of chemical equilibration achieved between liquid metal bodies and a silicate magma ocean during core formation, which can be estimated using chemical diffusion data. In order to estimate the time and length scales of metal-silicate chemical equilibration, we have measured chemical diffusion rates of Si, O and Cr in liquid iron over the P-T range of 1-18 GPa and 1873-2643 K using a multi-anvil apparatus. We have also performed first-principles molecular dynamic simulations of comparable binary liquid compositions, in addition to pure liquid Fe, over a much wider P-T range (1 bar-330 GPa, 2200-5500 K) in order to both validate the simulation results with experimental data at conditions accessible in the laboratory and to extend our dataset to conditions of the Earth's core. Over the entire P-T range studied using both methods, diffusion coefficients are described consistently and well using an exponential function of the homologous temperature relation. Si, Cr and Fe diffusivities of approximately 5 × 10-9 m2 s-1 are constant along the melting curve from ambient to core pressures, while oxygen diffusion is 2-3 times faster. Our results indicate that in order for the composition of the Earth's core to represent chemical equilibrium, impactor cores must have broken up into liquid droplet sizes no larger than a few tens of cm. Structural properties, analyzed using partial radial distribution functions from the molecular dynamics simulations, reveal a pressure-induced structural change in liquid Fe0.96O0.04 at densities of 8 g cm-3, in agreement with previous experimental studies. For densities above 8 g cm-3, the liquid is essentially close packed with a local CsCl-like (B2) packing of Fe around O under conditions of the Earth's core.

  15. What We Have Learned About the Existing Trace Element Partitioning data During the Population Phase of traceDs

    NASA Astrophysics Data System (ADS)

    Nielsen, R. L.; Ghiorso, M. S.; Trischman, T.

    2015-12-01

    The database traceDs is designed to provide a transparent and accessible resource of experimental partitioning data. It now includes ~ 90% of all the experimental trace element partitioning data (~4000 experiments) produced over the past 45 years, and is accessible through a web based interface (using the portal lepr.ofm-research.org). We set a minimum standard for inclusion, with the threshold criteria being the inclusion of: Experimental conditions (temperature, pressure, device, container, time, etc.) Major element composition of the phases Trace element analyses of the phases Data sources that did not report these minimum components were not included. The rationale for not including such data is that the degree of equilibration is unknown, and more important, no rigorous approach to modeling the behavior of trace elements is possible without knowledge of composition of the phases, and the temperature and pressure of formation/equilibration. The data are stored using a schema derived from that of the Library of Experimental Phase Relations (LEPR), modified to account for additional metadata, and restructured to permit multiple analytical entries for various element/technique/standard combinations. In the process of populating the database, we have learned a number of things about the existing published experimental partitioning data. Most important are: ~ 20% of the papers do not satisfy one or more of the threshold criteria. The standard format for presenting data is the average. This was developed as the standard during the time where there were space constraints for publication in spite of fact that all the information can now be published as electronic supplements. The uncertainties that are published with the compositional data are often not adequately explained (e.g. 1 or 2 sigma, standard deviation of the average, etc.). We propose a new set of publication standards for experimental data that include the minimum criteria described above, the publication of all analyses with error based on peak count rates and background, plus information on the structural state of the mineral (e.g. orthopyroxene vs. pigeonite).

  16. Effect of equilibration times, freezing, and thawing rates on post-thaw quality of buffalo (Bubalus bubalis) bull spermatozoa.

    PubMed

    Shah, S A H; Andrabi, S M H; Qureshi, I Z

    2016-09-01

    The effects of equilibration times (E1, 2 h; E2, 4 h; E3, 6 h), freezing rates (FR1, manual, 5 cm above liquid nitrogen (LN2 ) for 10 min, plunging in LN2 ; FR2, programmable ultra-fast, holding at +4 °C for 2 min, from 4 to -10 °C at -10 °C/min, from -10 to -20 °C at -15 °C/min, from -20 to -120 °C at -60 °C/min, holding at -120 °C for 30 sec, plunging in LN2 ), and thawing rates (T1, 37 °C for 30 sec; T2, 50 °C for 15 sec; T3, 70 °C for 7 sec) were evaluated on quality of buffalo bull spermatozoa. Progressive motility (%), rapid velocity (%), average path velocity (VAP, μm/s), straight line velocity (VSL, μm/s), and mitochondrial transmembrane potential (%) were higher (p < 0.05) with E2, FR2, and T3 compared to other groups. Sperm curved line velocity (VCL, μm/s) was higher (p < 0.05) with E2 and FR2 compared to other groups. Sperm straightness (%) and linearity (LIN, %) were higher (p < 0.05) with E2 compared to other groups. Sperm LIN was affected (p < 0.05) with T3 compared to other groups. Supravital-plasma membrane integrity (%), viability and acrosome integrity (%) of spermatozoa were higher (p < 0.05) with E2 and FR2 compared to other groups. Sperm DNA integrity (%) was higher (p < 0.05) with FR2 and T1 compared to other groups. We concluded that inclusion of 4 h-equilibration time, programmable ultra-fast freezing rate, and rapid thawing at 70 °C for 7 sec in cryopreservation protocol improves the post-thaw quality of buffalo bull spermatozoa. © 2016 American Society of Andrology and European Academy of Andrology.

  17. Development of Bicarbonate-Activated Peroxide as a Chemical and Biological Warfare Agent Decontaminant

    DTIC Science & Technology

    2006-06-30

    may operate for certain substrates. The reaction of equation 1 proceeds with the intermediacy of CO2 as shown in Figure 1. Although it is well...competition between paths 5 and 6 will depend on the conditions and the nature of the substrate S. Note that figures, equations , etc. in the...1 shows the complete reaction scheme used to model the equilibration reaction at low temperature. Table 1 Kinetic equations and their

  18. Design considerations of a thermally stabilized continuous flow electrophoresis chamber 2

    NASA Technical Reports Server (NTRS)

    Jandebeur, T. S.

    1982-01-01

    The basic adjustable parameters of a Beckman Continouous Particle Electrophoresis (CPE) Apparatus are investigated to determine the optimum conditions for ground based operation for comparison with space experiments. The possible application of electrically insulated copper/aluminum chamber walls is evaluated as a means to thermally stabilize or equilibrate lateral temperature gradients which exist on the walls of conventional plastic chambers and which distort the rectilinear base flow of buffer through the chamber, significantly affecting sample resolution.

  19. Does attenuated skin blood flow lower sweat rate and the critical environmental limit for heat balance during severe heat exposure?

    PubMed Central

    Cramer, Matthew N.; Gagnon, Daniel; Crandall, Craig G.; Jay, Ollie

    2016-01-01

    Attenuated skin blood flow (SkBF) is often assumed to impair core temperature (Tc) regulation. Profound pharmacologically-induced reductions in SkBF (~85%) lead to impaired sweating but whether the smaller attenuations in SkBF (~20%) more associated with ageing and certain diseases lead to decrements in sweating and maximum heat loss potential is unknown. Seven healthy males (28±4y) completed a 30-min equilibration period at 41°C and a vapour pressure (Pa) of 2.57 kPa followed by incremental steps in Pa of 0.17 kPa every 6-min to 5.95 kPa. Differences in heat loss potential were assessed by identifying the critical vapour pressure (Pcrit) at which an upward inflection in Tc occurred. Three separate treatments elicited changes in plasma volume to achieve three distinct levels of SkBF: control (CON), diuretic-induced iso-osmotic dehydration to lower SkBF (DEH), and continuous saline infusion to maintain SkBF (SAL). Tc, mean skin temperature (Tsk), heart rate, mean laser-Doppler flux (forearm, thigh; LDFmean), mean local sweat rate (forearm, thigh; LSRmean), and metabolic rate were measured. In DEH, a 14.2±5.7% lower plasma volume resulted in a ~20% lower LDFmean (DEH: 139±23, CON: 176±22, SAL: 186±22 PU; P=0.034). However, LSRmean and whole-body sweat losses were unaffected by treatment throughout (P>0.482). Pcrit for Tc was similar between treatments (CON: 5.05±0.30, DEH: 4.93±0.16, SAL: 5.12±0.10 kPa; P=0.166). Further, no differences were observed in the Tsk−Ta gradient, metabolic rate, or changes in Tc (P>0.197). In conclusion, a ~20% reduction in SkBF alters neither sweat rate nor the upper limit for heat loss from the skin during non-encapsulated passive heat stress. PMID:27859929

  20. Experimental Investigation of Gas/Slag/Matte/Spinel Equilibria in the Cu-Fe-O-S-Si System at 1473 K (1200 °C) and P(SO2) = 0.25 atm

    NASA Astrophysics Data System (ADS)

    Hidayat, Taufiq; Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

    2018-04-01

    New experimental data were obtained on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C) and P(SO2) = 0.25 atm covering Cu concentrations in matte between 42 and 78 wt pct Cu. Accurate measurements were obtained using high-temperature equilibration and the rapid quenching technique, followed by electron-probe X-ray microanalysis of equilibrium phase compositions. The use of spinel substrates made to support the samples ensures equilibrium with this primary phase solid, eliminates crucible contamination, and facilitates direct gas-condensed phase equilibrium and high quenching rates. Particular attention was given to the confirmation of the achievement of equilibrium. The results quantify the relationship between Cu in matte and oxygen partial pressure, sulfur in matte, oxygen in matte, Fe/SiO2 at slag liquidus, sulfur in slag, and dissolved copper in slag.

  1. Dialysate Flow Rate and Delivered Kt/Vurea for Dialyzers with Enhanced Dialysate Flow Distribution

    PubMed Central

    Idoux, John W.; Hamdan, Hiba; Ouseph, Rosemary; Depner, Thomas A.; Golper, Thomas A.

    2011-01-01

    Summary Background and objectives Previous in vitro and clinical studies showed that the urea mass transfer-area coefficient (KoA) increased with increasing dialysate flow rate. This observation led to increased dialysate flow rates in an attempt to maximize the delivered dose of dialysis (Kt/Vurea). Recently, we showed that urea KoA was independent of dialysate flow rate in the range 500 to 800 ml/min for dialyzers incorporating features to enhance dialysate flow distribution, suggesting that increasing the dialysate flow rate with such dialyzers would not significantly increase delivered Kt/Vurea. Design, setting, participants, & measurements We performed a multi-center randomized clinical trial to compare delivered Kt/Vurea at dialysate flow rates of 600 and 800 ml/min in 42 patients. All other aspects of the dialysis prescription, including treatment time, blood flow rate, and dialyzer, were kept constant for a given patient. Delivered single-pool and equilibrated Kt/Vurea were calculated from pre- and postdialysis plasma urea concentrations, and ionic Kt/V was determined from serial measurements of ionic dialysance made throughout each treatment. Results Delivered Kt/Vurea differed between centers; however, the difference in Kt/Vurea between dialysate flow rates of 800 and 600 ml/min was NS by any measure (95% confidence intervals of −0.064 to 0.024 for single-pool Kt/Vurea, −0.051 to 0.023 for equilibrated Kt/Vurea, and −0.029 to 0.099 for ionic Kt/V). Conclusions These data suggest that increasing the dialysate flow rate beyond 600 ml/min for these dialyzers offers no benefit in terms of delivered Kt/Vurea. PMID:21799145

  2. Emplacement, rapid burial, and exhumation of 90-Ma plutons in southeastern Alaska

    USGS Publications Warehouse

    Himmelberg, G.R.; Haeussler, Peter J.; Brew, D.A.

    2004-01-01

    In southeastern Alaska, granodiorite-tonalite plutons of the Admiralty-Revillagigedo belt intruded the Jurassic-Cretaceous Gravina belt along the eastern side of the Alexander terrane around 90 Ma. These plutons postdate some deformation related to a major contractional event between the previously amalgamated Wrangellia and Alexander terranes and the previously accreted terranes of the North American margin. We studied the aureole mineral assemblages of these plutons near Petersburg, Alaska, determined pressure and temperature of equilibration, and examined structures that developed within and adjacent to these plutons. Parallelism of magmatic and submagmatic fabrics with fabrics in the country rock indicates synchroneity of pluton emplacement with regional deformation and suggests that magma transport to higher crustal levels was assisted by regional deformation. Replacement of andalusite by kyanite or sillimanite indicates crustal thickening soon after pluton emplacement. Regional structural analysis indicates the crustal thickening was accomplished by thrust burial. Thermobarometric analyses indicate the aureoles reached near-peak temperatures of 525 to 635 ??C at pressures of 570 to 630 MPa. Consideration of the rate of thermal decay of the aureoles suggests that burial was rapid and occurred at rates around 5 to 8 mm/year. Structural observations indicate there was contractional deformation before, during, and after emplacement of the 90-Ma plutons. Initial exhumation of the Admiralty-Revillagedo belt in the Petersburg area may have occurred along a thrust west of the pluton belt within the Gravina belt. ?? 2004 NRC Canada.

  3. Dipolar Spin Ice States with a Fast Monopole Hopping Rate in CdEr2X4 (X =Se , S)

    NASA Astrophysics Data System (ADS)

    Gao, Shang; Zaharko, O.; Tsurkan, V.; Prodan, L.; Riordan, E.; Lago, J.; Fâk, B.; Wildes, A. R.; Koza, M. M.; Ritter, C.; Fouquet, P.; Keller, L.; Canévet, E.; Medarde, M.; Blomgren, J.; Johansson, C.; Giblin, S. R.; Vrtnik, S.; Luzar, J.; Loidl, A.; Rüegg, Ch.; Fennell, T.

    2018-03-01

    Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr2 Se4 is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy2 Ti2 O7 . In this Letter we use diffuse neutron scattering to show that both CdEr2 Se4 and CdEr2 S4 support a dipolar spin ice state—the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy2 Ti2 O7 , i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er3 + ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr2X4 (X =Se , S) are primarily due to much faster monopole hopping. Our work suggests that CdEr2X4 offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

  4. Theoretical and computer models of detonation in solid explosives

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tarver, C.M.; Urtiew, P.A.

    1997-10-01

    Recent experimental and theoretical advances in understanding energy transfer and chemical kinetics have led to improved models of detonation waves in solid explosives. The Nonequilibrium Zeldovich - von Neumann - Doring (NEZND) model is supported by picosecond laser experiments and molecular dynamics simulations of the multiphonon up-pumping and internal vibrational energy redistribution (IVR) processes by which the unreacted explosive molecules are excited to the transition state(s) preceding reaction behind the leading shock front(s). High temperature, high density transition state theory calculates the induction times measured by laser interferometric techniques. Exothermic chain reactions form product gases in highly excited vibrational states,more » which have been demonstrated to rapidly equilibrate via supercollisions. Embedded gauge and Fabry-Perot techniques measure the rates of reaction product expansion as thermal and chemical equilibrium is approached. Detonation reaction zone lengths in carbon-rich condensed phase explosives depend on the relatively slow formation of solid graphite or diamond. The Ignition and Growth reactive flow model based on pressure dependent reaction rates and Jones-Wilkins-Lee (JWL) equations of state has reproduced this nanosecond time resolved experimental data and thus has yielded accurate average reaction zone descriptions in one-, two- and three- dimensional hydrodynamic code calculations. The next generation reactive flow model requires improved equations of state and temperature dependent chemical kinetics. Such a model is being developed for the ALE3D hydrodynamic code, in which heat transfer and Arrhenius kinetics are intimately linked to the hydrodynamics.« less

  5. Multiscale approach for the construction of equilibrated all-atom models of a poly(ethylene glycol)-based hydrogel

    PubMed Central

    Li, Xianfeng; Murthy, N. Sanjeeva; Becker, Matthew L.; Latour, Robert A.

    2016-01-01

    A multiscale modeling approach is presented for the efficient construction of an equilibrated all-atom model of a cross-linked poly(ethylene glycol) (PEG)-based hydrogel using the all-atom polymer consistent force field (PCFF). The final equilibrated all-atom model was built with a systematic simulation toolset consisting of three consecutive parts: (1) building a global cross-linked PEG-chain network at experimentally determined cross-link density using an on-lattice Monte Carlo method based on the bond fluctuation model, (2) recovering the local molecular structure of the network by transitioning from the lattice model to an off-lattice coarse-grained (CG) model parameterized from PCFF, followed by equilibration using high performance molecular dynamics methods, and (3) recovering the atomistic structure of the network by reverse mapping from the equilibrated CG structure, hydrating the structure with explicitly represented water, followed by final equilibration using PCFF parameterization. The developed three-stage modeling approach has application to a wide range of other complex macromolecular hydrogel systems, including the integration of peptide, protein, and/or drug molecules as side-chains within the hydrogel network for the incorporation of bioactivity for tissue engineering, regenerative medicine, and drug delivery applications. PMID:27013229

  6. Note: A dual temperature closed loop batch reactor for determining the partitioning of trace gases within CO{sub 2}-water systems

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Warr, Oliver, E-mail: oliver.warr@earth.ox.ac.uk; Ballentine, Christopher J.; Rochelle, Christopher A.

    An experimental approach is presented which can be used to determine partitioning of trace gases within CO{sub 2}-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magneticmore » stirrer and high-pressure liquid chromatography pump, respectively.« less

  7. Acoustical power amplification and damping by temperature gradients.

    PubMed

    Biwa, Tetsushi; Komatsu, Ryo; Yazaki, Taichi

    2011-01-01

    Ceperley proposed a concept of a traveling wave heat engine ["A pistonless Stirling engine-The traveling wave heat engine," J. Acoust. Soc. Am. 66, 1508-1513 (1979).] that provided a starting point of thermoacoustics today. This paper verifies experimentally his idea through observation of amplification and strong damping of a plane acoustic traveling wave as it passes through axial temperature gradients. The acoustic power gain is shown to obey a universal curve specified by a dimensionless parameter ωτα; ω is the angular frequency and τα is the relaxation time for the gas to thermally equilibrate with channel walls. As an application of his idea, a three-stage acoustic power amplifier is developed, which attains the gain up to 10 with a moderate temperature ratio of 2.3.

  8. Theoretical estimates of equilibrium 13C-18O clumping in carbonates and organic acids

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.; Eiler, J. M.

    2004-12-01

    The development of techniques for measuring small gas-phase molecules containing more than one rare stable isotope (e.g., 13C18O16O) at natural, ppm-level abundances1,2 has made it possible to track sources and sinks of atmospheric gases from a new perspective. Similar measurements of 13C-18O clumping in ancient samples could improve our understanding of ancient climates, if the abundances of `clumped' rare stable isotopes in materials that retain isotopic signatures over geologic time can be measured with sufficient precision. This theoretical study estimates the abundances of such 13C-18O `clumps' in carbonates and organic acids and discusses their potential applications. Accompanying abstracts by Eiler et al. and Ghosh et al. will present the analytical methods and some initial data for carbonate minerals to examine the applicability of our theoretical models. Equilibrium isotopic speciations in carbonate minerals and organic acids are calculated from the reduced partition function ratios of isotopically substituted crystals and molecules. Vibrational frequencies used as input for these calculations come from ab initio force fields, determined using density functional theory. Our calculations indicate that carbonate minerals, including calcite, dolomite, and aragonite, when equilibrated at earth-surface temperatures, will have a slight overabundance of CO32- groups containing both 13C and 18O (i.e., 13C18O16O22-) relative to what would be expected if carbon and oxygen isotopes were distributed randomly in the crystal lattice. Calcite and dolomite crystals are predicted to have 0.4‰ excesses of 13C18O16O22- at 298 K; in aragonite the excess will be about 0.05‰ larger. The excesses are smaller for crystals formed or equilibrated at higher temperatures, decreasing by 0.003\\permil/oC at room temperature and essentially disappearing at temperatures of 1000 K or higher. Similarly, there is an excess of both 13C18O16OH and 13C16O18OH groups in organic acids like formic acid (HCOOH) and pyruvic acid (CH3COCOOH) that equilibrate at low temperatures. For gas-phase carboxylic acids, 13C-18O clumping in the COOH group is strongest at the C=O double bond, with an 1.0-1.1‰ excess at room temperature. The C-O-H subgroup has an ~0.4‰ 13C-18O excess, and thus the average anomaly for the whole COOH group is 0.7-0.8\\permil. As with carbonate minerals, these excesses decrease at higher temperatures. The magnitude of 13C-18O clumping in carboxylic acid is similar to gas-phase CO2 1,2,3, while in carbonate minerals the effect is about one-half as large. The temperature sensitivity of these isotopic clumping effects suggests that measurements of abundances of 13C-18O bonds in carbonates and organic acids could be useful for paleothermometry. The clumping equilibrium is an internal property of each phase, so temperature information can be obtained even when the isotopic composition of the fluid phase from which a sample precipitated is unknown. Clumping effects may also be able to distinguish pristine, unaltered sedimentary and biogenic carbonates and organic deposits from those that have undergone post-depositional diagenesis or metamorphism, even in samples that have not suffered extensive open-system exchange. Refs: 1Eiler et al. 2004, GCA in press; 2Schauble et al. in prep.; 3Wang et al. 2004, GCA in press.

  9. Calculation of H2-He Flow with Nonequilibrium Ionization and Radiation: an Interim Report

    NASA Technical Reports Server (NTRS)

    Furudate, Michiko; Chang, Keun-Shik

    2005-01-01

    The nonequilibrium ionization process in hydrogen-helium mixture behind a strong shock wave is studied numerically using the detailed ionization rate model developed recently by Park which accounts for emission and absorption of Lyman lines. The study finds that, once the avalanche ionization is started, the Lyman line is self-absorbed. The intensity variation of the radiation at 5145 Angstroms found by Leibowitz in a shock tube experiment can be numerically reproduced by assuming that ionization behind the shock wave prior to the onset of avalanche ionization is 1.3%. Because 1.3% initial ionization is highly unlikely, Leibowitz s experimental data is deemed questionable. By varying the initial electron density value in the calculation, the calculated ionization equilibration time is shown to increase approximately as inverse square-root of the initial electron density value. The true ionization equilibration time is most likely much longer than the value found by Leibowitz.

  10. An experimental study of the effect of temperature, fluid chemistry and reaction rate on Sr-Ca partitioning in anhydrite: Implications for subseafloor hydrothermal alteration processes

    NASA Astrophysics Data System (ADS)

    Syverson, D.; Seyfried, W. E.

    2010-12-01

    Anhydrite (CaSO4) is an important mineral in subseafloor hydrothermal systems. Its solubility likely plays a role in controlling mass transfer reactions in the relatively low temperature and ultramafic-hosted Lost City Hydrothermal Field (LCHF), while also precipitating from seawater during recharge of more widespread high-temperature hydrothermal systems at mid-ocean ridges. Strontium partitions into anhydrite, although the magnitude and mechanism by which this occurs, is still unclear, as is the effect of precipitation rate. In the absence of these data it is not possible to predict accurately the geochemical implications of Sr/Ca ratios of vent fluids. Accordingly, the potential usefulness of these data to constrain temperature, and as a means to understand the flux of seawater derived Sr into deeper portions of subseafloor hydrothermal systems, is limited. Here we report results of experiments designed to assess Ca-Sr exchange during anhydrite-fluid reaction as a function of temperature, fluid chemistry and distance from equilibrium. Anhydrite used for the experiments was synthesized to avoid compositional impurities and annealed to achieve grain sizes (10-100 micron) and uniform crystalline properties. NaCl fluids (0.55 m) with known Sr/Ca ratios were used for the experiments. Experiments were performed at 200° and 250°C, 500 bars, while time series changes in fluid chemistry were monitored by fluid sampling at experimental conditions. Isobaric temperature change as well as chemical perturbation by addition of fluids with anomalous Sr/Ca ratio permitted phase equilibria to be unambiguously assed. Moreover, the chemical perturbation experiments provided information on the effect of rate of reaction on Sr-Ca exchange. Isobaric temperature jumps demonstrate that initially anhydrite precipitation incorporates Sr preferentially. With further reaction progress and approach to equilibrium Sr uptake by anhydrite recrystallization becomes less effective. Long-term equilibration (~3 months) of fluid and anhydrite at 250°C produces aSr/aCa*1000 of 2.8425. Results from the isothermal spike experiments indicate that the rate of exchange (dF/dt) for aSr/aCa is on the order of 0.01/day. Applying the experimentally determined Sr/Ca data to endmember vent fluids from LCHF suggests subseafloor temperatures near 200°C, in good agreement with constraints imposed by observed Ca and sulfate concentrations assuming anhydrite-fluid equilibria. Furthermore, the effect of supersaturated partitioning and experimentally determined rate at which Sr is incorporated into anhydrite suggests that seawater Sr uptake by anhydrite may be very effective, especially if the rate of formation is rapid, as might be expected owing to the sharply increasing geothermal gradient likely for the recharge portions of most of basalt-hosted hydrothermal systems at mid-ocean ridges. This would have important implications for the flux of radiogenic Sr and calculations of fluid/rock ratios at depth in the ocean crust.

  11. Henry's law constant for phosphine in seawater: determination and assessment of influencing factors

    NASA Astrophysics Data System (ADS)

    Fu, Mei; Yu, Zhiming; Lu, Guangyuan; Song, Xiuxian

    2013-07-01

    The Henry's Law constant ( k) for phosphine in seawater was determined by multiple phase equilibration combined with headspace gas chromatography. The effects of pH, temperature, and salinity on k were studied. The k value for phosphine in natural seawater was 6.415 at room temperature (approximately 23°C). This value increases with increases in temperature and salinity, but no obvious change was observed at different pH levels. At the same temperature, there was no significant difference between the k for phosphine in natural seawater and that in artificial seawater. This implies that temperature and salinity are major determining factors for k in marine environment. Double linear regression with Henry's Law constants for phosphine as a function of temperature and salinity confirmed our observations. These results provide a basis for the measurement of trace phosphine concentrations in seawater, and will be helpful for future research on the status of phosphine in the oceanic biogeochemical cycle of phosphorus.

  12. THE TEMPERATURE OF HOT GAS IN GALAXIES AND CLUSTERS: BARYONS DANCING TO THE TUNE OF DARK MATTER

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hansen, Steen H.; Maccio, Andrea V.; Romano-Diaz, Emilio

    2011-06-10

    The temperature profile of hot gas in galaxies and galaxy clusters is largely determined by the depth of the total gravitational potential and thereby by the dark matter (DM) distribution. We use high-resolution hydrodynamical simulations of galaxy formation to derive a surprisingly simple relation between the gas temperature and DM properties. We show that this relation holds not just for galaxy clusters but also for equilibrated and relaxed galaxies at radii beyond the central stellar-dominated region of typically a few kpc. It is then clarified how a measurement of the temperature and density of the hot gas component can leadmore » to an indirect measurement of the DM velocity anisotropy in galaxies. We also study the temperature relation for galaxy clusters in the presence of self-regulated, recurrent active galactic nuclei (AGNs), and demonstrate that this temperature relation even holds outside the inner region of {approx}30 kpc in clusters with an active AGN.« less

  13. First-order wetting transition at a liquid-vapor interface

    NASA Technical Reports Server (NTRS)

    Schmidt, J. W.; Moldover, M. R.

    1983-01-01

    Evidence from reflectance and contact angle measurements is presented that three-phase mixtures of i-C3H7OH-C7F14 exhibit a first-order wetting phase transition at the liquid-vapor interface at 38 C. Equilibration phenomena support this interpretation. Ellipsometry was used to measure the apparent thickness of the intruding layer in the three-phase mixture. At temperatures slightly above the wetting temperature T(w), the intruding layer's thickness is several hundred angstroms and its variation with temperature is extremely weak. Below T(w), three-phase contact can occur between the vapor and both the upper and lower liquid phases; one of the angles which characterizes this contact has a very simple temperature dependence. The thickness of the intruding layer, monitored as the solutions approached equilibrium, is found to depend quite weakly on the height spanned by the upper liquid phase in the vicinity of a first-order wetting transition.

  14. Determination of Activities of Niobium in Cu-Nb Melts Containing Dilute Nb

    NASA Astrophysics Data System (ADS)

    Wang, Daya; Yan, Baijun; Sichen, Du

    2015-04-01

    The activity coefficients of niobium in Cu-Nb melts were measured by equilibrating solid NbO2 with liquid copper under controlled oxygen potentials in the temperature range of 1773 K to 1898 K (1500 °C to 1625 °C). Either CO-CO2 gas mixture or H2-CO2 gas mixture was employed to obtain the desired oxygen partial pressures. Cu-Nb system was found to follow Henry's law in the composition range studied. The temperature dependence of Henry's constant in the Cu-Nb melts could be expressed as follows: The partial molar excess Gibbs energy change of niobium in Cu-Nb melts can be expressed as follows:

  15. Termination of a Magnetized Plasma on a Neutral Gas: The End of the Plasma

    NASA Astrophysics Data System (ADS)

    Cooper, C. M.; Gekelman, W.

    2013-06-01

    Experiments are performed at the Enormous Toroidal Plasma Device at UCLA to study the neutral boundary layer (NBL) between a magnetized plasma and a neutral gas along the direction of a confining magnetic field. This is the first experiment to measure plasma termination within a neutral gas without the presence of a wall or obstacle. A magnetized, current-free helium plasma created by a lanthanum hexaboride (LaB6) cathode terminates entirely within a neutral helium gas. The plasma is weakly ionized (ne/nn˜1%) and collisional λn≪Lplasma. The NBL occurs where the plasma pressure equilibrates with the neutral gas pressure, consistent with a pressure balance model. It is characterized by a field-aligned ambipolar electric field, developing self-consistently to maintain a current-free termination of the plasma on the neutral gas. Probes are inserted into the plasma to measure the plasma density, flow, temperature, current, and potential. These measurements confirm the presence of the ambipolar field and the pressure equilibration model of the NBL.

  16. Pickled egg production: effect of brine acetic acid concentration and packing conditions on acidification rate.

    PubMed

    Acosta, Oscar; Gao, Xiaofan; Sullivan, Elizabeth K; Padilla-Zakour, Olga I

    2014-05-01

    U.S. federal regulations require that acidified foods must reach a pH of 4.6 or lower within 24 h of packaging or be kept refrigerated until then. Processes and formulations should be designed to satisfy this requirement, unless proper studies demonstrate the safety of other conditions. Our objective was to determine the effect of brine acetic acid concentration and packing conditions on the acidification rate of hard-boiled eggs. Eggs were acidified (60/40 egg-to-brine ratio) at various conditions of brine temperature, heat treatment to filled jars, and postpacking temperature: (i) 25 °C/none/25 °C (cold fill), (ii) 25 °C/none/2 °C (cold fill/refrigerated), (iii) 85 °C/none/25 °C (hot fill), and (iv) 25 °C/100 °C for 16 min/25 °C (water bath). Three brine concentrations were evaluated (7.5, 4.9, and 2.5% acetic acid) and egg pH values (whole, yolk, four points within egg) were measured from 4 to 144 h, with eggs equilibrating at pH 3.8, 4.0, and 4.3, respectively. Experiments were conducted in triplicate, and effects were considered significant when P < 0.05. Multiple linear regression analysis was conducted to evaluate the effect on pH values at the center of the yolk. Regression analysis showed that brine concentration of 2.5% decreased the acidification rate, while packing conditions of the hot fill trial increased it. Inverse prediction was used to determine the time for the center of the yolk and the total yolk to reach a pH value of 4.6. These results demonstrate the importance of conducting acidification studies with proper pH measurements to determine safe conditions to manufacture commercially stable pickled eggs.

  17. 42 CFR Appendix - Tables to Subpart L of Part 84

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... respiratory protection against more than one gas of a type, as for use in chlorine and sulfur dioxide, the... Ammonia Equilibrated NH3 1000 32 4 50 50 Chlorine As received Cl2 500 64 3 5 35 Chlorine Equilibrated Cl2... Sulfur dioxide As received SO2 500 64 3 5 30 Sulfur dioxide Equilibrated SO2 500 32 4 5 30 1 Minimum life...

  18. Evaluation of short-term tracer fluctuations in groundwater and soil air in a two year study

    NASA Astrophysics Data System (ADS)

    Jenner, Florian; Mayer, Simon; Aeschbach, Werner; Weissbach, Therese

    2016-04-01

    The application of gas tracers like noble gases (NGs), SF6 or CFCs in groundwater studies such as paleo temperature determination requires a detailed understanding of the dynamics of reactive and inert gases in the soil air with which the infiltrating water equilibrates. Due to microbial gas consumption and production, NG partial pressures in soil air can deviate from atmospheric air, an effect that could bias noble gas temperatures estimates if not taken into account. So far, such an impact on NG contents in groundwater has not been directly demonstrated. We provide the first long-term study of the above mentioned gas tracers and physical parameters in both the saturated and unsaturated soil zone, sampled continuously for more than two years near Mannheim (Germany). NG partial pressures in soil air correlate with soil moisture and the sum value of O2+CO2, with a maximal significant enhancement of 3-6% with respect to atmospheric air during summer time. Observed seasonal fluctuations result in a mass dependent fractionation of NGs in soil air. Concentrations of SF6 and CFCs in soil air are determined by corresponding fluctuations in local atmospheric air, caused by industrial emissions. Arising concentration peaks are damped with increasing soil depth. Shallow groundwater shows short-term NG fluctuations which are smoothed within a few meters below the water table. A correlation between NG contents of soil air and of groundwater is observable during strong recharge events. However, there is no evidence for a permanent influence of seasonal variations of soil air composition on shallow groundwater. Fluctuating NG contents in shallow groundwater are rather determined by variations of soil temperature and water table level. Our data gives evidence for a further temperature driven equilibration of groundwater with entrapped air bubbles within the topmost saturated zone, which permanently occurs even some years after recharge. Local subsurface temperature fluctuations may thus lead to subsequent variations of NG contents in groundwater, independent of the former recharge temperature. This effect is of major importance for gas tracer applications in recent and shallow groundwater.

  19. MD simulations of phase stability of PuGa alloys: Effects of primary radiation defects and helium bubbles

    DOE PAGES

    Dremov, V. V.; Sapozhnikov, F. A.; Ionov, G. V.; ...

    2013-05-14

    We present classical molecular dynamics (MD) with Modified Embedded Atom Model (MEAM) simulations to investigate the role of primary radiation defects and radiogenic helium as factors affecting the phase stability of PuGa alloys in cooling–heating cycles at ambient pressure. The models of PuGa alloys equilibrated at ambient conditions were subjected to cooling–heating cycles in which they were initially cooled down to 100 K and then heated up to 500 K at ambient pressure. The rate of temperature change in the cycles was 10 K/ns. The simulations showed that the initial FCC phase of PuGa alloys undergo polymorphous transition in coolingmore » to a lower symmetry α'-phase. All the alloys undergo direct and reverse polymorphous transitions in the cooling–heating cycles. The alloys containing vacancies shift in both transitions to lower temperatures relative to the defect-free alloys. The radiogenic helium has much less effect on the phase stability compared to that of primary radiation defects (in spite of the fact that helium concentration is twice of that for the primary radiation defects). Lastly, this computational result agrees with experimental data on unconventional stabilization mechanism of PuGa alloys.« less

  20. Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping.

    PubMed

    Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

    2018-05-02

    Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b . First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.

  1. Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping

    NASA Astrophysics Data System (ADS)

    Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

    2018-05-01

    Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b. First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.

  2. A Controlled Agitation Process for Improving Quality of Canned Green Beans during Agitation Thermal Processing.

    PubMed

    Singh, Anika; Pratap Singh, Anubhav; Ramaswamy, Hosahalli S

    2016-06-01

    This work introduces the concept of a controlled agitation thermal process to reduce quality damage in liquid-particulate products during agitation thermal processing. Reciprocating agitation thermal processing (RA-TP) was used as the agitation thermal process. In order to reduce the impact of agitation, a new concept of "stopping agitations after sufficient development of cold-spot temperature" was proposed. Green beans were processed in No. 2 (307×409) cans filled with liquids of various consistency (0% to 2% CMC) at various frequencies (1 to 3 Hz) of RA-TP using a full-factorial design and heat penetration results were collected. Corresponding operator's process time to impart a 10-min process lethality (Fo ) and agitation time (AT) were calculated using heat penetration results. Accordingly, products were processed again by stopping agitations as per 3 agitation regimes, namely; full time agitation, equilibration time agitation, and partial time agitation. Processed products were photographed and tested for visual quality, color, texture, breakage of green beans, turbidity, and percentage of insoluble solids in can liquid. Results showed that stopping agitations after sufficient development of cold-spot temperatures is an effective way of reducing product damages caused by agitation (for example, breakage of beans and its leaching into liquid). Agitations till one-log temperature difference gave best color, texture and visual product quality for low-viscosity liquid-particulate mixture and extended agitations till equilibration time was best for high-viscosity products. Thus, it was shown that a controlled agitation thermal process is more effective in obtaining high product quality as compared to a regular agitation thermal process. © 2016 Institute of Food Technologists®

  3. A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(II) alpha-diimine catalyst.

    PubMed

    Popeney, Chris S; Guan, Zhibin

    2009-09-02

    A detailed mechanistic investigation of the copolymerization of ethylene and methyl acrylate (MA) by a Pd(II) cyclophane-based alpha-diimine catalyst is reported. Our previous observations of unusually high incorporations of acrylates in copolymerization using this catalyst (J. Am. Chem. Soc. 2007, 129, 10062) prompted us to conduct a full mechanistic study on ethylene/MA copolymerization, which indicates a dramatic departure from normal Curtin-Hammett kinetic behavior as observed in copolymerization using the normal Brookhart type of Pd(II) alpha-diimine catalysts. Further investigation reveals that this contrasting behavior originates from the axial blocking effect of the cyclophane ligand hindering olefin substitution and equilibration. In equilibrium studies of ethylene with nitriles, the cyclophane catalyst was found to more strongly favor the linearly binding nitrile ligands as compared to the standard acyclic Pd(II) alpha-diimine catalysts. Ethylene exchange rates in the complexes [(N--N)PdMe(C(2)H(4))](+) (N--N = diimine) were measured by 2D EXSY NMR spectroscopy and found to be over 100 times slower in the cyclophane case. Measurement of the slow equilibration of ethylene, methyl acrylate, and 4-methoxystyrene in cyclophane-based Pd(II) olefin complexes by (1)H NMR and fitting of the obtained kinetic plots allowed for the estimation of exchange rates and equilibrium constants of the olefins. After extrapolation to typical polymerization temperature, DeltaG(double dagger) = 20.6 and 16.4 kcal/mol for ethylene-methyl acrylate exchange in the forward (ethylene displacement by methyl acrylate) and reverse directions, respectively. These values are of similar magnitude to the previously determined migratory insertion barriers of ethylene (DeltaG(double dagger) = 18.9 kcal/mol) and methyl acrylate (DeltaG(double dagger) = 16.3 kcal/mol) under equivalent conditions, but contrast strongly to the rapid olefin exchange seen in the Brookhart acyclic catalyst. The large barrier to olefin exchange hinders olefin pre-equilibrium, decreasing the cyclophane catalyst's ability to preferentially incorporate one monomer (in this case ethylene) over the other, thus giving rise to high comonomer incorporations.

  4. Non-invasive monitoring of skin inflammation using an oxygen-sensing paint-on bandage

    PubMed Central

    Li, Zongxi; Navarro-Alvarez, Nalu; Keeley, Emily J.; Nowell, Nicholas H.; Goncalves, Beatriz M. M.; Huang, Christene A.; Evans, Conor L.

    2017-01-01

    Inflammation involves a cascade of cellular and molecular mediators that ultimately lead to the infiltration of immune cells into the affected area. This inflammatory process in skin is common to many diseases including acne, infection, and psoriasis, with the presence or absence of immune cells a potential diagnostic marker. Here we show that skin inflammation can be non-invasively measured and mapped using a paint-on oxygen sensing bandage in an in vivo porcine inflammation model. After injection of a known inflammatory agent, the bandage could track the increase, plateau, and decrease in oxygen consumption at the injury site over 7 weeks, as well as discern inflammation resultant from injection at various depths beneath the surface of the skin. Both the initial rate of pO2 change and the change in bandage pO2 at equilibration (CBP20) were found to be directly related to the metabolic oxygen consumption rate of the tissue in contact. Healthy skin demonstrated an initial pO2 decrease rate of 6.5 mmHg⋅min−1, and CBP20 of 84 mmHg. Inflamed skin had a significantly higher initial consumption rate of 55 mmHg⋅min−1, and a larger CBP20 of 140 mmHg. The change in the bandage pO2 before and after equilibration with tissue was found to correlate well with histological evidence of skin inflammation in the animals. PMID:29082091

  5. Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process.

    PubMed

    Gusev, Andrey A; Psarras, Antonios C; Triantafyllidis, Konstantinos S; Lappas, Angelos A; Diddams, Paul A

    2017-10-21

    ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n -Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C 12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher conversion levels. Coke remained low with both fresh and steam-deactivated P/ZSM-5 additives.

  6. Component and Technology Development for Advanced Liquid Metal Reactors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Anderson, Mark

    2017-01-30

    The following report details the significant developments to Sodium Fast Reactor (SFR) technologies made throughout the course of this funding. This report will begin with an overview of the sodium loop and the improvements made over the course of this research to make it a more advanced and capable facility. These improvements have much to do with oxygen control and diagnostics. Thus a detailed report of advancements with respect to the cold trap, plugging meter, vanadium equilibration loop, and electrochemical oxygen sensor is included. Further analysis of the university’s moving magnet pump was performed and included in a section ofmore » this report. A continuous electrical resistance based level sensor was built and tested in the sodium with favorable results. Materials testing was done on diffusion bonded samples of metal and the results are presented here as well. A significant portion of this work went into the development of optical fiber temperature sensors which could be deployed in an SFR environment. Thus, a section of this report presents the work done to develop an encapsulation method for these fibers inside of a stainless steel capillary tube. High temperature testing was then done on the optical fiber ex situ in a furnace. Thermal response time was also explored with the optical fiber temperature sensors. Finally these optical fibers were deployed successfully in a sodium environment for data acquisition. As a test of the sodium deployable optical fiber temperature sensors they were installed in a sub-loop of the sodium facility which was constructed to promote the thermal striping effect in sodium. The optical fibers performed exceptionally well, yielding unprecedented 2 dimensional temperature profiles with good temporal resolution. Finally, this thermal striping loop was used to perform cross correlation velocimetry successfully over a wide range of flow rates.« less

  7. Modeling ground thermal regime of an ancient buried ice body in Beacon Valley, Antarctica using a 1-D heat equation with latent heat effect

    NASA Astrophysics Data System (ADS)

    Liu, L.; Sletten, R. S.; Hallet, B.; Waddington, E. D.; Wood, S. E.

    2013-12-01

    An ancient massive ice body buried under several decimeters of debris in Beacon Valley, Antarctica is believed to be over one million years old, making it older than any known glacier or ice cap. It is fundamentally important as a reservoir of water, proxy for climatic information, and an expression of the periglacial landscape. It is also one of Earth's closest analog for widespread, near-surface ice found in Martian soils and ice-cored landforms. We are interested in understanding controls on how long this ice may persist since our physical model of sublimation suggests it should not be stable. In these models, the soil temperatures and the gradient are important because it determines the direction and magnitude of the vapor flux, and thus sublimation rates. To better understand the heat transfer processes and constrain the rates of processes governing ground ice stability, a model of the thermal behavior of the permafrost is applied to Beacon Valley, Antarctica. It calculates soil temperatures based on a 1-D thermal diffusion equation using a fully implicit finite volume method (FVM). This model is constrained by soil physical properties and boundary conditions of in-situ ground surface temperature measurements (with an average of -23.6oC, a maximum of 20.5oC and a minimum of -54.3oC) and ice-core temperature record at ~30 m. Model results are compared to in-situ temperature measurements at depths of 0.10 m, 0.20 m, 0.30 m, and 0.45 m to assess the model's ability to reproduce the temperature profile for given thermal properties of the debris cover and ice. The model's sensitivity to the thermal diffusivity of the permafrost and the overlaying debris is also examined. Furthermore, we incorporate the role of ice condensation/sublimation which is calculated using our vapor diffusion model in the 1-D thermal diffusion model to assess potential latent heat effects that in turn affect ground ice sublimation rates. In general, the model simulates the ground thermal regime well. Detailed temperature comparison suggests that the 1-D thermal diffusion model results closely approximate the measured temperature at all depths with the average square root of the mean squared error (SRMSE) of 0.15oC; a linear correlation between modeled and measured temperatures yields an average R2 value of 0.9997. Prominent seasonal temperature variations diminish with depth, and it equilibrates to mean annual temperature at about 21.5 m depth. The amount of heat generated/consumed by ice condensation/sublimation is insufficient to significantly impact the thermal regime.

  8. Magnesium isotope fractionation in co-existing clino-pyroxene and garnet: implications for geothermometry and mantle source characterization

    NASA Astrophysics Data System (ADS)

    Chakrabarti, R.; Jacobsen, S. B.; Basu, A. R.

    2011-12-01

    It is now well established that the Mg isotopic composition of the bulk silicate Earth, as represented by olivines, peridotites and basalts is identical to bulk meteorites and the Moon. However, small differences have been documented between co-existing olivines and clino-pyroxenes in mantle xenoliths as well as co-existing hornblendes and biotites in granitoids; spinels show some of the heaviest δ26Mg (deviation of the 26Mg/24Mg ratio from the Dead Sea Metal standard). A recent study has documented a large Mg isotopic fractionation between co-existing omphacite and garnet (Δ26MgOMP-GT = δ26MgOMP - δ26MgGT ~1.14) from eclogites in the Dabie orogen of China. This large equilibrium Mg isotope fractionation is explained by the difference in coordination number of Mg in omphacite (six) and garnet (eight). We report stable Mg isotopic compositions of co-existing garnet and clino-pyroxenes from different mantle-derived rocks. Garnet-omphacite pairs analyzed are from an eclogite xenolith from the Roberts Victor kimberlite pipe, the ultra-high pressure Tso Morari eclogite from the Ladakh Himalayas and the Healdsburg eclogite from the Franciscan Subduction Complex, which have a wide range in estimated temperatures of equilibration. Although, the latter two eclogites were exhumed in orogenic belts, our selective picking of the mineral cores for analysis avoided retrograded compositions. We have also analyzed Cr-diopside and pyrope-rich garnet pairs from several southern African kimberlite pipes. These include granular garnet peridotite xenoliths (P = 30-40 kbar, T =950-10500C) as well as the deeper sheared xenoliths (P = 50-60 kbar, T = 13500C). Rapid quenching of the kimberlite-hosted xenoliths ensures minimal low temperature pervasive alteration of these samples. Also analyzed are samples from the Gore Mt. amphibolite and a wollastonite-diopside-garnet skarn from the Adirondacks with equilibration temperatures of 700-7260C. Minerals were separated by hand-picking under a binocular microscope. Mg was quantitatively separated from other matrix elements using cation exchange chromatography. All three Mg isotopes were simultaneously measured using the IsoProbe-P MC-ICPMS at Harvard University by sample-standard bracketing. Our results from 11 garnet-clinopyroxene mineral pairs with widely varying temperatures of equilibration indicate that δ26Mg in garnet (-0.6 to -2.3) is much lower than that in co-existing clino-pyroxenes (-0.1 to -0.6 and -1.3 in the wollastonite skarn). This result is consistent with theoretical predictions as well as recent results from the Dabie orogen. Δ26Mg between clino-pyroxene and garnet ranges from 0.7 to 2.3. Our results suggest a temperature dependence of Δ26Mg between clino-pyroxene and garnet in mantle-derived rocks which can potentially be used as a geothermometer. Large Mg isotopic fractionation between co-existing garnet and clino-pyroxenes has implications for source characterization (garnet peridotite versus eclogite) of mantle-derived melts.

  9. Equilibrator-based measurements of dissolved nitrous oxide in the surface ocean using an integrated cavity output laser absorption spectrometer

    NASA Astrophysics Data System (ADS)

    Grefe, I.; Kaiser, J.

    2014-06-01

    Dissolved nitrous oxide (N2O) concentrations are usually determined by gas chromatography (GC). Here we present laboratory tests and initial field measurements using a novel setup comprising a commercially available laser-based analyser for N2O, carbon monoxide and water vapour coupled to a glass-bed equilibrator. This approach is less labour-intensive and provides higher temporal and spatial resolution than the conventional GC technique. The standard deviation of continuous equilibrator or atmospheric air measurements was 0.2 nmol mol-1 (averaged over 5 min). The short-term repeatability for reference gas measurements within 1 h of each other was 0.2 nmol mol-1 or better. Another indicator of the long-term stability of the analyser is the standard deviation of the calibrated N2O mole fraction in marine air, which was between 0.5 and 0.7 nmol mol-1. The equilibrator measurements were compared with purge-and-trap gas chromatography-mass spectrometry (GC-MS) analyses of N2O concentrations in discrete samples from the Southern Ocean and showed agreement to within the 2% measurement uncertainty of the GC-MS method. The equilibrator response time to concentration changes in water was from 142 to 203 s, depending on the headspace flow rate. The system was tested at sea during a north-to-south transect of the Atlantic Ocean. While the subtropical gyres were slightly undersaturated, the equatorial region was a source of nitrous oxide to the atmosphere, confirming previous findings (Forster et al., 2009). The ability to measure at high temporal and spatial resolution revealed submesoscale variability in dissolved N2O concentrations. Mean sea-to-air fluxes in the tropical and subtropical Atlantic ranged between -1.6 and 0.11 μmol m-2 d-1 and confirm that the subtropical Atlantic is not an important source region for N2O to the atmosphere, compared to global average fluxes of 0.6-2.4 μmol m-2 d-1. The system can be easily modified for autonomous operation on voluntary observing ships (VOS). Future work should include an interlaboratory comparison exercise with other methods of dissolved N2O analyses.

  10. Cooling Atomic Gases With Disorder

    DOE PAGES

    Paiva, Thereza; Khatami, Ehsan; Yang, Shuxiang; ...

    2015-12-10

    Cold atomic gases have proven capable of emulating a number of fundamental condensed matter phenomena including Bose-Einstein condensation, the Mott transition, Fulde-Ferrell-Larkin-Ovchinnikov pairing, and the quantum Hall effect. Cooling to a low enough temperature to explore magnetism and exotic superconductivity in lattices of fermionic atoms remains a challenge. Here in this paper, we propose a method to produce a low temperature gas by preparing it in a disordered potential and following a constant entropy trajectory to deliver the gas into a nondisordered state which exhibits these incompletely understood phases. We show, using quantum Monte Carlo simulations, that we can approachmore » the Néel temperature of the three-dimensional Hubbard model for experimentally achievable parameters. Recent experimental estimates suggest the randomness required lies in a regime where atom transport and equilibration are still robust.« less

  11. Platinum catalytic effect on oxygen fugacity of CO 2H 2 gas mixtures measured with ZrO 2 oxygen sensor at 105 Pa from 1300 to 700°C

    NASA Astrophysics Data System (ADS)

    Miyamoto, M.; Mikouchi, T.

    1996-08-01

    The oxygen fugacity of CO 2H 2 gas mixtures were measured with a ZrO 2 oxygen sensor at high temperatures in a furnace. We confirmed that the oxygen fugacity values measured by the ZrO 2 cell are more reducing than those of the CO 2H 2 gas mixtures calculated by using JANAF data at temperatures below 1150°C as was previously reported by Huebner (1975). We successfully decreased the deviation of the measured oxygen-fugacity value from the calculated one down to temperature of 800°C by using a Pt catalyst. Our results suggest that the deviation is probably due to incomplete equilibration of the gases.

  12. Bose-Einstein Condensation of Long-Lifetime Polaritons in Thermal Equilibrium.

    PubMed

    Sun, Yongbao; Wen, Patrick; Yoon, Yoseob; Liu, Gangqiang; Steger, Mark; Pfeiffer, Loren N; West, Ken; Snoke, David W; Nelson, Keith A

    2017-01-06

    The experimental realization of Bose-Einstein condensation (BEC) with atoms and quasiparticles has triggered wide exploration of macroscopic quantum effects. Microcavity polaritons are of particular interest because quantum phenomena such as BEC and superfluidity can be observed at elevated temperatures. However, polariton lifetimes are typically too short to permit thermal equilibration. This has led to debate about whether polariton condensation is intrinsically a nonequilibrium effect. Here we report the first unambiguous observation of BEC of optically trapped polaritons in thermal equilibrium in a high-Q microcavity, evidenced by equilibrium Bose-Einstein distributions over broad ranges of polariton densities and bath temperatures. With thermal equilibrium established, we verify that polariton condensation is a phase transition with a well-defined density-temperature phase diagram. The measured phase boundary agrees well with the predictions of basic quantum gas theory.

  13. Approach to thermal equilibrium in atomic collisions.

    PubMed

    Zhang, P; Kharchenko, V; Dalgarno, A; Matsumi, Y; Nakayama, T; Takahashi, K

    2008-03-14

    The energy relaxation of fast atoms moving in a thermal bath gas is explored experimentally and theoretically. Two time scales characterize the equilibration, one a short time, in which the isotropic energy distribution profile relaxes to a Maxwellian shape at some intermediate effective temperature, and the second, a longer time in which the relaxation preserves a Maxwellian distribution and its effective temperature decreases continuously to the bath gas temperature. The formation and preservation of a Maxwellian distribution does not depend on the projectile to bath gas atom mass ratio. This two-stage behavior arises due to the dominance of small angle scattering and small energy transfer in the collisions of neutral particles. Measurements of the evolving Doppler profiles of emission from excited initially energetic nitrogen atoms traversing bath gases of helium and argon confirm the theoretical predictions.

  14. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Spycher, Nicolas; Peiffer, Loic; Finsterle, Stefan

    GeoT implements the multicomponent geothermometry method developed by Reed and Spycher (1984, Geochim. Cosmichim. Acta 46 513–528) into a stand-alone computer program, to ease the application of this method and to improve the prediction of geothermal reservoir temperatures using full and integrated chemical analyses of geothermal fluids. Reservoir temperatures are estimated from statistical analyses of mineral saturation indices computed as a function of temperature. The reconstruction of the deep geothermal fluid compositions, and geothermometry computations, are all implemented into the same computer program, allowing unknown or poorly constrained input parameters to be estimated by numerical optimization using existing parameter estimationmore » software, such as iTOUGH2, PEST, or UCODE. This integrated geothermometry approach presents advantages over classical geothermometers for fluids that have not fully equilibrated with reservoir minerals and/or that have been subject to processes such as dilution and gas loss.« less

  15. Olivine-Orthopyroxene Equilibrium in Metal-rich Systems: Applications to Achondrites and Equilibrated Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Benedix, G. K.; McCoy, T. J.

    2003-01-01

    Olivine and orthopyroxene are major minerals in every type of stony meteorite. The majority of achondritic meteorites and silicate-bearing iron meteorites have experienced high temperatures. If these temperatures persisted for an extended period of time then the iron contents of olivine and orthopyroxene should be in equilibrium. In their study of ungrouped clasts and chondritic meteorites, suggested that the equilibrium compositions of olivine and orthopyroxene should fall on a mixing line between LL chondrites and aubrites. Here we show that this is not necessarily the case and that a range of FeO contents in olivine and orthopyroxene can be in equilibrium with each other. The key parameters that determine the equilibrium Fe content in these minerals are temperature, oxygen fugacity (fO2), and silica activity (aSiO2).

  16. Example of a Fluid-Phase Change Examined with MD Simulation: Evaporative Cooling of a Nanoscale Droplet.

    PubMed

    Ao, Takashi; Matsumoto, Mitsuhiro

    2017-10-24

    We carried out a series of molecular dynamics simulations in order to examine the evaporative cooling of a nanoscale droplet of a Lennard-Jones liquid. After thermally equilibrating a droplet at a temperature T ini /T t ≃ 1.2 (T t is the triple-point temperature), we started the evaporation into vacuum by removing vaporized particles and monitoring the change in droplet size and the temperature inside. As free evaporation proceeds, the droplet reaches a deep supercooled liquid state of T/T t ≃ 0.7. The temperature was found to be uniform in spite of the fast evaporative cooling on the surface. The time evolution of the evaporating droplet properties was satisfactorily explained with a simple one-dimensional phase-change model. After a sufficiently long run, the supercooled droplet was crystallized into a polycrystalline fcc structure. The crystallization is a stochastic nucleation process. The time and the temperature of inception were evaluated over 42 samples, which indicate the existence of a stability limit.

  17. Golf-course and funnel energy landscapes: Protein folding concepts in martensites

    NASA Astrophysics Data System (ADS)

    Shankaraiah, N.

    2017-06-01

    We use protein folding energy landscape concepts such as golf course and funnel to study re-equilibration in athermal martensites under systematic temperature quench Monte Carlo simulations. On quenching below a transition temperature, the seeded high-symmetry parent-phase austenite that converts to the low-symmetry product-phase martensite, through autocatalytic twinning or elastic photocopying, has both rapid conversions and incubation delays in the temperature-time-transformation phase diagram. We find the rapid (incubation delays) conversions at low (high) temperatures arises from the presence of large (small) size of golf-course edge that has the funnel inside for negative energy states. In the incubating state, the strain structure factor enters into the Brillouin-zone golf course through searches for finite transitional pathways which close off at the transition temperature with Vogel-Fulcher divergences that are insensitive to Hamiltonian energy scales and log-normal distributions, as signatures of dominant entropy barriers. The crossing of the entropy barrier is identified through energy occupancy distributions, Monte Carlo acceptance fractions, heat emission, and internal work.

  18. Long-term frequency and amplitude stability of a solid-nitrogen-cooled, continuous wave THz quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Danylov, Andriy A.; Waldman, Jerry; Light, Alexander R.; Goyette, Thomas M.; Giles, Robert H.; Qian, Xifeng; Chandrayan, Neelima; Goodhue, William D.; Nixon, William E.

    2012-02-01

    Operational temperature increase of CW THz QCLs to 77 K has enabled us to employ solid nitrogen (SN2) as the cryogen. A roughing pump was used to solidify liquid nitrogen and when the residual vapor pressure in the nitrogen reservoir reached the pumping system's minimum pressure the temperature equilibrated and remained constant until all the nitrogen sublimated. The hold time compared to liquid helium has thereby increased approximately 70-fold, and at a greatly reduced cost. The milliwatt CW QCL was at a temperature of approximately 60 K, dissipating 5 W of electrical power. To measure the long-term frequency, current, and temperature stability, we heterodyned the free-running 2.31 THz QCL with a CO2 pumped far-infrared gas laser line in methanol (2.314 THz) in a corner-cube Schottky diode and recorded the IF frequency, current and temperature. Under these conditions the performance characteristics of the QCL, which will be reported, exceeded that of a device mounted in a mechanical cryocooler.

  19. Studies of peripheral thyroxine distribution in thyrotoxicosis and hypothyroidism.

    PubMed

    Nicoloff, J T; Dowling, J T

    1968-09-01

    Compartmental analysis of the peripheral distribution of labeled thyroxine was applied to various groups of subjects with thyrotoxicosis and hypothyroidism. It was observed that the hepatic incorporation of thyroxine was augmented in subjects with Graves' disease when compared to non-Graves' disease control groups at all levels of thyroid function. Decreased values of hepatic incorporation occurred in primary hypothyroid subjects. These lowered values were not acutely corrected by elevation of the serum thyroxine level, but were observed to be rectified after several months' therapy with exogenous thyroid hormone. These alterations of the hepatic thyroxine-(131)I incorporation were independently verified by direct quantitative liver scintiscan determinations. Employing a dual thyroxine tracer system, we were able to demonstrate that during the early phases of equilibration of a tracer dose of thyroxine, alterations in the rate of deiodination were observed to be present in the various thyroid disease states. Increased deiodination rates were found in subjects with Graves' disease and the reverse was noted in patients with primary hypothyroidism. Kinetic analysis of thyroxine compartmental distribution during this early phase of equilibration of a labeled thyroxine tracer indicated that the primary tissue uptake occurred in the liver. These findings supported the contention that the amount of labeled thyroxine incorporated in the liver may be directly related to the deiodination rate of thyroxine by that organ. The pathogenetic basis of these alterations is presently unknown.

  20. The Precise Measurement of Vapor-Liquid Equilibrium Properties of the CO2/Isopentane Binary Mixture, and Fitted Parameters for a Helmholtz Energy Mixture Model

    NASA Astrophysics Data System (ADS)

    Miyamoto, H.; Shoji, Y.; Akasaka, R.; Lemmon, E. W.

    2017-10-01

    Natural working fluid mixtures, including combinations of CO2, hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor-liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm3 equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO2/ethanol and CO2/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.

  1. Nitrite transport into pig erythrocytes and its potential biological role.

    PubMed

    Jensen, F B

    2005-07-01

    To study nitrite transport and its oxygenation dependency in pig erythrocytes, as this is fundamental to the possible participation of nitrite in blood flow regulation via its reduction to nitric oxide by deoxygenated haemoglobin (Hb). Pig red blood cells (RBCs) were tonometer-equilibrated to physiological pCO2 in oxygenated and deoxygenated states. Nitrite was added and the kinetics of NO2- influx and methaemoglobin (metHb) formation were assessed at variable temperature and haematocrit. Nitrite quickly permeated and equilibrated across the membrane, and then continued to enter RBCs as a consequence of its intracellular removal (via reactions with Hb to form nitrate and metHb in oxygenated cells, and NO and metHb in deoxygenated cells). The membrane permeation as such showed little oxygenation dependency, but as metHb formation was significantly higher in oxygenated than deoxygenated RBCs, nitrite transport tended to be largest into oxygenated RBCs. This contrasts with a preferential permeation of deoxygenated RBCs in some fish species. Nitrite transport showed low temperature sensitivity but was speeded up at low haematocrit via more rapid intracellular nitrite removal (metHb formation). Nitrite influx was not affected by inhibitors of facilitated diffusion (DIDS, phloretin and PCMB) and may occur via conductive transport. Extracellular pH was stable during nitrite transport. Nitrite extensively permeates both oxygenated and deoxygenated pig RBCs, which may enable a dual function of nitrite entry: viz. conversion to NO at low pO2 to promote blood flow and detoxification to non-toxic nitrate at inappropriate high nitrite levels.

  2. Phase Equilibria Study in the TeO2-Na2O-SiO2 System in Air Between 723 K (500 °C) and 1473 K (1200 °C)

    NASA Astrophysics Data System (ADS)

    Santoso, Imam; Taskinen, Pekka

    2016-08-01

    Knowledge of phase equilibria in the TeO2-Na2O-SiO2 system at elevated temperatures is important for ceramic and glass industries and for improving the operation of the smelting process of tellurium-containing materials. A review of previous investigations has indicated, however, that there are omissions in the available datasets on the liquidus temperatures of the molten TeO2-Na2O-SiO2 mixtures. The employed experimental method included equilibration of mixtures made from high purity oxides, rapid quenching of the equilibrated samples in water and followed by compositional analysis of the phases using an electron probe X-ray microanalyzer. The liquidus and phase equilibria in the TeO2-SiO2, TeO2-Na2O, and SiO2-TeO2-Na2O systems have been studied for a wide range of compositions between 723 K (500 °C) and 1473 K (1200 °C) at TeO2, SiO2, and Na2SiO3 saturations. New data have been generated in the SiO2-TeO2-Na2O system at SiO2 saturation. The liquidus compositions in the TeO2-Na2O system at TeO2 saturation have been compared with the previous data and an assessed phase diagram.

  3. Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

    1997-01-01

    Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

  4. Modeling of thermalization phenomena in coaxial plasma accelerators

    NASA Astrophysics Data System (ADS)

    Subramaniam, Vivek; Panneerchelvam, Premkumar; Raja, Laxminarayan L.

    2018-05-01

    Coaxial plasma accelerators are electromagnetic acceleration devices that employ a self-induced Lorentz force to produce collimated plasma jets with velocities ~50 km s‑1. The accelerator operation is characterized by the formation of an ionization/thermalization zone near gas inlet of the device that continually processes the incoming neutral gas into a highly ionized thermal plasma. In this paper, we present a 1D non-equilibrium plasma model to resolve the plasma formation and the electron-heavy species thermalization phenomena that take place in the thermalization zone. The non-equilibrium model is based on a self-consistent multi-species continuum description of the plasma with finite-rate chemistry. The thermalization zone is modelled by tracking a 1D gas-bit as it convects down the device with an initial gas pressure of 1 atm. The thermalization process occurs in two stages. The first is a plasma production stage, associated with a rapid increase in the charged species number densities facilitated by cathode surface electron emission and volumetric production processes. The production stage results in the formation of a two-temperature plasma with electron energies of ~2.5 eV in a low temperature background gas of ~300 K. The second, a temperature equilibration stage, is characterized by the energy transfer between the electrons and heavy species. The characteristic length scale for thermalization is found to be comparable to axial length of the accelerator thus putting into question the equilibrium magnetohydrodynamics assumption used in modeling coaxial accelerators.

  5. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  6. Supercooled spin liquid state in the frustrated pyrochlore Dy 2Ti 2O 7

    DOE PAGES

    Kassner, Ethan R.; Eyvazov, Azar B.; Pichler, Benjamin; ...

    2015-06-30

    A “supercooled” liquid develops when a fluid does not crystallize upon cooling below its ordering temperature. Instead, the microscopic relaxation times diverge so rapidly that, upon further cooling, equilibration eventually becomes impossible and glass formation occurs. Classic supercooled liquids exhibit specific identifiers including microscopic relaxation times diverging on a Vogel–Tammann–Fulcher (VTF) trajectory, a Havriliak–Negami (HN) form for the dielectric function ε(ω,T), and a general Kohlrausch–Williams–Watts (KWW) form for time-domain relaxation. Recently, the pyrochlore Dy 2Ti 2O 7 has become of interest because its frustrated magnetic interactions may, in theory, lead to highly exotic magnetic fluids. However, its true magnetic statemore » at low temperatures has proven very difficult to identify unambiguously. Here, we introduce high-precision, boundary-free magnetization transport techniques based upon toroidal geometries and gain an improved understanding of the time- and frequency-dependent magnetization dynamics of Dy 2Ti 2O 7. We demonstrate a virtually universal HN form for the magnetic susceptibility χ(ω,T), a general KWW form for the real-time magnetic relaxation, and a divergence of the microscopic magnetic relaxation rates with the VTF trajectory. Low-temperature Dy 2Ti 2O 7 therefore exhibits the characteristics of a supercooled magnetic liquid. Lastly, one implication is that this translationally invariant lattice of strongly correlated spins may be evolving toward an unprecedented magnetic glass state, perhaps due to many-body localization of spin.« less

  7. Effect of NaCrSi2O6 component on Lindsley's pyroxene thermometer: An evaluation based on strongly metamorphosed LL chondrites

    NASA Astrophysics Data System (ADS)

    Nakamuta, Y.; Urata, K.; Shibata, Y.; Kuwahara, Y.

    2017-03-01

    In Lindsley's thermometry, a revised sequence of calculation of components is proposed for clinopyroxene, in which kosmochlor component is added. Temperatures obtained for the components calculated by the revised method are about 50 °C lower than those obtained for the components calculated by the Lindsley's original method and agree well with temperatures obtained from orthopyroxenes. Ca-partitioning between clino- and orthopyroxenes is then thought to be equilibrated in types 5 to 7 ordinary chondrites. The temperatures for Tuxtuac (LL5), Dhurmsala (LL6), NWA 2092 (LL6/7), and Dho 011 (LL7) are 767-793°, 818-835°, 872-892°, and 917-936°C, respectively, suggesting that chondrites of higher petrographic types show higher equilibrium temperatures of pyroxenes. The regression equations which relate temperature and Wo and Fs contents in the temperature-contoured pyroxene quadrilateral of 1 atm of Lindsley (1983) are also determined by the least squares method. It is possible to reproduce temperatures with an error less than 20 °C (2SE) using the regression equations.

  8. Measuring the temperature dependent thermal diffusivity of geomaterials using high-speed differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    von Aulock, Felix W.; Wadsworth, Fabian B.; Vasseur, Jeremie; Lavallée, Yan

    2016-04-01

    Heat diffusion in the Earth's crust is critical to fundamental geological processes, such as the cooling of magma, heat dissipation during and following transient heating events (e.g. during frictional heating along faults), and to the timescales of contact metamorphosis. The complex composition and multiphase nature of geomaterials prohibits the accurate modeling of thermal diffusivities and measurements over a range of temperatures are sparse due to the specialized nature of the equipment and lack of instrument availability. We present a novel method to measure the thermal diffusivity of geomaterials such as minerals and rocks with high precision and accuracy using a commercially available differential scanning calorimeter (DSC). A DSC 404 F1 Pegasus® equipped with a Netzsch high-speed furnace was used to apply a step-heating program to corundum single crystal standards of varying thicknesses. The standards were cylindrical discs of 0.25-1 mm thickness with 5.2-6 mm diameter. Heating between each 50 °C temperature interval was conducted at a rate of 100 °C/min over the temperature range 150-1050 °C. Such large heating rates induces temperature disequilibrium in the samples used. However, isothermal segments of 2 minutes were used during which the temperature variably equilibrated with the furnace between the heating segments and thus the directly-measured heat-flow relaxed to a constant value before the next heating step was applied. A finite-difference 2D conductive heat transfer model was used in cylindrical geometry for which the measured furnace temperature was directly applied as the boundary condition on the sample-cylinder surfaces. The model temperature was averaged over the sample volume per unit time and converted to heat-flow using the well constrained thermal properties for corundum single crystals. By adjusting the thermal diffusivity in the model solution and comparing the resultant heat-flow with the measured values, we obtain a model calibration for the thermal diffusivity of corundum. Preliminary calibration tests suggest a very good correlation between the measured results compared with literature values of the thermal diffusivity of this standard material. However, more measurements on standard materials are needed to guarantee the accuracy of the presented technique for measuring the thermal diffusion of materials and apply this method to numerical models for relevant processes in geoscience.

  9. High-resolution measurement of DMS and volatile organic compounds dissolved in seawater using equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS)

    NASA Astrophysics Data System (ADS)

    Kameyama, S.; Tanimoto, H.; Inomata, S.; Tsunogai, U.; Ooki, A.; Yokouchi, Y.; Takeda, S.; Obata, H.; Tsuda, A.; Uematsu, M.

    2010-12-01

    We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) for high-resolution measurement of multiple volatile organic compounds (VOCs) dissolved in seawater. The equilibration of six VOC species (dimethyl sulfide (DMS), isoprene, propene, acetone, acetaldehyde, and methanol) between seawater and carrier gas, and the response time of the system were evaluated in the laboratory. While isoprene and propene are not in equilibrium associated with slow response time (≈ 15 min) due to low solubility, other species achieve complete equilibrium with overall response time within 2 min under the condition without water droplets on the inner wall of the headspace of the equilibrator. The EI-PTR-MS instrument was deployed during a cruise in the western North Pacific. For DMS and isoprene, comparison of EI-PTR-MS with a membrane tube equilibrator-gas chromatography/mass spectrometry was made, showing generally good agreement. EI-PTR-MS captured temporal variations of dissolved VOCs including small-scale variability, demonstrating the performance of EI-PTR-MS technique for continuous measurement of multiple VOCs in seawater.

  10. Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Haichao; Iglesia, Enrique

    RuO2 domains supported on SnO2, ZrO2, TiO2, Al2O3, and SiO2 catalyze the oxidative conversion of methanol to formaldehyde, methylformate, and dimethoxymethane with unprecedented rates and high combined selectivity (>99 percent) and yield at low temperatures (300-400 K). Supports influence turnover rates and the ability of RuO2 domains to undergo redox cycles required for oxidation turnovers. Oxidative dehydrogenation turnover rates and rates of stoichiometric reduction of RuO2 in H2 increased in parallel when RuO2 domains were dispersed on more reducible supports. These support effects, the kinetic effects of CH3OH and O2 on reaction rates, and the observed kinetic isotope effects withmore » CH3OD and CD3OD reactants are consistent with a sequence of elementary steps involving kinetically relevant H-abstraction from adsorbed methoxide species using lattice oxygen atoms and with methoxide formation in quasi-equilibrated CH3OH dissociation on nearly stoichiometric RuO2 surfaces. Anaerobic transient experiments confirmed that CH3OH oxidation to HCHO requires lattice oxygen atoms and that selectivities are not influenced by the presence of O2. Residence time effects on selectivity indicate that secondary HCHO-CH3OH acetalization reactions lead to hemiacetal or methoxymethanol intermediates that convert to dimethoxymethane in reactions with CH3OH on support acid sites or dehydrogenate to form methylformate on RuO2 and support redox sites. These conclusions are consistent with the tendency of Al2O3 and SiO2 supports to favor dimethoxymethane formation, while SnO2, ZrO2, and TiO2 preferentially form methylformate. These support effects on secondary reactions were confirmed by measured CH3OH oxidation rates and selectivities on physical mixtures of supported RuO2 catalysts and pure supports. Ethanol also reacts on supported RuO2 domains to form predominately acetaldehyde and diethoxyethane at 300-400 K. The bifunctional nature of these reaction pathways and the remarkable ability of RuO2-based catalysts to oxidize CH3OH to HCHO at unprecedented low temperatures introduce significant opportunities for new routes to complex oxygenates, including some containing C-C bonds, using methanol or ethanol as intermediates derived from natural gas or biomass.« less

  11. Hydrogen peroxide release and acid-base status in exhaled breath condensate at rest and after maximal exercise in young, healthy subjects.

    PubMed

    Marek, E; Platen, P; Volke, J; Mückenhoff, K; Marek, W

    2009-12-07

    Exhaled breath condensate (EBC) contains among a large number of mediators hydrogen peroxide (H2O2) as a marker of airway inflammation and oxidative stress. Similarly EBC pH also changes in respiratory diseases. It was the aim of our investigation to prove if hydrogen peroxide release and changes in pH of EBC changes with exercise. EBC was collected from 100 litres exhaled air along with samples of arterialized blood of 16 healthy subjects (9 males, 7 females, age 23 +/- 1 years). EBC hydrogen peroxide was analyzed with EcoCheck amperometer (FILT, Berlin). The rate of H(2)O(2) release was calculated from the concentration and collection time. pH and PCO(2) in blood and in EBC were measured with the Radiometer blood gas analyzer, EBC was equilibrated with a gas mixture (5% CO(2) in O(2)). The bicarbonate concentration was calculated according to the law of mass action for CO(2) and HCO(3)(-) (pK = 6.1). H(2)O(2) concentration in EBC was 190 +/- 109 nmol/l, and H (2)O(2) release at rest was 31.0 +/- 18.3 pmol/min. At maximal exercise, the H(2)O(2) concentration in EBC increased to 250 +/- 120 nmol/l, and H(2)O(2) release significantly increased at maximal exercise to 84.4 +/- 39.9 pmol/min (P<0.01). At rest pH of the CO(2) equilibrated EBC was at 6.08 +/- 0.23 and the [HCO(3)(-)] was 1.03 +/- 0.40 mmol/l. At maximum exercise, pH 6.18 +/- 0.17 and [HCO(3)(-)] 1.23 +/- 0.30 mmol/l remained almost unaltered. The rate of H(2)O(2) release in EBC increased during exhausting exercise (external load: 300 Watt) by a factor of 2, whereas the pH and the bicarbonate concentration of the EBC, equilibrated with 5% CO(2) at 37 degrees C were not significantly altered. It has to be proven by further experiments whether there is a linear relationship between the rates of H(2)O(2) release in EBC in graded submaximal exercise.

  12. Kinetics of Ca2+ binding to parvalbumin in bovine chromaffin cells: implications for [Ca2+] transients of neuronal dendrites

    PubMed Central

    Lee, Suk-Ho; Schwaller, Beat; Neher, Erwin

    2000-01-01

    The effect of parvalbumin (PV) on [Ca2+] transients was investigated by perfusing adrenal chromaffin cells with fura-2 and fluorescein isothiocyanate (FITC)-labelled PV. As PV diffused into cells, the decay of [Ca2+] transients was transformed from monophasic into biphasic. The proportion of the initial fast decay phase increased in parallel with the fluorescence intensity of FITC, indicating that PV is responsible for the initial fast decay phase.The relationship between the fast decay phase and the [Ca2+] level was investigated using depolarizing trains of stimuli. Within a train the relative amplitude of the fast decay phase was inversely dependent on the [Ca2+] level preceding a given stimulus.Based on these observations, we estimated the Ca2+ binding ratio of PV (κP), the apparent dissociation constant of PV for Ca2+ (Kdc,app), and the unbinding rate constant of Ca2+ from PV (kc-) in the cytosol of chromaffin cells. Assuming free [Mg2+] to be 0.14 mm, we obtained values of 51.4 ± 2.0 nm (n = 3) and 0.95 ± 0.026 s−1 (n = 3), for Kdc,app and kc-, respectively.With the parameters obtained in the perfusion study, we simulated [Ca2+] transients, using two different Ca2+ extrusion rates (γ) – 20 and 300 s−1– which represent typical values for chromaffin cells and neuronal dendrites, respectively. The simulation indicated that Ca2+ is pumped out before it is equilibrated with PV, when γ is comparable to the equilibration rates between PV and Ca2+, resulting in the fast decay phase of a biexponential [Ca2+] transient.From these results we conclude that Ca2+ buffers with slow kinetics, such as PV, may cause biexponential decays in [Ca2+] transients, thereby complicating the analysis of endogenous Ca2+ binding ratios (κS) based on time constants. Nevertheless, estimates of κS based on Ca2+ increments provide reasonable estimates for Ca2+ binding ratios before equilibration with PV. PMID:10835044

  13. Americium, Cesium, and Plutonium Colloid-Facilitated Transport in a Groundwater/Bentonite/Fracture Fill Material System: Column Experiments and Model Results

    NASA Astrophysics Data System (ADS)

    Dittrich, T. M.; Boukhalfa, H.; Reimus, P. W.

    2014-12-01

    The objective of this study was to investigate and quantify the effects of desorption kinetics and colloid transport on radionuclides with different sorption affinities. We focused on quantifying transport mechanisms important for upscaling in time and distance. This will help determine the long-term fate and transport of radionuclides to aid in risk assessments. We selected a fractured/weathered granodiorite at the Grimsel Test Site (GTS) in Switzerland as a model crystalline rock repository system because the system has been thoroughly studied and field experiments involving radionuclides have already been conducted. Working on this system provides a unique opportunity to compare lab experiments with field-scale observations. Weathered fracture fill material (FFM) and bentonite used as backfill at the GTS were characterized (e.g., BET, SEM/EDS, QXRD), and batch and breakthrough column experiments were conducted. Solutions were prepared in synthetic groundwaters that matched the natural water chemistry. FFM samples were crushed, rinsed, sieved (150-355 μm), and equilibrated with synthetic groundwater. Bentonite was crushed, sodium-saturated, equilibrated with synthetic groundwater, and settled to yield a stable suspension. Suspensions were equilibrated with Am, Cs, or Pu. All experiments were conducted with Teflon®materials to limit sorption to system components. After radionuclide/colloid injections reached stability, radionuclide-free solutions were injected to observe the desorption and release behavior. Aliquots of effluent were measured for pH, colloid concentration, and total and dissolved radionuclides. Unanalyzed effluent from the first column was then injected through a second column of fresh material. The process was repeated for a third column and the results of all three breakthrough curves were modeled with a multi-site/multi-rate MATLAB code to elucidate the sorption rate coefficients and binding site densities of the bentonite colloids and fracture fill material. Nearly 50% of the sorbed Am was exchanged from the colloids to the fracture filling material in each of the three columns; whereas, less Cs and Pu was desorbed with each pass through a new column. Using a two-site kinetic model allowed for interrogation of desorption rates and dominant transport parameters.

  14. Factors influencing survival of mammalian cells exposed to hypothermia. VI. Effects of prehypothermic hypoxia followed by aerobic or hypoxic storage at various hypothermic temperatures.

    PubMed

    Kruuv, J; Lepock, J R

    1995-04-01

    The Arrhenius plot of inactivation (killing) rates of V-79 Chinese hamster cells exposed to hypothermia in air-equilibrated (aerobic) medium contains a break at about 8 degrees C, which corresponds to the minimum inactivation rate, implying that there are distinct hypothermic damage mechanisms above (range I, 8 to 25 degrees C) and below (range II, 0 to 8 degrees C) 8 degrees C. Prehypothermic hypoxia (PHH) for 75 min at room temperature sensitizes cells to subsequent aerobic hypothermia at both 5 and 10 degrees C (range II and I). However, PHH followed by severe hypoxia (0.03 microM oxygen in the medium) protected cells during 10 degrees C (range I) storage by increasing the shoulder, but not the slope, of the cell survival curve compared to the PHH plus 10 degrees C aerobic hypothermia case. On the other hand, PHH plus severe hypoxia during 5 degrees C storage (range II) protected cells by decreasing the slope, but not the shoulder, of the cell survival curve compared to the PHH plus 5 degrees C aerobic hypothermia case. Furthermore, PHH plus severe hypoxia during 5 degrees C storage was not significantly worse than aerobic storage without PHH at 5 degrees C. With or without severe hypoxia, 10 degrees C storage is preferable to 5 degrees C storage in this cell line. Extrapolated to organ storage, the results may imply that if warm ischemia (PHH) has occurred, subsequent hypoxic hypothermic perfusion storage may be preferable to aerobic hypothermic perfusion storage.

  15. Equilibrated moisture content of several carbon phenolics and their relationship to resin, fiber, and interface properties

    NASA Technical Reports Server (NTRS)

    Stokes, E. H.

    1991-01-01

    This study focuses on the relationship between relative humidity and the equilibrated moisture content of several variants of two distinctly different carbon phenolic composites. One of the materials gives a typical exponential relationship between RH and equilibrated moisture content while the second gives an inverse sigmoidal relationship with the largest increase in moisture between 45-60 percent relative humidity. The possible relationship between the shape of the curves and the nature of the material constituents is discussed.

  16. Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

    NASA Technical Reports Server (NTRS)

    Carter, H. G.; Bullock, R. E.

    1972-01-01

    Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

  17. Bow Shock in Merging Cluster A520: The Edge of the Radio Halo and the Electron–Proton Equilibration Timescale

    NASA Astrophysics Data System (ADS)

    Wang, Qian H. S.; Giacintucci, Simona; Markevitch, Maxim

    2018-04-01

    We studied the prominent bow shock in the merging galaxy cluster A520 using a deep Chandra X-ray observation and archival VLA radio data. This shock is a useful diagnostic tool, owing to its clear geometry and relatively high Mach number. At the “nose” of the shock, we measure a Mach number of M={2.4}-0.2+0.4. The shock becomes oblique away from the merger axis, with the Mach number falling to ≃1.6 around 30° from the nose. The electron temperature immediately behind the shock nose is consistent with that from the Rankine–Hugoniot adiabat, and is higher (at a 95% confidence) than expected for adiabatic compression of electrons followed by Coulomb electron–proton equilibration, indicating the presence of equilibration mechanisms faster than Coulomb collisions. This is similar to an earlier finding for the Bullet cluster. We also combined four archival VLA data sets to obtain a better image of the cluster’s giant radio halo at 1.4 GHz. An abrupt edge of the radio halo traces the shock front, and no emission is detected in the pre-shock region. If the radio edge were due only to adiabatic compression of relativistic electrons in pre-shock plasma, we would expect a pre-shock radio emission detectable in this radio data set; however, an interferometric artifact dominates the uncertainty, so we cannot rule this model out. Other interesting features of the radio halo include a peak at the remnant of the cool core, suggesting that the core used to have a radio minihalo, and a peak marking a possible region of high turbulence.

  18. A Last Glacial Maximum world-ocean simulation at eddy-permitting resolution - Part 1: Experimental design and basic evaluation

    NASA Astrophysics Data System (ADS)

    Ballarotta, M.; Brodeau, L.; Brandefelt, J.; Lundberg, P.; Döös, K.

    2013-01-01

    Most state-of-the-art climate models include a coarsely resolved oceanic component, which has difficulties in capturing detailed dynamics, and therefore eddy-permitting/eddy-resolving simulations have been developed to reproduce the observed World Ocean. In this study, an eddy-permitting numerical experiment is conducted to simulate the global ocean state for a period of the Last Glacial Maximum (LGM, ~ 26 500 to 19 000 yr ago) and to investigate the improvements due to taking into account these higher spatial scales. The ocean general circulation model is forced by a 49-yr sample of LGM atmospheric fields constructed from a quasi-equilibrated climate-model simulation. The initial state and the bottom boundary condition conform to the Paleoclimate Modelling Intercomparison Project (PMIP) recommendations. Before evaluating the model efficiency in representing the paleo-proxy reconstruction of the surface state, the LGM experiment is in this first part of the investigation, compared with a present-day eddy-permitting hindcast simulation as well as with the available PMIP results. It is shown that the LGM eddy-permitting simulation is consistent with the quasi-equilibrated climate-model simulation, but large discrepancies are found with the PMIP model analyses, probably due to the different equilibration states. The strongest meridional gradients of the sea-surface temperature are located near 40° N and S, this due to particularly large North-Atlantic and Southern-Ocean sea-ice covers. These also modify the locations of the convection sites (where deep-water forms) and most of the LGM Conveyor Belt circulation consequently takes place in a thinner layer than today. Despite some discrepancies with other LGM simulations, a glacial state is captured and the eddy-permitting simulation undertaken here yielded a useful set of data for comparisons with paleo-proxy reconstructions.

  19. Cathodic behaviour of stainless steel in coastal Indian seawater: calcareous deposits overwhelm biofilms.

    PubMed

    Eashwar, M; Subramanian, G; Palanichamy, S; Rajagopal, G; Madhu, S; Kamaraj, P

    2009-01-01

    Type-316 stainless steel (SS) was investigated as the cathode in galvanic couples in full-strength seawater from the Gulf of Mannar on the southeast coast of India. Tests were devised to examine the impact of SS cathodes on anode materials with or without the accrual of marine biofilms. Biofilmed SS cathodes significantly enhanced the rate of corrosion of nickel, causing noble shifts in the couple potentials. With mild steel and zinc as the anodes, calcareous deposits developed quite rapidly on the SS cathodes and led to a significant reduction of bacterial numbers. The calcareous deposits also caused substantial reduction of galvanic corrosion rates for mild steel, whereas there was no difference for zinc. The deposits were identified by XRD as essentially carbonates, oxides and hydroxides of calcium and magnesium. Potentiodynamic polarization performed on the actual couples after disconnection and equilibration provided reasonable interpretations of the galvanic corrosion trends. Data from this work suggest that a potential of about -0.70 V vs. saturated calomel electrode (SCE) should provide optimum protection of SS in warmer, full-strength seawater that supports the precipitation of calcareous deposits. The criterion commonly recommended for temperate conditions of lower water temperature and estuarine waters of lower alkalinity is -1.0 V (SCE).

  20. Morphology Controls on Calcite Recrystallization.

    PubMed

    Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

    2016-11-01

    Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

  1. Effect of potential oocyte transport protocols on blastocyst rates after intracytoplasmic sperm injection in the horse.

    PubMed

    Foss, R; Ortis, H; Hinrichs, K

    2013-12-01

    Intracytoplasmic sperm injection (ICSI) is used to produce foals from otherwise infertile mares and from stallions with limited sperm stores, but requires expensive equipment and is technically demanding. Methods to transport oocytes to ICSI laboratories would allow collection of oocytes by the referring veterinarian and enable greater application of this technique. This study was conducted to evaluate protocols that could be used to transport immature and maturing oocytes for ICSI. In vitro experiment. Oocytes were recovered by transvaginal ultrasound-guided follicular aspiration either from dominant follicles 24 h after deslorelin administration (dominant stimulated follicle [DSF]), or from subordinate (immature) follicles at the same time. To mimic transport, DSF oocytes were incubated overnight under differing conditions before ICSI; immature oocytes were placed in varying conditions overnight before in vitro maturation, followed by ICSI. The rate of blastocyst production was compared among treatments. Blastocysts were produced in all groups. Dominant stimulated follicle oocytes held in sealed tubes in pre-equilibrated control maturation medium maintained at 37°C yielded blastocyst development equal to that obtained for control incubated oocytes (70%). Dominant stimulated follicle oocytes held similarly in a warm passive device yielded poor blastocyst development (10%). Immature oocytes held for one or 2 nights in modified M199 medium, or for one night in commercial embryo holding solution, in air at room temperature, yielded 35-37% blastocyst development per injected oocyte. A commercially available medium can be used for shipping immature oocytes at room temperature with good resulting blastocyst rates. Better blastocyst rates per oocyte are obtained from DSF oocytes; however, these require maintenance at 37°C and as they are already maturing at the time of collection, are more sensitive to delays. This new, practical information supporting transport of both immature and DSF oocytes for ICSI may allow wider use of this procedure. © 2013 EVJ Ltd.

  2. Non-Immunogenic Structurally and Biologically Intact Tissue Matrix Grafts for the Immediate Repair of Ballistic-Induced Vascular and Nerve Tissue Injury in Combat

    DTIC Science & Technology

    2004-12-01

    and -2. However, there was no product breakage. The product stabilizers breakage can be addressed by either using stronger Styrofoam or using the same...dry ice shipper is suitable for use as a 72hrs shipping container for the frozen UVG and that, if necessary, the shipping time can be extended to at...concentrations for two hours at room temperature under constant agitation (85 rpm). The step-wise equilibration was measured using a refractometer

  3. The stochastic thermodynamics of a rotating Brownian particle in a gradient flow

    PubMed Central

    Lan, Yueheng; Aurell, Erik

    2015-01-01

    We compute the entropy production engendered in the environment from a single Brownian particle which moves in a gradient flow, and show that it corresponds in expectation to classical near-equilibrium entropy production in the surrounding fluid with specific mesoscopic transport coefficients. With temperature gradient, extra terms are found which result from the nonlinear interaction between the particle and the non-equilibrated environment. The calculations are based on the fluctuation relations which relate entropy production to the probabilities of stochastic paths and carried out in a multi-time formalism. PMID:26194015

  4. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

    NASA Astrophysics Data System (ADS)

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized N P T ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  5. Nonisothermal fluctuating hydrodynamics and Brownian motion

    NASA Astrophysics Data System (ADS)

    Falasco, G.; Kroy, K.

    2016-03-01

    The classical theory of Brownian dynamics follows from coarse graining the underlying linearized fluctuating hydrodynamics of the solvent. We extend this procedure to globally nonisothermal conditions, requiring only a local thermal equilibration of the solvent. Starting from the conservation laws, we establish the stochastic equations of motion for the fluid momentum fluctuations in the presence of a suspended Brownian particle. These are then contracted to the nonisothermal generalized Langevin description of the suspended particle alone, for which the coupling to stochastic temperature fluctuations is found to be negligible under typical experimental conditions.

  6. NICMOS Filter Wheel Test

    NASA Astrophysics Data System (ADS)

    Malhotra, Sangeeta

    2003-07-01

    This is an engineering test to verify the aliveness, functionality, operability, and electro-mechanical calibration of the NICMOS filter wheel motors and assembly after NCS restart in August 2003. This test has been designed to obviate concerns over possible deformation or breakage of the fitter wheel "soda-straw" shafts due to excess rotational drag torque and/or bending moments which may be imparted due to changes in the dewar metrology from warm-up/cool-down. This test should be executed after the NCS {and filter wheel housing} has reached and approximately equilibrated to its nominal Cycle 11 operating temperature.

  7. Entropic description of gas hydrate ice/liquid equilibrium via enhanced sampling of coexisting phases

    DOE PAGES

    Malolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-04-28

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid/liquid equilibrium is of interest. However, aqueous crystal/liquid transitions are very difficult to simulate. A new MD algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. Furthermore, with replicas spanning the range between β ice and liquid water we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  8. Photon calorimeter

    DOEpatents

    Chow, Tze-Show

    1988-04-22

    A photon calorimeter is provided that comprises a laminar substrate that is uniform in density and homogeneous in atomic composition. A plasma-sprayed coating, that is generally uniform in density and homogeneous in atomic composition within the proximity of planes that are parallel to the surfaces of the substrate, is applied to either one or both sides of the laminar substrate. The plasma-sprayed coatings may be very efficiently spectrally tailored in atomic number. Thermocouple measuring junctions, are positioned within the plasma-sprayed coatings. The calorimeter is rugged, inexpensive, and equilibrates in temperature very rapidly. 4 figs.

  9. A Proposed Dynamic Pressure and Temperature Primary Standard

    PubMed Central

    Rosasco, Gregory J.; Bean, Vern E.; Hurst, Wilbur S.

    1990-01-01

    Diatomic gas molecules have a fundamental vibrational motion whose frequency is affected by pressure in a simple way. In addition, these molecules have well defined rotational energy levels whose populations provide a reliable measure of the thermodynamic temperature. Since information concerning the frequency of vibration and the relative populations can be determined by laser spectroscopy, the gas molecules themselves can serve as sensors of pressure and temperature. Through measurements under static conditions, the pressure and temperature dependence of the spectra of selected molecules is now understood. As the time required for the spectroscopic measurement can be reduced to nanoseconds, the diatomic gas molecule is an excellent candidate for a dynamic pressure/temperature primary standard. The temporal response in this case will be limited by the equilibration time for the molecules to respond to changes in local thermodynamic variables. Preliminary feasibility studies suggest that by using coherent anti-Stokes Raman spectroscopy we will be able to measure dynamic pressure up to 108 Pa and dynamic temperature up to 1500 K with an uncertainty of 5%. PMID:28179756

  10. A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling

    USGS Publications Warehouse

    Palandri, James L.; Kharaka, Yousif K.

    2004-01-01

    Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. The compiled dissolution rate constants range from -0.21 log moles m-2 s-1 for halite, to -17.44 log moles m-2 s-1 for kyanite, for conditions far from equilibrium, at 25 ?C, and pH near neutral. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

  11. Global variation of the para hydrogen fraction in Jupiter's atmosphere and implications for dynamics on the outer planets

    NASA Technical Reports Server (NTRS)

    Conrath, B. J.; Gierasch, P. J.

    1984-01-01

    A detailed analysis of the Voyager infrared spectrometer measurements on Jupiter's atmosphere is presented, and possible implications of para hydrogen disequilibrium for the energetics and dynamics of that atmosphere are examined. The method of data analysis is described, and results for the large scale latitude variation of the para hydrogen fraction are presented. The Jovian results show pronounced latitude variation, and are compared with other parameters including wind fields, thermal structure, and various indicators of atmospheric clouds. The problem of equilibration rate is reexamined, and it is concluded that on Jupiter the equilibration time is longer than the radiative time constant at the level of emission to space, but that this inequality reverses at greater depths. A model for the interaction of fluid motions with the ortho-para conversion process is presented, and a consistent mixing length theory for the reacting ortho-para mixture is developed. Several implications of the Jovian data for atmospheric energetics and stability on the outer planets are presented.

  12. Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

    NASA Astrophysics Data System (ADS)

    Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

    2017-11-01

    In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

  13. Spatial glass transition temperature variations in polymer glass: application to a maltodextrin-water system.

    PubMed

    van Sleeuwen, Rutger M T; Zhang, Suying; Normand, Valéry

    2012-03-12

    A model was developed to predict spatial glass transition temperature (T(g)) distributions in glassy maltodextrin particles during transient moisture sorption. The simulation employed a numerical mass transfer model with a concentration dependent apparent diffusion coefficient (D(app)) measured using Dynamic Vapor Sorption. The mass average moisture content increase and the associated decrease in T(g) were successfully modeled over time. Large spatial T(g) variations were predicted in the particle, resulting in a temporary broadening of the T(g) region. Temperature modulated differential scanning calorimetry confirmed that the variation in T(g) in nonequilibrated samples was larger than in equilibrated samples. This experimental broadening was characterized by an almost doubling of the T(g) breadth compared to the start of the experiment. Upon reaching equilibrium, both the experimental and predicted T(g) breadth contracted back to their initial value.

  14. Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

    PubMed

    Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

    2017-07-21

    Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

  15. The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering

    NASA Astrophysics Data System (ADS)

    Sjöström, J.; Kargl, F.; Fernandez-Alonso, F.; Swenson, J.

    2007-10-01

    The dynamics of water in fresh and in rehydrated white bread is studied using quasielastic neutron scattering (QENS). A diffusion constant for water in fresh bread, without temperature gradients and with the use of a non-destructive technique, is presented here for the first time. The self-diffusion constant for fresh bread is estimated to be Ds = 3.8 × 10-10 m2 s-1 and the result agrees well with previous findings for similar systems. It is also suggested that water exhibits a faster dynamics than previously reported in the literature using equilibration of a hydration-level gradient monitored by vibrational spectroscopy. The temperature dependence of the dynamics of low hydration bread is also investigated for T = 280-350 K. The average relaxation time at constant momentum transfer (Q) shows an Arrhenius behavior in the temperature range investigated.

  16. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jiang, J.; Walters, D. M.; Zhou, D.

    Vapor-deposited glasses can be anisotropic and molecular orientation is important for organic electronics applications. In organic light emitting diodes (OLEDs), for example, the orientation of dye molecules in two-component emitting layers significantly influences emission efficiency. Here we investigate how substrate temperature during vapor deposition influences the orientation of dye molecules in a model two-component system. We determine the average orientation of a linear blue light emitter 1,4-di-[4-( N,N-diphenyl)amino]styrylbenzene (DSA-Ph) in mixtures with aluminum-tris(8-hydroxyquinoline) (Alq 3) by spectroscopic ellipsometry and IR dichroism. We find that molecular orientation is controlled by the ratio of the substrate temperature during deposition and the glassmore » transition temperature of the mixture. Furthermore, these findings extend recent results for single component vapor-deposited glasses and suggest that, during vapor deposition, surface mobility allows partial equilibration towards orientations preferred at the free surface of the equilibrium liquid.« less

  17. Radial magnetic compression in the expelled jet of a plasma deflagration accelerator

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Loebner, Keith T. K., E-mail: kloebner@stanford.edu; Underwood, Thomas C.; Mouratidis, Theodore

    2016-02-29

    A spectroscopic study of a pulsed plasma deflagration accelerator is carried out that confirms the existence of a strong compression in the emerging jet at the exit plane of the device. An imaging spectrometer is used to collect broadened Hα emission from a transaxial slice of the emerging jet at high spatial resolution, and the radial plasma density profile is computed from Voigt fits of the Abel inverted emissivity profiles. The plasma temperature, determined via Doppler broadening of impurity line emission, is compared against the temperature predictions of a radial magnetohydrodynamic equilibrium model applied to the measured density profiles. Empiricalmore » scaling laws developed for the plasma density, combined with the measured and predicted temperatures, indicate that a radially equilibrated Z-pinch is formed within the expelled plasma jet at the exit plane during the deflagration process.« less

  18. Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

    NASA Astrophysics Data System (ADS)

    Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

    2017-07-01

    Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

  19. Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

    PubMed

    Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

    2015-04-09

    In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

    NASA Technical Reports Server (NTRS)

    Sheng, Y. J.; Wasserburg, G. J.; Hutcheon, I. D.

    1992-01-01

    An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

  1. Evidence for Extremely-High-Temperature Melting in the Solar Nebula from a CaAl4O7-bearing Spherule from Murchison

    NASA Astrophysics Data System (ADS)

    Simon, S. B.; Grossman, L.; Davis, A. M.; Beckett, J. R.; Chamberlin, L.

    1993-07-01

    We have recovered a unique refractory spherule (B6) from the Murchison C2 chondrite. Approximately 140 micrometers in diameter, it is concentrically zoned, with an outer rim sequence, from outermost to innermost, of aluminous diopside (10 micrometers thick), anorthite (3 micrometers) and melilite (3 micrometers). Inside the melilite layer is a 7-micrometer-thick, nearly pure (except for a single, diverging-inward spray of hibonite crystals) layer of spinel. Inward from this layer is a 22-micrometer-wide zone of hibonite (~5.5 wt% TiO2) + spinel, in which hibonite laths, 1-4 micrometers across and up to 10 micrometers wide, are predominantly radially oriented and enclosed in spinel. Inward from this zone, presumably at the core of the inclusion, are CaAl4O7, occurring as anhedral grains ~10 micrometers across, and minor perovskite. Some of the hibonite laths protrude into the CaAl4O7. The sequence of mineral assemblages from the spinel shell inward parallels that expected for fractional crystallization of a melt of the composition of B6. Based on this, the inclusion's spherical shape, and its texture (radially oriented hibonite laths, including a diverging-inward spray; laths enclosed in spinel and protruding into CaAl4O7), we conclude that the oxide phases in B6 crystallized from a liquid. The spinel layer indicates that at least some of the spinel was molten; from the bulk composition, calculated liquidus phase relations in the system Al2O3-MgO-CaO [1], and the amount of spinel contained in the layer, we infer a melting temperature >2000 degrees C. This is >500 degrees higher than the maximum temperature at which any condensed major phase is stable at 10-3 atm in a gas of solar composition, but we see no evidence of evaporation. First, the inclusion has a Group II REE pattern, rather than a Group III or an ultrarefractory pattern, which could reflect devolatilization. Second, although evaporation of molten (but not solid) Mg2SiO4 leads to Mg isotopic mass fractionation [2], we found the Mg isotopic composition of spinel and hibonite in B6 to be essentially normal (DELTA 25Mg = 0 +- 2.5 permil). This means that no more than ~15% of the Mg could have evaporated, which, by analogy with experiments with forsterite at 2050 degrees C [2], suggests that the melt was exposed to the solar nebula for a very short time, perhaps as little as two minutes. This could indicate rapid formation of the spinel shell in B6, sealing off the molten interior from the solar nebula. Evaporation of solid spinel could have occurred, but would probably not fractionate Mg isotopes significantly. Evidence of an unusually high temperature history is preserved in the spinel of B6. It averages 1.7 +- 0.4 mol% excess Al2O3 relative to MgAl2O4, unlike the stoichiometric (within analytical error) spinel found in most CAIs. Much larger Al2O3 solubilities than observed in B6 spinel have been produced in synthetic systems at temperatures as low as 1300 degrees C [3]. In our crystallization experiments, excess Al2O3 ranges from 2 mol% in spinel equilibrated with melilite + hibonite + liquid at 1400 degrees C to 30 mol% in spinel equilibrated with liquid at 1499 degrees C. In corundum-bearing runs, excess Al2O3 in spinel increases from 12 mol% at 1349 degrees C to 24 mol% at 1450 degrees C, consistent with [3]. Excess Al2O3 in spinel is directly correlated with aAl2O3/aMgO based on experiments with solids [4]; it should also be correlated with aAl2O3/aMgO of coexisting liquids, and with temperature at constant aAl2O3/aMgO [1]. Spinels in our experiments have large excess Al2O3 contents because coexisting liquids have aAl2O3/aMgO >6 [1]. The bulk composition of B6 and residual liquids produced by crystallization of spinel from this composition have aAl2O3/aMgO ~1 [1], resulting in lower excess Al2O3 in B6 spinel than in our synthetic spinel. In type B inclusions, liquids with which spinel equilibrated also had aAl2O3/aMgO ratios ~1, but because equilibration temperatures were <~1500 degrees C, this spinel has negligible excess Al2O3, consistent with the results of [4]. The larger amounts of excess Al2O3 in B6 spinel indicate that its equilibration temperature was substantially higher than in type Bs (i.e., >~ 1500 degrees C), consistent with the above observations. References: [1] Berman R. G. (1983) Ph.D. thesis, U. British Columbia. [2] Davis A. M. et al. (1990) Nature, 347, 655-658. [3] Viertel H. U. and Seifert F. (1980) N. Jb. Miner. Abh., 140, 89-101. [4] Chamberlin L. et al. (1992) GSA Abs. with Prog., 24, A257.

  2. Electron storage in single wall carbon nanotubes. Fermi level equilibration in semiconductor-SWCNT suspensions.

    PubMed

    Kongkanand, Anusorn; Kamat, Prashant V

    2007-08-01

    The use of single wall carbon nanotubes (SWCNTs) as conduits for transporting electrons in a photoelectrochemical solar cell and electronic devices requires better understanding of their electron-accepting properties. When in contact with photoirradiated TiO(2) nanoparticles, SWCNTs accept and store electrons. The Fermi level equilibration with photoirradiated TiO(2) particles indicates storage of up to 1 electron per 32 carbon atoms in the SWCNT. The stored electrons are readily discharged on demand upon addition of electron acceptors such as thiazine and oxazine dyes (reduction potential less negative than that of the SWCNT conduction band) to the TiO(2)-SWCNT suspension. The stepwise electron transfer from photoirradiated TiO(2) nanoparticles --> SWCNT --> redox couple has enabled us to probe the electron equilibration process and determine the apparent Fermi level of the TiO(2)-SWCNT system. A positive shift in apparent Fermi level (20-30 mV) indicates the ability of SWCNTs to undergo charge equilibration with photoirradiated TiO(2) particles. The dependence of discharge capacity on the reduction potential of the dye redox couple is compared for TiO(2) and TiO(2)-SWCNT systems under equilibration conditions.

  3. Contact lenses and the rate of evaporation measured in vitro; the influence of wear, squalene and wax.

    PubMed

    Vishnubhatla, Sravya; Borchman, Douglas; Foulks, Gary N

    2012-12-01

    Accelerated evaporation of tears may contribute to dry eye symptoms. It is not clear whether contact lenses decrease or increase the rate of evaporation of tears. In this study, the rates of evaporation through contact lenses (ERTCL) were measured in vitro to gain insight to this question. Contact lenses were equilibrated with various solutions to determine if they influenced ERTCL in vitro. ERTCL was measured gravimetrically. ERTCL measured in vitro for used contact lenses was about 20% faster than for buffer alone suggesting that natural tear components bound to the lenses changed the ERTCL. One natural tear component that binds to contact lenses is waxes. Equilibration of contact lenses with wax increased the ERTCL by about 30% suggesting that waxes might potentially increase ERTCL in vivo. Squalene, found in sebum and possibly meibum was infused into the contact lenses as a step toward decreasing the ERTCL. Squalene decreased ERTCL by over 60% in vitro. Soaking a contact lens in DuraSite(®) with benzalkonium chloride (BAK) did not alter the ERTCL. ERTCL were about 40% higher than the evaporation rate of DuraSite(®) alone or without BAK. In addition to lowering the ERTCL, the squalene in contact lenses could be a source of terpenoids to replace the terpenoids deficient in patients with MGD. If the ERTCL could be minimized in vivo, contact lenses could potentially be used to relieve dry eye symptoms in patients with evaporative dry eye. Copyright © 2012 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.

  4. Airborne filter pack measurements of S and Cl in the plume of Redoubt Volcano, Alaska February–May 2009

    USGS Publications Warehouse

    Pfeffer, Melissa; Doukas, Michael P.; Werner, Cynthia A.; Evans, William C.

    2013-01-01

    Filter pack data from six airborne campaigns at Redoubt Volcano, Alaska are reported here. These measurements provide a rare constraint on Cl output from an andesitic eruption at high emission rate (> 104 t d− 1 SO2). Four S/Cl ratios measured during a period of lava dome growth indicate a depth of last magma equilibration of 2–5 km. The S/Cl ratios in combination with COSPEC SO2 emission rate measurements indicate HCl emission rates of 1500–3600 t d− 1 during dome growth. SO2 and HCl emission rates at Redoubt Volcano correlate with each other and were low prior to the eruption, high during the eruption, and low after the eruption. S/Cl ratios measured by filter pack at andesitic volcanoes have a small range of variance, with no clear trends seen for eruptive versus passive activity. The very few S/Cl ratio measurements by filter pack at andesitic volcanoes are not as predictive of future volcanic activity as has been demonstrated for basaltic volcanoes. This may be because there are so few of these measurements. We have demonstrated it is possible to collect these samples by air between explosions during lava dome-building eruptions. We recommend more filter pack sampling be performed at andesitic volcanoes to determine the technique's utility for volcano monitoring. Filter pack data has been demonstrated to be useful for calculating the depth of magma equilibration at volcanoes including Redoubt Volcano.

  5. A comparative study on the cryogenic preservation of semen from the sandhill crane and the domestic fowl

    USGS Publications Warehouse

    Sexton, T.J.; Gee, G.F.; Watson, P.F.

    1978-01-01

    SYNOPSIS: Recent findings on the cryogenic preservation of semen from the crane, Grus canadensis pratensis and the domestic fowl, Gallus domesticus, are compared. Highest levels of post-thaw motility for crane semen (55%) were obtained when semen was diluted 1:1 with the Beltsville Poultry Semen Extender (BPSE) and held for 30 min at 5 C before it was equilibrated with 4% dimethyl sulfoxide (DMSO) for 15 min. In contrast, post-thaw motility for fowl spermatozoa was highest (80%) when semen was diluted 1:3 with BPSE and held for 60 min at 5 C before it was equilibrated with 4% DMSO for 60 min. Post-thaw motility of spermatozoa of both species was highest when the following freezing rates were used: l C per min from +5 to -20 C, 50 C per min from -20 to -80 C, then plunging into liquid nitrogen which resulted in a rate of 160 C per min from -80 to -196 C. One of four crane eggs resulting from insemination with frozen-thawed semen was fertile, whereas 27 of 55 fowl eggs were fertile, but this difference may have been due largely to fewer spermatozoa being inseminated into the female crane than into the fowl.

  6. Petrology of Two Itokawa Particles: Comparison with Equilibrated LL Chondrites

    NASA Technical Reports Server (NTRS)

    Komatsu, M.; Mikouchi, T.; Arai, T.; Fagan, T. J.; Zolensky, M.; Hagiya, K.; Ohsumi, K.; Karouji, Y.

    2015-01-01

    A strong link between Itokawa particles and LL chondrites was confirmed by preliminary examinations of Hayabusa particles [e.g., 1, 2]. Both poorly equilibrated and highly equilibrated particles have been found among the grains returned from Itokawa [1], and it is suggested that they correspond to LL4 and LL5-6, respectively. Here we report the petrography of two Itokawa particles and TEM study of one, and compare them to Antarctic LL chondrites with variable petrologic types (LL4-LL7) in order to understand the metamorphic history of asteroid Itokawa.

  7. Facet-controlled phase separation in supersaturated Au-Ni nanoparticles upon shape equilibration

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Rossberg, D.; Hentschel, M.

    2015-08-17

    Solid-state dewetting is used to fabricate supersaturated, submicron-sized Au-Ni solid solution particles out of thin Au/Ni bilayers by means of a rapid thermal annealing technique. Phase separation in such particles is studied with respect to their equilibrium crystal (or Wulff) shape by subsequent annealing at elevated temperature. It is found that (100) faceting planes of the equilibrated particles are enriched with Ni and (111) faces with Au. Both phases are considered by quantum-mechanical calculations in combination with an error-reduction scheme that was developed to compensate for a missing exchange-correlation potential that would reliably describe both Au and Ni. The observedmore » phase configuration is then related to the minimization of strongly anisotropic elastic energies of Au- and Ni-rich phases and results in a rather unique nanoparticle composite state that is characterized by nearly uniform value of elastic response to epitaxial strains all over the faceted surface. The same conclusion is yielded also by evaluating bi-axial elastic moduli when employing interpolated experimental elastic constants. This work demonstrates a useful route for studying features of physical metallurgy at the mesoscale.« less

  8. Membrane potential and human erythrocyte shape.

    PubMed Central

    Gedde, M M; Huestis, W H

    1997-01-01

    Altered external pH transforms human erythrocytes from discocytes to stomatocytes (low pH) or echinocytes (high pH). The process is fast and reversible at room temperature, so it seems to involve shifts in weak inter- or intramolecular bonds. This shape change has been reported to depend on changes in membrane potential, but control experiments excluding roles for other simultaneously varying cell properties (cell pH, cell water, and cell chloride concentration) were not reported. The present study examined the effect of independent variation of membrane potential on red cell shape. Red cells were equilibrated in a set of solutions with graduated chloride concentrations, producing in them a wide range of membrane potentials at normal cell pH and cell water. By using assays that were rapid and accurate, cell pH, cell water, cell chloride, and membrane potential were measured in each sample. Cells remained discoid over the entire range of membrane potentials examined (-45 to +45 mV). It was concluded that membrane potential has no independent effect on red cell shape and does not mediate the membrane curvature changes known to occur in red cells equilibrated at altered pH. Images FIGURE 2 FIGURE 9 PMID:9138568

  9. Exsolution of Iron-Titanium Oxides in Magnetite in Miller Range (MIL) 03346 Nakhlite: Evidence for Post Crystallization Reduction in the Nakhlite Cumulate Pile

    NASA Technical Reports Server (NTRS)

    Righter, Kevin; Keller, L. P.; Rahman, Z.; Christoffersen, R.

    2012-01-01

    MIL 03346 is one of the most mesostasis-rich nakhlites [1] and thought to have equilibrated at oxygen fugacities near the fayalite-magnetite-quartz oxygen (FMQ) buffer ([2,3]). Studies of FeTi oxides in nakhlites have led to additional constraints on their equilibration temperatures and fO2s [4,5,6,7]. Comparison of these results to fO2s calculated for shergottites indicates that nakhlites are among the most oxidized samples from the martian meteorite suite [2]. The mesostasis of MIL 03346 contains skeletal titanomagnetite. Several scientists noticed several years ago (e.g. [8]) that this titanomagnetite contains very fine oxidation-driven exsolution lamellae (Figure 1). However, the lamellae are so small that they cannot be characterized by electron microprobe analysis (EMPA). Here we select several areas for focused ion beam (FIB) extraction, prepare transmission electron microscopy (TEM) foils, and identify and analyze the lamellae using TEM at the Johnson Space Center (JSC). The resulting analyses are combined with previous work on nakhlites to interpret the thermal and oxidation history of this meteorite group.

  10. Modelling the Evolution of Sea Spray Droplets on a Global Scale

    NASA Astrophysics Data System (ADS)

    Staniec, A.; Vlahos, P.; Monahan, E. C.

    2017-12-01

    Sea spray droplets are an important mechanism for the transport of moisture, heat, and organic material between the ocean and the atmosphere. Spume droplets are the largest of the size spectrum and as such have the potential to transport significant amounts of energy and gases despite their generally short residence time in the atmosphere. A model is developed based on the physical parameterizations from Andreas et al. (1995, 2005)and a range of spume generation functions, coupled with a biogeochemical exchange model for gases developed here to examine the equilibrium temperature and gas exchange of spume droplets under representative open ocean conditions. The modelling approach uses micro-physics to simulate the expected changes to the droplet as it equilibrates with the atmospheric temperature and relative humidity. The effect of temperature differentials and relative humidity variations is explored. A global approach is simulated by using average summer and winter values for SST, salinity, and air temperature throughout the various ocean basins.

  11. The electrolyte challenge for a direct methanol-air polymer electrolyte fuel cell operating at temperatures up to 200 C

    NASA Technical Reports Server (NTRS)

    Savinell, Robert; Yeager, Ernest; Tryk, Donald; Landau, Uziel; Wainright, Jesse; Gervasio, Dominic; Cahan, Boris; Litt, Morton; Rogers, Charles; Scherson, Daniel

    1993-01-01

    Novel polymer electrolytes are being evaluated for use in a direct methanol-air fuel cell operating at temperatures in excess of 100 C. The evaluation includes tests of thermal stability, ionic conductivity, and vapor transport characteristics. The preliminary results obtained to date indicate that a high temperature polymer electrolyte fuel cell is feasible. For example, Nafion 117 when equilibrated with phosphoric acid has a conductivity of at least 0.4 Omega(exp -1)cm(exp -1) at temperatures up to 200 C in the presence of 400 torr of water vapor and methanol vapor cross over equivalent to 1 mA/cm(exp 2) under a one atmosphere methanol pressure differential at 135 C. Novel polymers are also showing similar encouraging results. The flexibility to modify and optimize the properties by custom synthesis of these novel polymers presents an exciting opportunity to develop an efficient and compact methanol fuel cell.

  12. Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

    USGS Publications Warehouse

    Komor, S.C.

    1995-01-01

    The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

  13. Properties of charmonia in a hot equilibrated medium

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Giannuzzi, Floriana; Mannarelli, Massimo

    2009-09-01

    We investigate the properties of charmonia in a thermal medium, showing that with increasing temperature the decay widths of these mesons behave in a nontrivial way. Our analysis is based on a potential model with interaction potential extracted from thermal lattice QCD calculations of the free-energy of a static quark-antiquark pair. We find that in the crossover region some decay widths are extremely enhanced. In particular, at temperatures T{approx}T{sub c} the decay widths of the J/{psi} that depend on the value of the wave function at the origin are enhanced with respect to the values in vacuum by about amore » factor 2. In the same temperature range the decay width of the process {chi}{sub cJ}{yields}J/{psi}+{gamma} is enhanced by approximately a factor 6 with respect to the value in vacuum. At higher temperatures the charmonia states dissociate and the widths of both decay processes become vanishing small.« less

  14. Substrate temperature controls molecular orientation in two-component vapor-deposited glasses

    DOE PAGES

    Jiang, J.; Walters, D. M.; Zhou, D.; ...

    2016-02-22

    Vapor-deposited glasses can be anisotropic and molecular orientation is important for organic electronics applications. In organic light emitting diodes (OLEDs), for example, the orientation of dye molecules in two-component emitting layers significantly influences emission efficiency. Here we investigate how substrate temperature during vapor deposition influences the orientation of dye molecules in a model two-component system. We determine the average orientation of a linear blue light emitter 1,4-di-[4-( N,N-diphenyl)amino]styrylbenzene (DSA-Ph) in mixtures with aluminum-tris(8-hydroxyquinoline) (Alq 3) by spectroscopic ellipsometry and IR dichroism. We find that molecular orientation is controlled by the ratio of the substrate temperature during deposition and the glassmore » transition temperature of the mixture. Furthermore, these findings extend recent results for single component vapor-deposited glasses and suggest that, during vapor deposition, surface mobility allows partial equilibration towards orientations preferred at the free surface of the equilibrium liquid.« less

  15. Studies on the phase diagram of Pb-Fe-O system and standard molar Gibbs energy of formation of 'PbFe5O8.5' and Pb2Fe2O5

    NASA Astrophysics Data System (ADS)

    Sahu, Sulata Kumari; Ganesan, Rajesh; Gnanasekaran, T.

    2012-07-01

    Partial phase diagram of Pb-Fe-O system has been established by phase equilibration studies over a wide temperature range coupled with high temperature solid electrolyte based emf cells. Ternary oxides are found to coexist with liquid lead only at temperatures above 900 K. At temperatures below 900 K, iron oxides coexist with liquid lead. Standard molar Gibbs energy of formation of ternary oxides 'PbFe5O8.5' and Pb2Fe2O5 were determined by measuring equilibrium oxygen partial pressures over relevant phase fields using emf cells and are given by the following expressions: ΔfGmo 'PbFeO'±1.0(kJ mol)=-2208.1+0.6677(T/K) (917⩽T/K⩽1117) ΔfGmo PbFeO±0.8(kJ mol)=-1178.4+0.3724(T/K) (1050⩽T/K⩽1131) .

  16. eQuilibrator--the biochemical thermodynamics calculator.

    PubMed

    Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

    2012-01-01

    The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like 'how much Gibbs energy is released by ATP hydrolysis at pH 5?' are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use.

  17. eQuilibrator—the biochemical thermodynamics calculator

    PubMed Central

    Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

    2012-01-01

    The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like ‘how much Gibbs energy is released by ATP hydrolysis at pH 5?’ are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use. PMID:22064852

  18. Achieving swift equilibration of a Brownian particle using flow-fields

    NASA Astrophysics Data System (ADS)

    Patra, Ayoti; Jarzynski, Christopher

    Can a system be driven to a targeted equilibrium state on a timescale that is much shorter than its natural equilibration time? In a recent experiment, the swift equilibration of an overdamped Brownian particle was achieved by use of an appropriately designed, time-dependent optical trap potential. Motivated by these results, we develop a general theoretical approach for guiding an ensemble of Brownian particles to track the instantaneous equilibrium distribution of a desired potential U (q , t) . In our approach, we use flow-fields associated with the parametric evolution of the targeted equilibrium state to construct an auxiliary potential U (q , t) , such that dynamics under the composite potential U (t) + U (t) achieves the desired evolution. Our results establish a close connection between the swift equilibration of Brownian particles, quantum shortcuts to adiabaticity, and the dissipationless driving of a classical, Hamiltonian system.

  19. Fundamental aspects of the freezing of cells, with emphasis on mammalian ova and embryos. (Aspectos fundamentales de la congelacion de celulas, especialmente ovulos y embriones de mamiferos

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mazur, P.

    1980-01-01

    For most cells there exists an optimum cooling rate. Both supraoptimal rates and suboptimal rates can be very damaging. The optimal rate varies enormously from less than or equal to 1/sup 0/C/min for mammalian preimplantation embryos to greater than or equal to 800/sup 0/C/min for the human red cell. Death at supraoptimal rates is the result of the formation of intracellular ice and its recrystallization during warming. Intracellular ice occurs when cells are cooled too rapidly to allow them to equilibrate by the osmotic withdrawal of intracellular water. The definition of too rapid depends chiefly on the size of themore » cell and its permeability to water. Death at suboptimal rates is a consequence of the major alterations in aqueous solutions produced by ice formation. The chief effects are a major reduction in the fraction of the solution remaining unfrozen at a given temperature and a major increase in the solute concentration of that fraction. Presumably, slow freezing injury is a consequence of one or both of these solution effects. The introduction of molar concentrations of protective solutes (additives) greatly reduces both the fraction frozen and the concentration of electrolytes in the unfrozen channels and in the cell interior. Usually, freezing either kills cells outright or it yields survivors that retain full capacity to function. Although there is the possibility that in some cases survivors may in fact be impaired genetically, all evidence indicates that genetic damage does not occur. But there are clear examples in which freezing does induce nonlethal physiological damage. Particularly striking examples are found in certain mammalian sperm.« less

  20. Using artificial intelligence to predict the equilibrated postdialysis blood urea concentration.

    PubMed

    Fernández, E A; Valtuille, R; Willshaw, P; Perazzo, C A

    2001-01-01

    Total dialysis dose (Kt/V) is considered to be a major determinant of morbidity and mortality in hemodialyzed patients. The continuous growth of the blood urea concentration over the 30- to 60-min period following dialysis, a phenomenon known as urea rebound, is a critical factor in determining the true dose of hemodialysis. The misestimation of the equilibrated (true) postdialysis blood urea or equilibrated Kt/V results in an inadequate hemodialysis prescription, with predictably poor clinical outcomes for the patients. The estimation of the equilibrated postdialysis blood urea (eqU) is therefore crucial in order to estimate the equilibrated (true) Kt/V. In this work we propose a supervised neural network to predict the eqU at 60 min after the end of hemodialysis. The use of this model is new in this field and is shown to be better than the currently accepted methods (Smye for eqU and Daugirdas for eqKt/V). With this approach we achieve a mean difference error of 0.22 +/- 7.71 mg/ml (mean % error: 1.88 +/- 13.46) on the eqU prediction and a mean difference error for eqKt/V of -0.01 +/- 0.15 (mean % error: -0.95 +/- 14.73). The equilibrated Kt/V estimated with the eqU calculated using the Smye formula is not appropriate because it showed a great dispersion. The Daugirdas double-pool Kt/V estimation formula appeared to be accurate and in agreement with the results of the HEMO study. Copyright 2001 S. Karger AG, Basel.

  1. A randomized prospective study of desflurane versus isoflurane in minimal flow anesthesia using “equilibration time” as the change-over point to minimal flow

    PubMed Central

    Mallik, Tanuja; Aneja, S; Tope, R; Muralidhar, V

    2012-01-01

    Background: In the administration of minimal flow anesthesia, traditionally a fixed time period of high flow has been used before changing over to minimal flow. However, newer studies have used “equilibration time” of a volatile anesthetic agent as the change-over point. Materials and Methods: A randomized prospective study was conducted on 60 patients, who were divided into two groups of 30 patients each. Two volatile inhalational anesthetic agents were compared. Group I received desflurane (n = 30) and group II isoflurane (n = 30). Both the groups received an initial high flow till equilibration between inspired (Fi) and expired (Fe) agent concentration were achieved, which was defined as Fe/Fi = 0.8. The mean (SD) equilibration time was obtained for both the agent. Then, a drift in end-tidal agent concentration during the minimal flow anesthesia and recovery profile was noted. Results: The mean equilibration time obtained for desflurane and isoflurane were 4.96 ± 1.60 and 16.96 ± 9.64 min (P < 0.001). The drift in end-tidal agent concentration over time was minimal in the desflurane group (P = 0.065). Recovery time was 5.70 ± 2.78 min in the desflurane group and 8.06 ± 31 min in the isoflurane group (P = 0.004). Conclusion: Use of equilibration time of the volatile anesthetic agent as a change-over point, from high flow to minimal flow, can help us use minimal flow anesthesia, in a more efficient way. PMID:23225926

  2. Ikaite solubility in seawater-derived brines at 1 atm and sub-zero temperatures to 265 K

    NASA Astrophysics Data System (ADS)

    Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

    2013-05-01

    The concentration-based (stoichiometric) equilibrium solubility product of ikaite (CaCO3·6H2O) in seawater and cryogenic seawater-derived brines was determined at 1 atm total pressure over the temperature range from -1.1 to -7.5 °C and the salinity range from 34 to 124 in temperature-salinity pairs representative of sea ice brines. The solubility measurements were obtained in solutions that were undersaturated and supersaturated with respect to ikaite by equilibration with CO2/N2 gas mixtures of known pCO2 (20-400 μatm). The solutions were then equilibrated with synthetic ikaite (seed) for up to 3 months in a closed system. Arrival of the solid-solution system at a long-term chemical equilibrium was indicated by attainment of constant chemical solution composition with respect to total dissolved calcium, total dissolved inorganic carbon, and total alkalinity. Using these measurements, the stoichiometric equilibrium solubility product of ikaite (Ksp,ikaite∗=[Ca][CO32-], in molkgsolution-2) was determined, with the carbonate ion concentration computed from the measured total alkalinity and total dissolved inorganic carbon concentrations. The computed carbonate ion concentration and, by extension, the Ksp,ikaite∗ are both contingent on solving the system of equations that describe the parameters of the CO2 system in seawater by extrapolation to the experimental salinity and temperature conditions. The results show that the pKsp,ikaite∗=-logKsp,ikaite∗ in seawater of salinity 34 at -1.1 °C was 5.362 ± 0.004 and that the pKsp,ikaite∗ in sea ice at the freezing point of brines of salinity greater than 34 can be described as a function of temperature (T, in K) by the equation, pKsp,ikaite∗=-15489.09608+623443.70216T-1+2355.14596lnT, in the temperature range of 265.15 K < T < 271.15 K (-8 °C < t < -2 °C). Brines of low pCO2 (20 μatm) yielded a much slower (>1 month) approach to chemical equilibrium when incubated without seeding ikaite crystals. Simple modeling indicated that ikaite should not precipitate from sea ice brines evolving under closed system conditions with respect to CO2 exchange. To facilitate ikaite precipitation, brine pCO2 reduction due to photosynthesis or CO2 degassing, or both, is necessary.

  3. Native characterization of nucleic acid motif thermodynamics via non-covalent catalysis

    PubMed Central

    Wang, Chunyan; Bae, Jin H.; Zhang, David Yu

    2016-01-01

    DNA hybridization thermodynamics is critical for accurate design of oligonucleotides for biotechnology and nanotechnology applications, but parameters currently in use are inaccurately extrapolated based on limited quantitative understanding of thermal behaviours. Here, we present a method to measure the ΔG° of DNA motifs at temperatures and buffer conditions of interest, with significantly better accuracy (6- to 14-fold lower s.e.) than prior methods. The equilibrium constant of a reaction with thermodynamics closely approximating that of a desired motif is numerically calculated from directly observed reactant and product equilibrium concentrations; a DNA catalyst is designed to accelerate equilibration. We measured the ΔG° of terminal fluorophores, single-nucleotide dangles and multinucleotide dangles, in temperatures ranging from 10 to 45 °C. PMID:26782977

  4. A Coulomb collision algorithm for weighted particle simulations

    NASA Technical Reports Server (NTRS)

    Miller, Ronald H.; Combi, Michael R.

    1994-01-01

    A binary Coulomb collision algorithm is developed for weighted particle simulations employing Monte Carlo techniques. Charged particles within a given spatial grid cell are pair-wise scattered, explicitly conserving momentum and implicitly conserving energy. A similar algorithm developed by Takizuka and Abe (1977) conserves momentum and energy provided the particles are unweighted (each particle representing equal fractions of the total particle density). If applied as is to simulations incorporating weighted particles, the plasma temperatures equilibrate to an incorrect temperature, as compared to theory. Using the appropriate pairing statistics, a Coulomb collision algorithm is developed for weighted particles. The algorithm conserves energy and momentum and produces the appropriate relaxation time scales as compared to theoretical predictions. Such an algorithm is necessary for future work studying self-consistent multi-species kinetic transport.

  5. Ortho and parahydrogen in interstellar material

    NASA Technical Reports Server (NTRS)

    Reeves, R. R.; Harteck, P.

    1979-01-01

    The ortho/para molecular hydrogen ratio in the interstellar medium is considered. It is shown that the ortho/para ratio will be 3:1 in practically all chemical reactions, even at relatively low temperatures. Two examples of exothermic processes that will result in the formation of a 3:1 ortho:para ratio, corresponding to a high-temperature equilibrium, are examined: H2 formation via three-body or surface recombination and catalytic recombination involving electrons and H(-) ions. Gas-phase scrambling ion reactions are also discussed, and it is suggested that virtually all the H2 equilibrated via scrambling reactions involving H(+) and H3(+) ions should exist as parahydrogen in the J ? 0 quantum state. Arguments are given that deuterium cannot interfere with the long scrambling chain that results in parahydrogen formation.

  6. Population Annealing Monte Carlo for Frustrated Systems

    NASA Astrophysics Data System (ADS)

    Amey, Christopher; Machta, Jonathan

    Population annealing is a sequential Monte Carlo algorithm that efficiently simulates equilibrium systems with rough free energy landscapes such as spin glasses and glassy fluids. A large population of configurations is initially thermalized at high temperature and then cooled to low temperature according to an annealing schedule. The population is kept in thermal equilibrium at every annealing step via resampling configurations according to their Boltzmann weights. Population annealing is comparable to parallel tempering in terms of efficiency, but has several distinct and useful features. In this talk I will give an introduction to population annealing and present recent progress in understanding its equilibration properties and optimizing it for spin glasses. Results from large-scale population annealing simulations for the Ising spin glass in 3D and 4D will be presented. NSF Grant DMR-1507506.

  7. Thermodynamic sorption analysis and glass transition temperature of faba bean (Vicia faba L.) protein.

    PubMed

    Alpizar-Reyes, E; Castaño, J; Carrillo-Navas, H; Alvarez-Ramírez, J; Gallardo-Rivera, R; Pérez-Alonso, C; Guadarrama-Lezama, A Y

    2018-03-01

    Freeze-dried faba bean ( Vicia faba L.) protein adsorption isotherms were determined at 25, 35 and 40 °C and fitted with the Guggenheim-Anderson-de Boer model. The pore radius of protein was in the range of 0.87-6.44 nm, so that they were considered as micropores and mesopores. The minimum integral entropy ranged between 4.33 and 4.44 kg H 2 O/100 kg d.s., was regarded as the point of maximum of stability. The glass transition temperature of the protein equilibrated at the different conditions of storage was determined, showing that the protein remained in glassy state for all cases. The protein showed compact and rigid structures, evidenced by microscopy analysis.

  8. Two-Step Calibration of a Multiwavelength Pyrometer for High Temperature Measurement Using a Quartz Lamp

    NASA Technical Reports Server (NTRS)

    Ng, Daniel

    2001-01-01

    There is no theoretical upper temperature limit for pyrometer application in temperature measurements. NASA Glenn's multiwavelength pyrometer can make measurements over wide temperature ranges. However, the radiation spectral response of the pyrometer's detector must be calibrated before any temperature measurement is attempted, and it is recommended that calibration be done at temperatures close to those for which measurements will be made. Calibration is a determination of the constants of proportionality at all wavelengths between the detector's output (voltage) and its input signals (usually from a blackbody radiation source) in order to convert detector output into radiation intensity. To measure high temperatures, the detectors are chosen to be sensitive in the spectral range from 0.4 to 2.5 micrometers. A blackbody furnace equilibrated at around 1000 C is often used for this calibration. Though the detector may respond sensitively to short wavelengths radiation, a blackbody furnace at 1000 C emits only feebly at very short wavelengths. As a consequence, the calibration constants that result may not be the most accurate. For pyrometry calibration, a radiation source emitting strongly at the short wavelengths is preferred. We have chosen a quartz halogen lamp for this purpose.

  9. Thermal-safety margins and the necessity of thermoregulatory behavior across latitude and elevation

    PubMed Central

    Sunday, Jennifer M.; Bates, Amanda E.; Kearney, Michael R.; Colwell, Robert K.; Dulvy, Nicholas K.; Longino, John T.; Huey, Raymond B.

    2014-01-01

    Physiological thermal-tolerance limits of terrestrial ectotherms often exceed local air temperatures, implying a high degree of thermal safety (an excess of warm or cold thermal tolerance). However, air temperatures can be very different from the equilibrium body temperature of an individual ectotherm. Here, we compile thermal-tolerance limits of ectotherms across a wide range of latitudes and elevations and compare these thermal limits both to air and to operative body temperatures (theoretically equilibrated body temperatures) of small ectothermic animals during the warmest and coldest times of the year. We show that extreme operative body temperatures in exposed habitats match or exceed the physiological thermal limits of most ectotherms. Therefore, contrary to previous findings using air temperatures, most ectotherms do not have a physiological thermal-safety margin. They must therefore rely on behavior to avoid overheating during the warmest times, especially in the lowland tropics. Likewise, species living at temperate latitudes and in alpine habitats must retreat to avoid lethal cold exposure. Behavioral plasticity of habitat use and the energetic consequences of thermal retreats are therefore critical aspects of species’ vulnerability to climate warming and extreme events. PMID:24616528

  10. Thermal-safety margins and the necessity of thermoregulatory behavior across latitude and elevation.

    PubMed

    Sunday, Jennifer M; Bates, Amanda E; Kearney, Michael R; Colwell, Robert K; Dulvy, Nicholas K; Longino, John T; Huey, Raymond B

    2014-04-15

    Physiological thermal-tolerance limits of terrestrial ectotherms often exceed local air temperatures, implying a high degree of thermal safety (an excess of warm or cold thermal tolerance). However, air temperatures can be very different from the equilibrium body temperature of an individual ectotherm. Here, we compile thermal-tolerance limits of ectotherms across a wide range of latitudes and elevations and compare these thermal limits both to air and to operative body temperatures (theoretically equilibrated body temperatures) of small ectothermic animals during the warmest and coldest times of the year. We show that extreme operative body temperatures in exposed habitats match or exceed the physiological thermal limits of most ectotherms. Therefore, contrary to previous findings using air temperatures, most ectotherms do not have a physiological thermal-safety margin. They must therefore rely on behavior to avoid overheating during the warmest times, especially in the lowland tropics. Likewise, species living at temperate latitudes and in alpine habitats must retreat to avoid lethal cold exposure. Behavioral plasticity of habitat use and the energetic consequences of thermal retreats are therefore critical aspects of species' vulnerability to climate warming and extreme events.

  11. An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

    NASA Technical Reports Server (NTRS)

    Kiefer, Walter S.; Mittlefehldt, David W.

    2016-01-01

    Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

  12. Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

    2013-04-01

    Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity up to full saturation. References Lécuyer, C. et al. (2009). Chem. Geol., 264, 122-126. [doi:10.1016/j.chemgeo.2009.02.017] Martineau, F. et al. (2012). Chem. Geol., 291, 236-240. [doi:10.1016/j.chemgeo.2011.10.017] Stadler, S. et al. (2012). Chem. Geol., 294-295, 226-242. [doi:10.1016/j.chemgeo.2011.12.006

  13. Stereodirectional Origin of anti-Arrhenius Kinetics for a Tetraatomic Hydrogen Exchange Reaction: Born-Oppenheimer Molecular Dynamics for OH + HBr.

    PubMed

    Coutinho, Nayara D; Aquilanti, Vincenzo; Silva, Valter H C; Camargo, Ademir J; Mundim, Kleber C; de Oliveira, Heibbe C B

    2016-07-14

    Among four-atom processes, the reaction OH + HBr → H2O + Br is one of the most studied experimentally: its kinetics has manifested an unusual anti-Arrhenius behavior, namely, a marked decrease of the rate constant as the temperature increases, which has intrigued theoreticians for a long time. Recently, salient features of the potential energy surface have been characterized and most kinetic aspects can be considered as satisfactorily reproduced by classical trajectory simulations. Motivation of the work reported in this paper is the investigation of the stereodirectional dynamics of this reaction as the prominent reason for the peculiar kinetics: we started in a previous Letter ( J. Phys. Chem. Lett. 2015 , 6 , 1553 - 1558 ) a first-principles Born-Oppenheimer "canonical" molecular dynamics approach. Trajectories are step-by-step generated on a potential energy surface quantum mechanically calculated on-the-fly and are thermostatically equilibrated to correspond to a specific temperature. Here, refinements of the method permitted a major increase of the number of trajectories and the consideration of four temperatures -50, +200, +350, and +500 K, for which the sampling of initial conditions allowed us to characterize the stereodynamical effect. The role is documented of the adjustment of the reactants' mutual orientation to encounter the entrance into the "cone of acceptance" for reactivity. The aperture angle of this cone is dictated by a range of directions of approach compatible with the formation of the specific HOH angle of the product water molecule; and consistently the adjustment is progressively less effective the higher the kinetic energy. Qualitatively, this emerging picture corroborates experiments on this reaction, involving collisions of aligned and oriented molecular beams, and covering a range of energies higher than the thermal ones. The extraction of thermal rate constants from this molecular dynamics approach is discussed and the systematic sampling of the canonical ensemble is indicated as needed for quantitative comparison with the kinetic experiments.

  14. Exercise thermoregulation after 6 h of chair rest, 6 degrees head-down bed-rest, and water immersion deconditioning in men

    NASA Technical Reports Server (NTRS)

    Greenleaf, J. E.; Hutchinson, T.; Shaffer-Bailey, M.; Looft-Wilson, R.

    1996-01-01

    The purpose was to investigate the mechanism for the excessive exercise hyperthermia following deconditioning (reduction of physical fitness). Rectal (Tre) and mean skin (Tsk) temperatures and thermoregulatory responses were measured in six men [mean (SD) age, 32 (6) years; mass, 78.26 (5.80) kg; surface area, 1.95 (0.11) m2; maximum oxygen uptake (VO2max), 48 (6) ml.min-1.kg-1; whilst supine in air at dry bulb temperature 23.2 (0.6) degree C, relative humidity 31.1 (11.1)% and air speed 5.6 (0.1) m.min-1] during 70 min of leg cycle exercise [51 (4)% VO2max] in ambulatory control (AC), or following 6 h of chair rest (CR), 6 degree head-down bed rest (BR), and 20 degree (WI20) and 80 degree (WI80) foot-down water immersion [water temperature, 35.0 (0.1) degree C]. Compared with the AC exercise delta Tre [mean (SD) 0.77 (0.13) degree C (*P < 0.05), after WI80 0.96 (0.13) degree C*, and after WI20 1.03 (0.09) degree C*. All Tsk responded similarly to exercise: they decreased (NS) by 0.5-0.7 degree C in minutes 4-8 and equilibrated at +0.1 to +0.5 degree C at 60-70. Skin heat conductance was not different among the five conditions (range = 147-159 kJ.m-2.h-1.degree C-1). Results from an intercorrelation matrix suggested that total body sweat rate was more closely related to Tre at 70 min (Tre70) than limb sweat rate or blood flow. Only 36% of the variability in Tre70 could be accounted for by total sweating, and less than 10% from total body dehydration. It would appear that multiple factors are involved which may include change in sensitivity of thermo- and osmoreceptors.

  15. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lienhard, D. M.; Huisman, A. J.; Krieger, U. K.

    New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4HSO 4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous icemore » nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.« less

  16. Transport modeling of convection dominated helicon discharges in Proto-MPEX with the B2.5-Eirene code

    NASA Astrophysics Data System (ADS)

    Owen, L. W.; Rapp, J.; Canik, J.; Lore, J. D.

    2017-11-01

    Data-constrained interpretative analyses of plasma transport in convection dominated helicon discharges in the Proto-MPEX linear device, and predictive calculations with additional Electron Cyclotron Heating/Electron Bernstein Wave (ECH/EBW) heating, are reported. The B2.5-Eirene code, in which the multi-fluid plasma code B2.5 is coupled to the kinetic Monte Carlo neutrals code Eirene, is used to fit double Langmuir probe measurements and fast camera data in front of a stainless-steel target. The absorbed helicon and ECH power (11 kW) and spatially constant anomalous transport coefficients that are deduced from fitting of the probe and optical data are additionally used for predictive simulations of complete axial distributions of the densities, temperatures, plasma flow velocities, particle and energy fluxes, and possible effects of alternate fueling and pumping scenarios. The somewhat hollow electron density and temperature radial profiles from the probe data suggest that Trivelpiece-Gould wave absorption is the dominant helicon electron heating source in the discharges analyzed here. There is no external ion heating, but the corresponding calculated ion temperature radial profile is not hollow. Rather it reflects ion heating by the electron-ion equilibration terms in the energy balance equations and ion radial transport resulting from the hollow density profile. With the absorbed power and the transport model deduced from fitting the sheath limited discharge data, calculated conduction limited higher recycling conditions were produced by reducing the pumping and increasing the gas fueling rate, resulting in an approximate doubling of the target ion flux and reduction of the target heat flux.

  17. Induction Speed Is Not a Determinant of Propofol Pharmacodynamics

    PubMed Central

    Doufas, Anthony G.; Bakhshandeh, Maryam; Bjorksten, Andrew R.; Shafer, Steven L.; Sessler, Daniel I.

    2005-01-01

    Summary We used individual pharmacodynamic modeling to demonstrate that different sedation endpoints occur at the same effect site propofol concentration, independent of the infusion rate of propofol. Background Evidence suggests that the rate at which they are infused may influence plasma-effect site equilibration of intravenous anesthetics. We used 5 different rates of propofol administration to test the hypothesis that different sedation endpoints occur at the same effect site propofol concentration, independent of the infusion rate. We concurrently evaluated the automated responsiveness monitor (ARM) against other sedation measures and the propofol effect site concentration. Methods With Human Studies Committee approval, 18 healthy volunteers received 5 consecutive target-controlled propofol infusions. During each infusion the effect site concentration was increased by a rate of 0.1, 0.3, 0.5, 0.7, or 0.9 μg·ml−1·min−1. Bispectral index and ARM were recorded at frequent intervals. The times of syringe drop and loss and recovery of responsiveness were noted. Pharmacokinetic and pharmacodynamic modeling was performed using NONMEM. Results Once the correct rate of plasma-effect site equilibration (ke0) was determined for each individual (ke0 = 0.17 min−1, time-to-peak effect = 2.7 min), the effect site concentrations associated with each clinical measure were not affected by the rate of rise of effect site propofol concentration. ARM correlated with all clinical measures of drug effect. Subjects invariably stopped responding to ARM at lower effect site propofol concentrations than those associated with loss of responsiveness. Conclusions Population-based pharmacokinetics, combined with real-time electroencephalographic measures of drug effect, may provide a means to individualize pharmacodynamic modeling during target-controlled drug delivery. ARM appears useful as an automated measure of sedation and may provide the basis for automated monitoring and titration of sedation for a propofol delivery system. PMID:15505446

  18. Glass transition of polymers in bulk, confined geometries, and near interfaces

    NASA Astrophysics Data System (ADS)

    Napolitano, Simone; Glynos, Emmanouil; Tito, Nicholas B.

    2017-03-01

    When cooled or pressurized, polymer melts exhibit a tremendous reduction in molecular mobility. If the process is performed at a constant rate, the structural relaxation time of the liquid eventually exceeds the time allowed for equilibration. This brings the system out of equilibrium, and the liquid is operationally defined as a glass—a solid lacking long-range order. Despite almost 100 years of research on the (liquid/)glass transition, it is not yet clear which molecular mechanisms are responsible for the unique slow-down in molecular dynamics. In this review, we first introduce the reader to experimental methodologies, theories, and simulations of glassy polymer dynamics and vitrification. We then analyse the impact of connectivity, structure, and chain environment on molecular motion at the length scale of a few monomers, as well as how macromolecular architecture affects the glass transition of non-linear polymers. We then discuss a revised picture of nanoconfinement, going beyond a simple picture based on interfacial interactions and surface/volume ratio. Analysis of a large body of experimental evidence, results from molecular simulations, and predictions from theory supports, instead, a more complex framework where other parameters are relevant. We focus discussion specifically on local order, free volume, irreversible chain adsorption, the Debye-Waller factor of confined and confining media, chain rigidity, and the absolute value of the vitrification temperature. We end by highlighting the molecular origin of distributions in relaxation times and glass transition temperatures which exceed, by far, the size of a chain. Fast relaxation modes, almost universally present at the free surface between polymer and air, are also remarked upon. These modes relax at rates far larger than those characteristic of glassy dynamics in bulk. We speculate on how these may be a signature of unique relaxation processes occurring in confined or heterogeneous polymeric systems.

  19. Thermalized axion inflation

    NASA Astrophysics Data System (ADS)

    Ferreira, Ricardo Z.; Notari, Alessio

    2017-09-01

    We analyze the dynamics of inflationary models with a coupling of the inflaton phi to gauge fields of the form phi F tilde F/f, as in the case of axions. It is known that this leads to an instability, with exponential amplification of gauge fields, controlled by the parameter ξ= dot phi/(2fH), which can strongly affect the generation of cosmological perturbations and even the background. We show that scattering rates involving gauge fields can become larger than the expansion rate H, due to the very large occupation numbers, and create a thermal bath of particles of temperature T during inflation. In the thermal regime, energy is transferred to smaller scales, radically modifying the predictions of this scenario. We thus argue that previous constraints on ξ are alleviated. If the gauge fields have Standard Model interactions, which naturally provides reheating, they thermalize already at ξgtrsim2.9, before perturbativity constraints and also before backreaction takes place. In absence of SM interactions (i.e. for a dark photon), we find that gauge fields and inflaton perturbations thermalize if ξgtrsim3.4 however, observations require ξgtrsim6, which is above the perturbativity and backreaction bounds and so a dedicated study is required. After thermalization, though, the system should evolve non-trivially due to the competition between the instability and the gauge field thermal mass. If the thermal mass and the instabilities equilibrate, we expect an equilibrium temperature of Teq simeq ξ H/bar g where bar g is the effective gauge coupling. Finally, we estimate the spectrum of perturbations if phi is thermal and find that the tensor to scalar ratio is suppressed by H/(2T), if tensors do not thermalize.

  20. Thermalized axion inflation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ferreira, Ricardo Z.; Notari, Alessio, E-mail: rferreira@icc.ub.edu, E-mail: notari@ub.edu

    2017-09-01

    We analyze the dynamics of inflationary models with a coupling of the inflaton φ to gauge fields of the form φ F F-tilde / f , as in the case of axions. It is known that this leads to an instability, with exponential amplification of gauge fields, controlled by the parameter ξ= φ-dot /(2 fH ), which can strongly affect the generation of cosmological perturbations and even the background. We show that scattering rates involving gauge fields can become larger than the expansion rate H , due to the very large occupation numbers, and create a thermal bath of particlesmore » of temperature T during inflation. In the thermal regime, energy is transferred to smaller scales, radically modifying the predictions of this scenario. We thus argue that previous constraints on ξ are alleviated. If the gauge fields have Standard Model interactions, which naturally provides reheating, they thermalize already at ξ∼>2.9, before perturbativity constraints and also before backreaction takes place. In absence of SM interactions (i.e. for a dark photon), we find that gauge fields and inflaton perturbations thermalize if ξ∼>3.4; however, observations require ξ∼>6, which is above the perturbativity and backreaction bounds and so a dedicated study is required. After thermalization, though, the system should evolve non-trivially due to the competition between the instability and the gauge field thermal mass. If the thermal mass and the instabilities equilibrate, we expect an equilibrium temperature of T {sub eq} ≅ ξ H / g-bar where g-bar is the effective gauge coupling. Finally, we estimate the spectrum of perturbations if φ is thermal and find that the tensor to scalar ratio is suppressed by H /(2 T ), if tensors do not thermalize.« less

  1. Collision efficiency of water in the unimolecular reaction CH4 (+H2O) ⇆ CH3 + H (+H2O): one-dimensional and two-dimensional solutions of the low-pressure-limit master equation.

    PubMed

    Jasper, Ahren W; Miller, James A; Klippenstein, Stephen J

    2013-11-27

    The low-pressure-limit unimolecular decomposition of methane, CH4 (+M) ⇆ CH3 + H (+M), is characterized via low-order moments of the total energy, E, and angular momentum, J, transferred due to collisions. The low-order moments are calculated using ensembles of classical trajectories, with new direct dynamics results for M = H2O and new results for M = O2 compared with previous results for several typical atomic (M = He, Ne, Ar, Kr) and diatomic (M = H2 and N2) bath gases and one polyatomic bath gas, M = CH4. The calculated moments are used to parametrize three different models of the energy transfer function, from which low-pressure-limit rate coefficients for dissociation, k0, are calculated. Both one-dimensional and two-dimensional collisional energy transfer models are considered. The collision efficiency for M = H2O relative to the other bath gases (defined as the ratio of low-pressure limit rate coefficients) is found to depend on temperature, with, e.g., k0(H2O)/k0(Ar) = 7 at 2000 K but only 3 at 300 K. We also consider the rotational collision efficiency of the various baths. Water is the only bath gas found to fully equilibrate rotations, and only at temperatures below 1000 K. At elevated temperatures, the kinetic effect of "weak-collider-in-J" collisions is found to be small. At room temperature, however, the use of an explicitly two-dimensional master equation model that includes weak-collider-in-J effects predicts smaller rate coefficients by 50% relative to the use of a statistical model for rotations. The accuracies of several methods for predicting relative collision efficiencies that do not require solving the master equation and that are based on the calculated low-order moments are tested. Troe's weak collider efficiency, βc, includes the effect of saturation of collision outcomes above threshold and accurately predicts the relative collision efficiencies of the nine baths. Finally, a brief discussion is presented of mechanistic details of the energy transfer process, as inferred from the trajectories.

  2. Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.

    A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

  3. Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

    NASA Astrophysics Data System (ADS)

    Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

    2012-09-01

    Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

  4. Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

    DOE PAGES

    Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.; ...

    2017-11-04

    A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

  5. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    PubMed

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  6. Numerical modelling of erosion and assimilation of sulfur-rich substrate by martian lava flows: Implications for the genesis of massive sulfide mineralization on Mars

    NASA Astrophysics Data System (ADS)

    Baumgartner, Raphael J.; Baratoux, David; Gaillard, Fabrice; Fiorentini, Marco L.

    2017-11-01

    Mantle-derived volcanic rocks on Mars display physical and chemical commonalities with mafic-ultramafic ferropicrite and komatiite volcanism on the Earth. Terrestrial komatiites are common hosts of massive sulfide mineralization enriched in siderophile-chalcophile precious metals (i.e., Ni, Cu, and the platinum-group elements). These deposits correspond to the batch segregation and accumulation of immiscible sulfide liquids as a consequence of mechanical/thermo-mechanical erosion and assimilation of sulfur-rich bedrock during the turbulent flow of high-temperature and low-viscosity komatiite lava flows. This study adopts this mineralization model and presents numerical simulations of erosion and assimilation of sulfide- and sulfate-rich sedimentary substrates during the dynamic emplacement of (channelled) mafic-ultramafic lava flows on Mars. For sedimentary substrates containing adequate sulfide proportions (e.g., 1 wt% S), our simulations suggest that sulfide supersaturation in low-temperature (< 1350 °C) flows could be attained at < 200 km distance, but may be postponed in high-temperature lavas flows (> 1400 °C). The precious-metals tenor in the derived immiscible sulfide liquids may be significantly upgraded as a result of their prolonged equilibration with large volumes of silicate melts along flow conduits. The influence of sulfate assimilation on sulfide supersaturation in martian lava flows is addressed by simulations of melt-gas equilibration in the Csbnd Hsbnd Osbnd S fluid system. However, prolonged sulfide segregation and deposit genesis by means of sulfate assimilation appears to be limited by lava oxidation and the release of sulfur-rich gas. The identification of massive sulfide endowments on Mars is not possible from remote sensing data. Yet the results of this study aid to define regions for the potential occurrence of such mineral systems, which may be the large canyon systems Noctis Labyrinthus and Valles Marineris, or the Hesperian channel systems of Mars' highlands (e.g., Kasei Valles), most of which have been periodically draped by mafic-ultramafic lavas.

  7. Vascular endothelial growth factor receptor-3 is a novel target to improve net ultrafiltration in methylglyoxal-induced peritoneal injury.

    PubMed

    Terabayashi, Takeshi; Ito, Yasuhiko; Mizuno, Masashi; Suzuki, Yasuhiro; Kinashi, Hiroshi; Sakata, Fumiko; Tomita, Takako; Iguchi, Daiki; Tawada, Mitsuhiro; Nishio, Ryosuke; Maruyama, Shoichi; Imai, Enyu; Matsuo, Seiichi; Takei, Yoshifumi

    2015-09-01

    Appropriate fluid balance is important for good clinical outcomes and survival in patients on peritoneal dialysis. We recently reported that lymphangiogenesis associated with fibrosis developed in the peritoneal cavity via the transforming growth factor-β1-vascular endothelial growth factor-C (VEGF-C) pathway. We investigated whether VEGF receptor-3 (VEGFR-3), the receptor for VEGF-C and -D, might be a new target to improve net ultrafiltration by using adenovirus-expressing soluble VEGFR-3 (Adeno-sVEGFR-3) in rodent models of peritoneal injury induced by methylglyoxal (MGO). We demonstrated that lymphangiogenesis developed in these MGO models, especially in the diaphragm, indicating that lymphangiogenesis is a common feature in the peritoneal cavity with inflammation and fibrosis. In MGO models, VEGF-D was significantly increased in the diaphragm; however, VEGF-C was not significantly upregulated. Adeno-sVEGFR-3, which was detected on day 50 after administration via tail vein injections, successfully suppressed lymphangiogenesis in the diaphragm and parietal peritoneum in mouse MGO models without significant effects on fibrosis, inflammation, or neoangiogenesis. Drained volume in the peritoneal equilibration test using a 7.5% icodextrin peritoneal dialysis solution (the 7.5% icodextrin peritoneal equilibration test) was improved by Adeno-sVEGFR-3 on day 22 (P<0.05) and day 50 after reduction of inflammation (P<0.01), indicating that the 7.5% icodextrin peritoneal equilibration test identifies changes in lymphangiogenesis. The solute transport rate was not affected by suppression of lymphangiogenesis. In human peritoneal dialysis patients, the dialysate to plasma ratio of creatinine positively correlated with the dialysate VEGF-D concentration (P<0.001). VEGF-D mRNA was significantly higher in the peritoneal membranes of patients with ultrafiltration failure, indicating that VEGF-D is involved in the development of lymphangiogenesis in peritoneal dialysis patients. These results indicate that VEGFR-3 is a new target to improve net ultrafiltration by suppressing lymphatic absorption and that the 7.5% icodextrin peritoneal equilibration test is useful for estimation of lymphatic absorption.

  8. A hydrogen isotope study of CO3 type carbonaceous chondrites; comparison with type 3 ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Morse, A. D.; Newton, J.; Pillinger, C. T.

    1993-01-01

    Meteorites of the Ornans type 3 carbonaceous chondrites exhibit a range in degree of equilibration, attributed to differing amounts of thermal metamorphism. These differences have been used to split the CO3 chondrites into petrologic sub-types from 3.0, least equilibrated, to 3.7, being most equilibrated. This is similar to the system of assigning the type 3 ordinary chondrites into petrologic sub-types 3.0 to 3.9 based upon thermoluminescence (TL) and other properties; however, the actual range of thermal metamorphism experienced by CO3 chondrites is much less than that of the type 3 ordinary chondrites. The least equilibrated ordinary chondrites show evidence of aqueous alteration and have high D/H ratios possibly due to a deuterium-rich organic carrier. The aim of this study was to determine whether the CO3 chondrites, which have experienced similar secondary conditions to the type 3 ordinary chondrites, also contain a similar deuterium-rich carrier. To date a total of 5 CO3 meteorites, out of a set of 11 for which carbon and nitrogen isotopic data are available, have been analyzed. Ornans has not been analyzed yet, because it does not appear to fit in with the metamorphic sequence exhibited by the other CO3 chondrites; it also has an extremely high delta-D value of +2150 percent, unusual for such a comparatively equilibrated meteorite (type 3.4). Initial results indicate that the more equilibrated CO3's tend to have lower delta-D values, analogous to the higher petrologic type ordinary chondrites. However this is complicated by the effects of terrestrial weathering and the small data-set.

  9. Transport of heat and mass in near-critical fluids

    NASA Astrophysics Data System (ADS)

    Garrabos, Yves; Leneindre, B.; Guenoun, P.; Perrot, F.; Beysens, Daniel

    1992-08-01

    In order to investigate some aspects of heat and mass transport in fluids in the absence of gravity, thermal cycles were performed near the liquid-phase critical point of CO2 and SF6 in the TEXUS 25 rocket and during the International Microgravity Laboratory (IML-1) Spacelab mission. In the absence of gravity driven convection, the heat transport is expected to be diffusive and very slow. Experimentally, although the local density and temperature gradients indeed relax by a diffusive process, clear evidence is found of fast and uniform thermal equilibration. This new mechanism is a 'piston effect'.

  10. Vitrification

    NASA Astrophysics Data System (ADS)

    A. Takahashi, Tsuneo

    Vitrification is an alternative to customary approaches to cryopreserve cell, tissue and organ. In this method, ice formation can be prevented by a combination of high solute concentration and rapid cooling, a solution become glassy without ice crystalline formation at temperatures below-115°C. The cell and tissue damage associated with ice formation is avoided, but thawing should be rapid enough to prevent ice growth during warming and they should be equilibrated with the vitrification medium without injury. This approach has been extensively studied in the past few years, and has the potential to be an alternative approach to the cryopreservation of a wide range of biological systems.

  11. Disulphide bond exchange inhibited by air - kinetic and thermodynamic products in a library of macrocyclic cysteine derivatives.

    PubMed

    Cholewiak, Agnieszka; Dobrzycki, Łukasz; Jurczak, Janusz; Ulatowski, Filip

    2018-04-04

    In this paper we present the synthesis and reactivity of dithiols comprising of two cysteine moieties attached to a dipicolinic acid core. Oxidation of these thiols provides oligomeric macrocycles. Monomers with 13-membered rings are kinetic products which are, however, strained and readily transform into higher oligomers under basic conditions or elevated temperature via a disulphide exchange reaction. Dimers, which are the most stable thermodynamic products, equilibrate only under inert conditions with thiolate as a catalyst. Under aerobic conditions, the thiols are oxidised before the equilibrium is reached.

  12. Kinetics and thermodynamics associated with Bi adsorption transitions at Cu and Ni grain boundaries

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tai, Kaiping; Feng, Lin; Dillon, Shen J.

    The grain boundary diffusivity of Au in Cu and Cu-Bi, and Cu in Ni and Ni-Bi are characterized by secondary ion mass spectroscopy depth profiling. Samples are equilibrated in a Bi containing atmosphere at temperatures above and below the onset of grain boundary adsorption transitions, sometimes called complexion transitions. A simple thermo-kinetic model is used to estimate the relative entropic contributions to the grain boundary energies. The results indicate that the entropy term plays a major role in promoting thermally and chemically induced grain boundary complexion transition.

  13. Experimental Techniques for Thermodynamic Measurements of Ceramics

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Putnam, Robert L.; Navrotsky, Alexandra

    1999-01-01

    Experimental techniques for thermodynamic measurements on ceramic materials are reviewed. For total molar quantities, calorimetry is used. Total enthalpies are determined with combustion calorimetry or solution calorimetry. Heat capacities and entropies are determined with drop calorimetry, differential thermal methods, and adiabatic calorimetry . Three major techniques for determining partial molar quantities are discussed. These are gas equilibration techniques, Knudsen cell methods, and electrochemical techniques. Throughout this report, issues unique to ceramics are emphasized. Ceramic materials encompass a wide range of stabilities and this must be considered. In general data at high temperatures is required and the need for inert container materials presents a particular challenge.

  14. Photon Calorimeter

    DOEpatents

    Chow, Tze-Show

    1989-01-01

    A photon calorimeter (20, 40) is provided that comprises a laminar substrate (10, 22, 42) that is uniform in density and homogeneous in atomic composition. A plasma-sprayed coating (28, 48, 52), that is generally uniform in density and homogeneous in atomic composition within the proximity of planes that are parallel to the surfaces of the substrate, is applied to either one or both sides of the laminar substrate. The plasma-sprayed coatings may be very efficiently spectrally tailored in atomic number. Thermocouple measuring junctions (30, 50, 54) are positioned within the plasma-sprayed coatings. The calorimeter is rugged, inexpensive, and equilibrates in temperature very rapidly.

  15. Effect of shape on bone cement polymerization time in knee joint replacement surgery

    PubMed Central

    Yoon, Jung-Ro; Ko, Young-Rok; Shin, Young-Soo

    2018-01-01

    Abstract Background: Although many factors are known to influence the polymerization time of bone cement, it remains unclear which bone cement shape predicts the precise polymerization time. The purpose of this study was to investigate whether different cement shapes influenced polymerization time and to identify the relationship between cement shape and ambient operating theater temperature, relative humidity, and equilibration time. Methods: Samples were gathered prospectively from 237 patients undergoing primary total knee arthroplasty. The cement components were made into 2 different shapes: lump and pan. The time at which no macroscopic indentation of both cement models was possible was recorded as the polymerization time. Results: There was no significant difference between hand mixing (lump shape: 789.3 ± 128.4 seconds, P = .591; pan shape: 899.3 ± 152.2 seconds, P = .584) and vacuum mixing (lump shape: 780.2 ± 131.1 seconds, P = .591; pan shape: 909.9 ± 143.3 seconds, P = .584) in terms of polymerization time. Conversely, the polymerization time was significantly shorter for Antibiotic Simplex (lump shape: 757.4 ± 114.9 seconds, P = .001; pan shape: 879.5 ± 125.0 seconds, P < .001) when compared with Palacos R+G (lump shape: 829.0 ± 139.3 seconds, P = .001; pan shape: 942.9 ± 172.0 seconds, P < .001). Polymerization time was also significantly longer (P < .001) for the pan shape model (904 ± 148.0 seconds) when compared with the lump shape model (785.2 ± 129.4 seconds). In addition, the polymerization time decreased with increasing temperature (lump shape: R2 = 0.334, P < .001; pan shape: R2 = 0.375, P < .001), humidity (lump shape: R2 = 0.091, P < .001; pan shape: R2 = 0.106, P < .001), and equilibration time (lump shape: R2 = 0.073, P < .001; pan shape: R2 = 0.044, P < .001). Conclusions: The polymerization time was equally affected by temperature, relative humidity, and equilibration time regardless of bone cement shape. Furthermore, the pan shape model better reflected the cement polymerization time between implant and bone compared with the lump shape model. The current findings suggest that, clinically, constant pressure with the knee in <45° of flexion needs to be applied until remaining pan shaped cement is completely polymerized. PMID:29703041

  16. A petrologic, thermodynamic and experimental study of brachinites: Partial melt residues of an R chondrite-like precursor

    NASA Astrophysics Data System (ADS)

    Gardner-Vandy, Kathryn G.; Lauretta, Dante S.; McCoy, Timothy J.

    2013-12-01

    The primitive achondrites provide a window into the initial melting of asteroids in the early solar system. The brachinites are olivine-dominated meteorites with a recrystallized texture that we and others interpret as evidence of partial melting and melt removal on the brachinite parent body. We present a petrologic, thermodynamic and experimental study of the brachinites to evaluate the conditions under which they formed and test our hypothesis that the precursor material to the brachinites was FeO-rich compared to the precursors of other primitive achondrites. Petrologic analysis of six brachinites (Brachina, Allan Hills (ALH) 84025, Hughes 026, Elephant Moraine (EET) 99402, Northwest Africa (NWA) 3151, and NWA 4969) and one brachinite-like achondrite (NWA 5400) shows that they are meteorites with recrystallized texture that are enriched in olivine (⩾80 vol.%) and depleted in other minerals with respect to a chondritic mineralogy. Silicates in the brachinites are FeO-rich (Fa32-36). Brachinite-like achondrite Northwest Africa 5400 is similar in mineralogy and texture to the brachinites but with a slightly lower FeO-content (Fa30). Thermodynamic calculations yield equilibration temperatures above the Fe,Ni-FeS cotectic temperature (∼950 °C) for all meteorites studied here and temperatures above the silicate eutectic (∼1050 °C) for all but two. Brachina formed at an fO2 of ∼IW, and the other brachinites and NWA 5400 formed at ∼IW - 1. All the meteorites show great evidence of formation by partial melting having approximately chondritic to depleted chondritic mineralogies, equilibrated mineral compositions, and recrystallized textures, and having reached temperatures above that required for melt generation. In an attempt to simulate the formation of the brachinite meteorites, we performed one-atmosphere, gas-mixing partial melting experiments of R4 chondrite LaPaz Ice Field 03639. Experiments at 1250 °C and an oxygen fugacity of IW - 1 produce residual phases that are within the mineralogy and mineral compositions of the brachinites. These experiments provide further evidence for the formation of brachinites as a result of partial melting of a chondritic precursor similar in mineralogy and mineral compositions to the R chondrites.

  17. A New Method of Estimating Atomic Charges by Electronegativity Equilibration.

    ERIC Educational Resources Information Center

    Smith, Derek W.

    1990-01-01

    Presented is a modification of Bratsch's prescription so that difficult problems are obviated while simple, familiar Pauling electronegativities are retained. Discussed are the equilibration of electronegativity in molecules, group electronegativities, coordination compounds and molecules with dative bonds, ions, and correlation with core…

  18. Diagenetic palaeotemperatures from aqueous fluid inclusions: re- equilibration of inclusions in carbonate cements by burial heating.

    USGS Publications Warehouse

    Burruss, R.C.

    1987-01-01

    Calculations based on the observed behaviour of inclusions in fluorite under external confining P allows prediction of the T and depths of burial necessary to initiate re-equilibration of aqueous inclusions in the common size range 40-4 mu m. Heating of 20-60oC over the initial trapping T may cause errors of 10-20oC in the homogenization T. This suggests that re-equilibration may cause aqueous inclusions in carbonates to yield a poor record of their low-T history, but a useful record of the maximum T experienced by the host rock. Previous work suggests that inclusions containing petroleum fluids will be less susceptible to re-equilibration.This and the following six abstracts represent papers presented at a joint meeting of the Applied Mineralogy Group of the Mineralogical Society and the Petroleum Group of the Geological Society held in Newcastle upon Tyne in April 1986.-R.A.H.

  19. A relationship between dissolved CO2 and the non-volatile chemistry of rainwater.

    NASA Astrophysics Data System (ADS)

    Durham, Brian; Pfrang, Christian

    2016-04-01

    Measurements of a volatile acid component in UK rainwater in 2009 implicated CO2, and speculated `a concentrating mechanism (that) could mean that this weakly soluble molecule is recycled at a faster rate than inferred by its Henry's Law constant'. Last year's EGU Presentation 2015-3386 confirmed that the `saturated CO2 content (of UK rainwater) is insignificant, the bulk transport being the volatile component'. However the atmospheric capture mechanism remains enigmatic. For pure water, improved temperature control has discounted the predicted upturn in the Henry coefficient for 450Pa CO2 as the temperature approached freezing point (http://presentations.copernicus.org/EGU2015-3386_presentation.pptx), and the focus has therefore turned to rainwater chemistry. For a mid-range sample the Henry value was: • significantly higher than pure water at 20'C; • but decreasing with lower temperatures. The higher Henry constant might suggest that, as an acid anhydride, CO2 is subject to selective capture where cloud water is alkaline (terrestrial dust or marine aerosol). Analysis has however shown no simple relationship between [CO2]aq and either acidity or conductivity of the carrier water. Seeking therefore a coherent distribution, stripped CO2 was plotted against Δ[H+], from which this paper presents a tight wedge-shaped distribution of 263 UK rain/snow events. The inference is that [CO2]aq is not related directly to [H+], but possibly to Group 1 and 2 cations from marine aerosol that are buffering the cloud water acidity. By contrast, the unexpected decrease in CO2 yield with lower temperatures proved to be an artefact of a progressively slower rate of de-gassing, cooler samples still equilibrating after 100 minutes. An ultrasound stripper is therefore being developed to speed the Henry measurements, and for reproducibility it is proposed to dilute a proprietary `standard Atlantic sea water' to a representative range of conductivities, to be called `standard rainwater'. Any temptation to extrapolate from English results to address the global boundary layer is resisted pending ΔpH values from other stations, which are herewith invited in anticipation of IPCC AR6.

  20. Comparative analysis of nitrite uptake and hemoglobin-nitrite reactions in erythrocytes: sorting out uptake mechanisms and oxygenation dependencies.

    PubMed

    Jensen, Frank B; Rohde, Sabina

    2010-04-01

    Nitrite uptake into red blood cells (RBCs) precedes its intracellular reactions with hemoglobin (Hb) that forms nitric oxide (NO) during hypoxia. We investigated the uptake of nitrite and its reactions with Hb at different oxygen saturations (So(2)), using RBCs with (carp and rabbit) and without (hagfish and lamprey) anion exchanger-1 (AE1) in the membrane, with the aim to unravel the mechanisms and oxygenation dependencies of nitrite transport. Added nitrite rapidly diffused into the RBCs until equilibrium. The distribution ratio of nitrite across the membrane agreed with that expected from HNO(2) diffusion and AE1-mediated facilitated NO(2)(-) diffusion. Participation of HNO(2) diffusion was emphasized by rapid transmembrane nitrite equilibration also in the natural AE1 knockouts. Following the equilibration, nitrite was consumed by reacting with Hb, which created a continued inward diffusion controlled by intracellular reaction rates. Changes in nitrite uptake with So(2), pH, or species were accordingly explained by corresponding changes in reaction rates. In carp, nitrite uptake rates increased linearly with decreasing So(2) over the entire So(2) range. In rabbit, nitrite uptake rates were highest at intermediate So(2), producing a bell-shaped relationship with So(2). Nitrite consumption increased approximately 10-fold with a 1 unit decrease in pH, as expected from the involvement of protons in the reactions with Hb. The reaction of nitrite with deoxyhemoglobin was favored over that with oxyhemoglobin at intermediate So(2). We propose a model for RBC nitrite uptake that involves both HNO(2) diffusion and AE1-mediated transport and that explains both the present and previous (sometimes puzzling) results.

  1. CO2-ECBM related coupled physical and mechanical transport processes

    NASA Astrophysics Data System (ADS)

    Gensterblum, Y.; Sartorius, M.; Busch, A.; Krooss, B. M.; Littke, R.

    2012-12-01

    The interrelation of cleat transport processes and mechanical properties was investigated by permeability tests at different stress levels (60% to 130% of in-situ stress) with sorbing (CH4, CO2) and inert gases (N2, Ar, He) on a subbituminous A coal from the Surat Basin, Queensland Australia (figure). From the flow tests under controlled triaxial stress conditions the Klinkenberg-corrected "true" permeability coefficients and the Klinkenberg slip factors were derived. The "true"-, absolute or Klinkenberg-corrected permeability depends on gas type. Following the approach of Seidle et al. (1992) the cleat volume compressibility (cf) was calculated from observed changes in apparent permeability upon variation of external stress (at equal mean gas pressures). The observed effects also show a clear dependence on gas type. Due to pore or cleat compressibility the cleat aperture decreases with increasing effective stress. Vice versa, with increasing mean pore pressure at lower confining pressure an increase in permeability is observed, which is attributed to a widening of cleat aperture. Non-sorbing gases like helium and argon show higher apparent permeabilities than sorbing gases like methane and CO2. Permeability coefficients measured with successively increasing mean gas pressures were consistently lower than those determined at decreasing mean gas pressures. The kinetics of matrix transport processes were studied by sorption tests on different particle sizes at various moisture contents and temperatures (cf. Busch et al., 2006). Methane uptake rates were determined from the pressure decline curves recorded for each particle-size fraction, and "diffusion coefficients" were calculated using several unipore and bidisperse diffusion models. While the CH4 sorption capacity of moisture-equilibrated coals was significantly lower (by 50%) than that of dry coals, no hysteresis was observed between sorption and desorption on dry and moisture-equilibrated samples and the sorption isotherms recorded for different particle sizes were essentially identical. The CH4 uptake rates were lower by a factor of two for moist coals than for dry coals. Busch, A., Gensterblum, Y., Krooss, B.M. and Siemons, N., 2006. Investigation of high-pressure selective adsorption/desorption behaviour of CO2 and CH4 on coals: An experimental study. International Journal of Coal Geology, 66(1-2): 53-68. Seidle, J.P., Jeansonne, M.W. and Erickson, D.J., 1992. Application of Matchstick Geometry to Stress-Dependent Permeability in Coals, SPE Rocky Mountain Regional Meeting, Casper, Wyoming.

  2. The acid-tolerant L-arabinose isomerase from the mesophilic Shewanella sp. ANA-3 is highly active at low temperatures

    PubMed Central

    2011-01-01

    Background L-arabinose isomerases catalyse the isomerization of L-arabinose into L-ribulose at insight biological systems. At industrial scale of this enzyme is used for the bioconversion of D-galactose into D-tagatose which has many applications in pharmaceutical and agro-food industries. The isomerization reaction is thermodynamically equilibrated, and therefore the bioconversion rates is shifted towards tagatose when the temperature is increased. Moreover, to prevent secondary reactions it will be of interest to operate at low pH. The profitability of this D-tagatose production process is mainly related to the use of lactose as cheaper raw material. In many dairy products it will be interesting to produce D-tagatose during storage. This requires an efficient L-arabinose isomerase acting at low temperature and pH values. Results The gene encoding the L-arabinose isomerase from Shewanella sp. ANA-3 was cloned and overexpressed in Escherichia coli. The purified protein has a tetrameric arrangement composed by four identical 55 kDa subunits. The biochemical characterization of this enzyme showed that it was distinguishable by its maximal activity at low temperatures comprised between 15-35°C. Interestingly, this biocatalyst preserves more than 85% of its activity in a broad range of temperatures from 4.0 to 45°C. Shewanella sp. ANA-3 L-arabinose isomerase was also optimally active at pH 5.5-6.5 and maintained over 80% of its activity at large pH values from 4.0 to 8.5. Furthermore, this enzyme exhibited a weak requirement for metallic ions for its activity evaluated at 0.6 mM Mn2+. Stability studies showed that this protein is highly stable mainly at low temperature and pH values. Remarkably, T268K mutation clearly enhances the enzyme stability at low pH values. Use of this L-arabinose isomerase for D-tagatose production allows the achievement of attractive bioconversion rates of 16% at 4°C and 34% at 35°C. Conclusions Here we reported the purification and the biochemical characterization of the novel Shewanella sp. ANA-3 L-arabinose isomerase. Determination of the biochemical properties demonstrated that this enzyme was highly active at low temperatures. The generated T268K mutant displays an increase of the enzyme stability essentially at low pH. These features seem to be very attractive for the bioconversion of D-galactose into D-tagatose at low temperature which is very interesting from industrial point of view. PMID:22074172

  3. Modeling Hf-W Evolution for Earth, Moon and Mars in Grand Tack Accretion Simulations: The Isotopic Consequences of Rapid Accretion

    NASA Astrophysics Data System (ADS)

    Zube, N.; Nimmo, F.; Jacobson, S. A.; Fischer, R. A.

    2017-12-01

    Short-lived isotopes, such as the decay of lithophile 182Hf into siderophile 182W with a half-life of 9 My, can provide constraints on the timescales of planetary core formation and accretion. Classical accretion scenarios have produced Hf-W isotopic outcomes like those measured presently on the Earth [2,3]. We examine Grand Tack accretion simulations [4,5] and determine the mantle equilibration conditions necessary to produce the observed tungsten isotopic anomaly. Additionally, we follow Hf-W evolution for pairs of bodies that experience a last giant impact fitting the conditions of Earth's Moon-forming collision. In this way, we determine the likelihood of producing the observed almost indistinguishable W isotope anomalies of the Earth and Moon mantles [6]. We model Hf-W evolution for growing planets in 141 N-body simulations during late accretion in the Grand Tack scenario. For each case, we vary the equilibration factor during collisions—the fraction of impactor core that experiences re-equilibration with the entire target mantle—in steps ranging from none (cores merging) to complete equilibration. For Earth-like and Mars-like surviving planets, we find that cases with a high equilibration factor (k > 0.8) and an intermediate (2:1 - 4:1) ratio of initial embryo mass to planetesimal mass were most frequently able to approximate the observed W measurements for Earth and Mars. The equilibration factor required is more restrictive than the one found for classical accretion scenarios [2,3] and may not be consistent with fluid-dynamical predictions [7]. Moons made of impactor material from Earth's last giant impact are only able to result in an Earth-Moon pair having sufficiently similar W anomalies with a likelihood of 8% or less across all simulations. This indicates that a scenario where the Moon isotopically equilibrated with the Earth's mantle after the impact [8] may be required to explain the measured values. [1] Kleine et al. 2009 [2] Nimmo et al. 2010 [3] Rudge et al. 2010 [4] Walsh et al. 2009 [5] Jacobson et al. 2014 [6] Touboul et al., 2007 [7] Deguen et al. 2014 [8] Pahlevan and Stevenson 2007

  4. Evaluation of alternative filter media for particulate matter emission testing of residential wood heating devices

    DOE PAGES

    Allen, George; Rector, Lisa; Butcher, Thomas; ...

    2017-07-31

    The performance of Teflon-coated glass fiber filter media (Pallflex Emfab TX40) is evaluated for particulate matter (PM) sampling of residential wood heating devices in a dilution tunnel. Thirty samples of varying duration and PM loading and concentration were collected from an U.S. Environmental Protection Agency (EPA) Method 28 dilution tunnel using dual Method 5G sample trains with untreated glass fiber and Emfab filters. Filters were weighed soon after the end of sampling and again the next day after equilibration at 35% relative humidity (RH). PM concentrations from both types of filters agreed very well with 1-day equilibration, demonstrating that Emfabmore » filters are appropriate for use in measuring PM from residential wood burning appliances in a dilution tunnel and have performance equal to or better than the glass fiber filter media. Agreement between filter media without equilibration was erratic, with PM from glass fiber filter samples varying from slightly less than the Emfab samples to as much as 2.8 times higher. Some of the glass fiber filters lost substantial mass with equilibration, with the highest percent loss at lower filter mass loadings. Mass loss for Emfab samples was a small percentage of the mass and very consistent across the range of mass loadings. Taken together, these results may indicate water uptake on the glass fiber media that is readily removed with 1-day equilibration at moderate RH conditions. Implications: EPA regulations now allow the use of either glass fiber or Teflon filter media for wood appliance PM emission testing. Teflon filter media minimizes the potential for acid-gas PM artifacts on glass fiber filters; this is important as EPA moves toward the use of locally sourced cordwood for testing that may have higher sulfur content. This work demonstrates that the use of Teflon-coated glass fiber filters can give similar PM measurement results to glass fiber filters after 1 day of equilibration. With no equilibration, measured PM from glass fiber filters was usually higher than from Teflon-coated glass fiber filters.« less

  5. Evaluation of alternative filter media for particulate matter emission testing of residential wood heating devices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Allen, George; Rector, Lisa; Butcher, Thomas

    The performance of Teflon-coated glass fiber filter media (Pallflex Emfab TX40) is evaluated for particulate matter (PM) sampling of residential wood heating devices in a dilution tunnel. Thirty samples of varying duration and PM loading and concentration were collected from an U.S. Environmental Protection Agency (EPA) Method 28 dilution tunnel using dual Method 5G sample trains with untreated glass fiber and Emfab filters. Filters were weighed soon after the end of sampling and again the next day after equilibration at 35% relative humidity (RH). PM concentrations from both types of filters agreed very well with 1-day equilibration, demonstrating that Emfabmore » filters are appropriate for use in measuring PM from residential wood burning appliances in a dilution tunnel and have performance equal to or better than the glass fiber filter media. Agreement between filter media without equilibration was erratic, with PM from glass fiber filter samples varying from slightly less than the Emfab samples to as much as 2.8 times higher. Some of the glass fiber filters lost substantial mass with equilibration, with the highest percent loss at lower filter mass loadings. Mass loss for Emfab samples was a small percentage of the mass and very consistent across the range of mass loadings. Taken together, these results may indicate water uptake on the glass fiber media that is readily removed with 1-day equilibration at moderate RH conditions. Implications: EPA regulations now allow the use of either glass fiber or Teflon filter media for wood appliance PM emission testing. Teflon filter media minimizes the potential for acid-gas PM artifacts on glass fiber filters; this is important as EPA moves toward the use of locally sourced cordwood for testing that may have higher sulfur content. This work demonstrates that the use of Teflon-coated glass fiber filters can give similar PM measurement results to glass fiber filters after 1 day of equilibration. With no equilibration, measured PM from glass fiber filters was usually higher than from Teflon-coated glass fiber filters.« less

  6. Monitoring local heating around an interventional MRI antenna with RF radiometry

    PubMed Central

    Ertürk, M. Arcan; El-Sharkawy, AbdEl-Monem M.; Bottomley, Paul A.

    2015-01-01

    Purpose: Radiofrequency (RF) radiometry uses thermal noise detected by an antenna to measure the temperature of objects independent of medical imaging technologies such as magnetic resonance imaging (MRI). Here, an active interventional MRI antenna can be deployed as a RF radiometer to measure local heating, as a possible new method of monitoring device safety and thermal therapy. Methods: A 128 MHz radiometer receiver was fabricated to measure the RF noise voltage from an interventional 3 T MRI loopless antenna and calibrated for temperature in a uniformly heated bioanalogous gel phantom. Local heating (ΔT) was induced using the antenna for RF transmission and measured by RF radiometry, fiber-optic thermal sensors, and MRI thermometry. The spatial thermal sensitivity of the antenna radiometer was numerically computed using a method-of-moment electric field analyses. The gel’s thermal conductivity was measured by MRI thermometry, and the localized time-dependent ΔT distribution computed from the bioheat transfer equation and compared with radiometry measurements. A “H-factor” relating the 1 g-averaged ΔT to the radiometric temperature was introduced to estimate peak temperature rise in the antenna’s sensitive region. Results: The loopless antenna radiometer linearly tracked temperature inside a thermally equilibrated phantom up to 73 °C to within ±0.3 °C at a 2 Hz sample rate. Computed and MRI thermometric measures of peak ΔT agreed within 13%. The peak 1 g-average temperature was H = 1.36 ± 0.02 times higher than the radiometric temperature for any media with a thermal conductivity of 0.15–0.50 (W/m)/K, indicating that the radiometer can measure peak 1 g-averaged ΔT in physiologically relevant tissue within ±0.4 °C. Conclusions: Active internal MRI detectors can serve as RF radiometers at the MRI frequency to provide accurate independent measures of local and peak temperature without the artifacts that can accompany MRI thermometry or the extra space needed to accommodate alternative thermal transducers. A RF radiometer could be integrated in a MRI scanner to permit “self-monitoring” for assuring device safety and/or monitoring delivery of thermal therapy. PMID:25735295

  7. ANALYSES OF FISH TISSUE BY VACUUM DISTILLATION/GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    EPA Science Inventory

    The analyses of fish tissue using VD/GC/MS with surrogate-based matrix corrections is described. Techniques for equilibrating surrogate and analyte spikes with a tissue matrix are presented, and equilibrated spiked samples are used to document method performance. The removal of a...

  8. Conventional slow freezing cryopreserves mouflon spermatozoa better than vitrification.

    PubMed

    Pradiee, J; Esteso, M C; Castaño, C; Toledano-Díaz, A; Lopez-Sebastián, A; Guerra, R; Santiago-Moreno, J

    2017-04-01

    This work examines the effectiveness of a TCG (Tris, citric acid, glucose, 6% egg yolk and 5% glycerol) and a TEST (TES, Tris, glucose, 6% egg yolk and 5% glycerol) sperm extender in the freezing of mouflon spermatozoa at slow cooling rates, using different pre-freezing equilibration times (2-3 hr). It also examines the tolerance of mouflon spermatozoa to different concentrations of cryoprotectants (5, 10, 20% glycerol; 5%, 10%, 20% dimethyl sulfoxide; 6% polyvinylpyrrolidone) and/or sucrose (100, 300, 500 mm). The highest quality (p < .01) thawed spermatozoa were obtained when using the TEST extender and an equilibration time of 3 hr. Sperm motility and membrane integrity were strongly reduced when using rapid freezing rates (60-85°C min -1 ), independent of the concentration of cryoprotectants. The lowest sucrose concentration (100 mm) provided the highest (p < .05) percentage of motile spermatozoa and live spermatozoa with an intact acrosome. Vitrified-warmed sperm variables were at their best when the spermatozoa was diluted in TCG-6% egg yolk + 100 mm sucrose and warmed at 60°C. Slow warming at 37°C strongly reduced (p < .05) sperm motility and viability. However, sperm vitrification returned lower fertility, sperm motility and sperm viability values than conventional sperm freezing. © 2016 Blackwell Verlag GmbH.

  9. The Calvin Cycle Inevitably Produces Sugar-Derived Reactive Carbonyl Methylglyoxal During Photosynthesis: A Potential Cause of Plant Diabetes

    PubMed Central

    Takagi, Daisuke; Inoue, Hironori; Odawara, Mizue; Shimakawa, Ginga; Miyake, Chikahiro

    2014-01-01

    Sugar-derived reactive carbonyls (RCs), including methylglyoxal (MG), are aggressive by-products of oxidative stress known to impair the functions of multiple proteins. These advanced glycation end-products accumulate in patients with diabetes mellitus and cause major complications, including arteriosclerosis and cardiac insufficiency. In the glycolytic pathway, the equilibration reactions between dihydroxyacetone phosphate and glyceraldehyde 3-phosphate (GAP) have recently been shown to generate MG as a by-product. Because plants produce vast amounts of sugars and support the same reaction in the Calvin cycle, we hypothesized that MG also accumulates in chloroplasts. Incubating isolated chloroplasts with excess 3-phosphoglycerate (3-PGA) as the GAP precursor drove the equilibration reaction toward MG production. The rate of oxygen (O2) evolution was used as an index of 3-PGA-mediated photosynthesis. The 3-PGA- and time-dependent accumulation of MG in chloroplasts was confirmed by HPLC. In addition, MG production increased with an increase in light intensity. We also observed a positive linear relationship between the rates of MG production and O2 evolution (R = 0.88; P < 0.0001). These data provide evidence that MG is produced by the Calvin cycle and that sugar-derived RC production is inevitable during photosynthesis. Furthermore, we found that MG production is enhanced under high-CO2 conditions in illuminated wheat leaves. PMID:24406631

  10. LEW 88180, LEW 87119, and ALH 85119: New EH6, EL7, and EL4 Enstatite Chondrites

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Benoit, P. H.; Sears, D. W. G.

    1993-07-01

    The EH and EL chondrites formed in a uniquely reducing environment, containing low-Fe pyroxene, abundant metal, and a number of unusual sulphides and other minerals [1]. An important aspect of their history is that while the EL chondrites consist predominantly of metamorphosed meteorites, the EH consist primarily of little-metamorphosed meteorites (e.g., [2]), and yet EL chondrites have lower equilibrium temperatures than EH chondrite [3,4]. To help understand this observation and its implication for the history of the classes, we have been searching for new enstatite chondrites, looking especially for meteorites of previously unknown chemical-petrologic class. Using our normal INAA methods [5] and sample splits of 100-200 mg, the bulk composition of nine Antarctic enstatite chondrites and one fall were determined. The data were used to assign the meteorites to chemical classes, the Ni/Ir vs. Al/V plot (Fig. 1) being especially useful since it uses the refractory element difference between EH and EL chondrites and is insensitive to metal-silicate heterogeneity. The well-analyzed Qingzhen was included to check our method. ALH84170, ALH84206, and EET87746, which Mason described as E3, E4, and E4 were all found to be EH chondrites [6]. Our data for the three paired EL3 chondrites were discussed earlier (MAC88136, 88180, and 88184) [7,8]. LEW88180, LEW87119, and ALH85119, which Mason described as type E6, E6, and E4 respectively [6], are EH, EL, and EL; thus LEW88180 and ALH85119 appear to be the first EH6 and EL4 chondrites. The compositions of kamacite, phosphide, and niningerite-alabandite (Fig. 2) for ALH84170, ALH84206, EET87746, LEW88180, and ALH85119 are consistent with Mason's petrologic type assignments [6]. The mineral composition of LEW88180 (2.7% Si and 9.4% Ni in the kamacite, 7.8% Ni in the phosphide, and 60% FeS in the niningerite) confirms our classification of this meteorite as EH6. ALH85119 contains kamacite with 0.5% Si and 7% Ni, phosphide with 46% Ni and alabandite with 22% FeS, confirming its classification as the first EL4 chondrite. The LEW87119 meteorite has kamacite with 1.5% Si and 9.1% Ni, troilite with 2.9% Cr and 0.64% Ti, and alabandite with the highest FeS (49%) recorded for EL chondrites. Since the meteorite does not appear to be shocked or impact melted (it has medium-grained texture with the slightest indication of chondrules and normal metal and sulfide distribution) and the phase chemistry clearly indicates a higher equilibration temperature than the EL6 chondrites, for the time being we propose to call LEW87119 an EL7 chondrite. With the discovery in the last decade or so of a number of low-petrologic-type EH chondrites and the present discovery of EH6 and EL7 chondrites, the EH class and the EL class now appear to be comparable in their range of mineral compositions and thereby equilibration temperatures. The highest equilibration temperature for the EL chondrites is now ~700 degrees C, which is close to that of EH6 chondrite (Fig. 2). Equilibration temperatures for the EL6 chondrites are similar to those of EH4 chondrites. It may be that EH and EL classes have more similar thermal histories than previously supposed and that it is purely the textures of the two classes that are widely different and in need of further research. References: [1] Keil K. (1968) JGR, 73, 6945-6976. [2] Sears D. W. G. and Weeks K. S. (1984) Nature, 308, 257-259. [3] Skinner B. J. and Luce F. D. (1971) Amer. Min., 56, 1269-1296. [4] Zhang Y. et al. (1992) Meteoritics, 27, 310-311. [5] Weeks K. S.and Sears D. W. G. (1985) GCA, 49, 1525-1536. [6] Mason in Antarctic Meteorite Newsletter (1986, 1987, 1989, and 1990) 9(3), 10(2), 12(1,3), and 13(2,3). [7] Lin Y. T. et al. (1991) LPSC XXII, 811-812. [8] Chang Y. et al. (1992) LPSC XXIII, 217-218.

  11. Kinetics and equilibria of redox systems at temperatures as low as 300°C

    NASA Astrophysics Data System (ADS)

    Burkhard, Dorothee J. M.; Ulmer, Gene C.

    1995-05-01

    ZrO 2 oxygen sensors, gas mixtures, and conventional solid buffers have been used for decades to either control or measure oxygen fugacity (ƒ O 2) at high temperatures. In dry systems below ca. 700°C these techniques were used cautiously, if at all, due to doubt that there was any equilibration at lower temperatures. We have re-investigated these three types of redox systems in a study where each system (two different Y 2O 3ZrO 2 cells, four different gas mixtures, and four different dry solid buffers) was simultaneously cross-checked with the other to temperatures below 300°C and compared to JANAF data, extrapolated down to low temperatures. Steady and reproducible readings were observed down to T ≤ 300°C, from which we infer fast kinetics for all three systems. Specifically, we find equilibration of various CO 2H 2 gas mixtures over the entire temperature range and to much lower temperature than previously predicted. We assign the reactivity (decomposition) of CO 2 at low T to the catalytic action of Pt, whereby chemisorption of H 2 on the platinum surface enhances the reactivity with CO 2. This catalytic reactivity is diminished over time due to a long-term irreversible reaction of Pt with H 2. Subsequent embrittling and aging after prolonged exposure to H 2 explains erroneously high emf readings. Oxygen sensing of ZrO 2 cells is linear in 1/ T-log ƒ O 2 space and Nernstian at high temperatures. However, for cells with a specific and complex trace element chemistry, one may observe a non-Nernstian behavior in the low T range, i.e., below 470° or lower, probably caused by partially blocked O 2- migration, dependent on the H 2 content in the gas mixture. Linearity and reproducibility of this deviation still allows, however, a useable calibration. Solid buffers of the metal-metal oxide type are known to alloy with noble metals and we therefore used AgPd electrodes, for consistency in all studies, including (IW), (IM), (FMQ), and (NNO). Whereas (IW) and (IM) can be used in the temperature range of consideration, (FMQ) and (NNO) react sluggishly. Complex defect structure of (FMQ) and age alteration of Ni surfaces by chemisorption of oxygen and/or AgNi alloying of (NNO) may be the reason. Fast kinetics and successful redox sensing of CO 2H 2 gas mixtures, of ZrO 2 cells and of at least some solid buffers are therefore promising for future research on low- T redox equilibria.

  12. Effect of Dihedral Angle and Porosity on Percolating-Sealing Capacity of Texturally Equilibrated Rock Salt

    NASA Astrophysics Data System (ADS)

    Ghanbarzadeh, S.; Hesse, M. A.; Prodanovic, M.; Gardner, J. E.

    2013-12-01

    Salt deposits in sedimentary basins have long been considered to be a seal against fluid penetration. However, experimental, theoretical and field evidence suggests brine (and oil) can wet salt crystal surfaces at higher pressures and temperatures, which can form a percolating network. This network may act as flow conduits even at low porosities. The aim of this work is to investigate the effects of dihedral angle and porosity on the formation of percolating paths in different salt network lattices. However, previous studies considered only simple homogeneous and isotropic geometries. This work extends the analysis to realistic salt textures by presenting a novel numerical method to describe the texturally equilibrated pore shapes in polycrystalline rock salt and brine systems. First, a theoretical interfacial topology was formulated to minimize the interfacial surface between brine and salt. Then, the resulting nonlinear system of ordinary differential equations was solved using the Newton-Raphson method. Results show that the formation of connected fluid channels is more probable in lower dihedral angles and at higher porosities. The connectivity of the pore network is hysteretic, because the connection and disconnection at the pore throats for processes with increasing or decreasing porosities occur at different porosities. In porous media with anisotropic solids, pores initially connect in the direction of the shorter crystal axis and only at much higher porosities in the other directions. Consequently, even an infinitesimal elongation of the crystal shape can give rise to very strong anisotropy in permeability of the pore network. Also, fluid flow was simulated in the resulting pore network to calculate permeability, capillary entry pressure and velocity field. This work enabled us to investigate the opening of pore space and sealing capacity of rock salts. The obtained pore geometries determine a wide range of petrophysical properties such as permeability and capillary entry pressure. This expanded knowledge of the salt textural behavior vs. depth could also improve drilling operations in salt. Second, a series of experiments in different P-T conditions was carried out to investigate the actual shape of equilibrated channels in salt. The synthetic salt samples were scanned at the High Resolution X-ray CT Facility at the Department of Geological Science, the University of Texas at Austin with resolution in 1-6 micron range. The experimental results show both equilibrated (tubular pores) and non-equilibrated (planar features) in salt structure. Image processing was carried out by two open source software programs: ImageJ, which is a public domain Java image processing program, and 3DMA-Rock, which is a software package for quantitative analyzing of the pore space in three-dimensional X-ray computed microtomographic images of rock. We obtain medial axis and medial surface of the pore space, as well as find and characterize the corresponding pore-throat network. We also report permeability of the pore space computed using Palabos software.

  13. Miscellaneous methods for measuring matric or water potential

    USGS Publications Warehouse

    Scanlon, Bridget R.; Andraski, Brian J.; Bilskie, Jim; Dane, Jacob H.; Topp, G. Clarke

    2002-01-01

    A variety of techniques to measure matric potential or water potential in the laboratory and in the field are described in this section. The techniques described herein require equilibration of some medium whose matric or water potential can be determined from previous calibration or can be measured directly. Under equilibrium conditions the matric or water potential of the medium is equal to that of the soil. The techniques can be divided into: (i) those that measure matric potential and (ii) those that measure water potential (sum of matric and osmotic potentials). Matric potential is determined when the sensor matrix is in direct contact with the soil, so salts are free to diffuse in or out of the sensor matrix, and the equilibrium measurement therefore reflects matric forces acting on the water. Water potential is determined when the sensor is separated from the soil by a vapor gap, so salts are not free to move in or out of the sensor, and the equilibrium measurement reflects the sum of the matric and osmotic forces acting on the water.Seven different techniques are described in this section. Those that measure matric potential include (i) heat dissipation sensors, (ii) electrical resistance sensors, (iii) frequency domain and time domain sensors, and (iv) electro-optical switches. A method that can be used to measure matric potential or water potential is the (v) filter paper method. Techniques that measure water potential include (vi) the Dew Point Potentiameter (Decagon Devices, Inc., Pullman, WA1) (water activity meter) and (vii) vapor equilibration.The first four techniques are electronically based methods for measuring matric potential. Heat dissipation sensors and electrical resistance sensors infer matric potential from previously determined calibration relations between sensor heat dissipation or electrical resistance and matric potential. Frequency-domain and timedomain matric potential sensors measure water content, which is related to matric potential of the sensor through calibration. Electro-optical switches measure changes in light transmission through thin, nylon filters as they absorb or desorb water in response to changes in matric potential. Heat dissipation sensors and electrical resistance sensors are used primarily in the field to provide information on matric potential. Frequency domain matric potential sensors are new and have not been widely used. Time domain matric potential sensors and electro-optical switches are new and have not been commercialized. For the fifth technique, filter paper is used as the standard matrix. The filter paper technique measures matric potential when the filter paper is in direct contact with soil or water potential when separated from soil by a vapor gap. The Dew Point Potentiameter calculates water potential from the measured dew point and sample temperature. The vapor equilibration technique involves equilibration of soil samples with salt solutions of known osmotic potential. The filter paper, Dew Point Potentiameter, and vapor equilibration techniques are generally used in the laboratory to measure water potential of disturbed field samples or to measure water potential for water retention functions.

  14. Effector diversification within compartments of the Leptosphaeria maculans genome affected by repeat induced point mutations

    USDA-ARS?s Scientific Manuscript database

    The genome sequence of the phytopathogenic fungus Leptosphaeria maculans has been determined. It has a unique bipartite structure, divided between distinct GC-equilibrated and AT-rich regions (isochores), reminiscent of some plants and animals but not previously observed in fungi. The GC-equilibrate...

  15. EVALUATION OF VAPOR EQUILIBRATION AND IMPACT OF PURGE VOLUME ON SOIL-GAS SAMPLING RESULTS

    EPA Science Inventory

    Sequential sampling was utilized at the Raymark Superfund site to evaluate attainment of vapor equilibration and the impact of purge volume on soil-gas sample results. A simple mass-balance equation indicates that removal of three to five internal volumes of a sample system shou...

  16. Thermodynamics of an ideal generalized gas: II. Means of order alpha.

    PubMed

    Lavenda, B H

    2005-11-01

    The property that power means are monotonically increasing functions of their order is shown to be the basis of the second laws not only for processes involving heat conduction, but also for processes involving deformations. This generalizes earlier work involving only pure heat conduction and underlines the incomparability of the internal energy and adiabatic potentials when expressed as powers of the adiabatic variable. In an L-potential equilibration, the final state will be one of maximum entropy, whereas in an entropy equilibration, the final state will be one of minimum L. Unlike classical equilibrium thermodynamic phase space, which lacks an intrinsic metric structure insofar as distances and other geometrical concepts do not have an intrinsic thermodynamic significance in such spaces, a metric space can be constructed for the power means: the distance between means of different order is related to the Carnot efficiency. In the ideal classical gas limit, the average change in the entropy is shown to be proportional to the difference between the Shannon and Rényi entropies for nonextensive systems that are multifractal in nature. The L potential, like the internal energy, is a Schur convex function of the empirical temperature, which satisfies Jensen's inequality, and serves as a measure of the tendency to uniformity in processes involving pure thermal conduction.

  17. Changes in ionic selectivity with changes in density of water in gels and cells

    PubMed Central

    Wiggins, Philippa M.; van Ryn, René T.

    1990-01-01

    Gels equilibrated with aqueous solutions of impermeant solutes reached a steady state in which, in the absence of a pressure difference, the activity of water in the pores of the gel was higher than that of water in the external solution. The chemical potential of water in the gel/polymer solution slurry was higher than that in the supernatant polymer solution removed from the gel. Water in the pores of the gel decreased in density to 0.96 as increasing osmotic stress was applied. It is argued that at constant temperature and pressure water can equilibrate between two compartments of unequal osmolality only by adjusting its molar volume. Experiments showed that when gel water had a higher activity than external water it was K+ selective; when it had a lower activity it was Na+ selective. It is proposed that a continuous spectrum of water structures can exist in these two compartment systems from dense, reactive, weakly-bonded water which selects highly hydrated ions, to expanded, stretched, unreactive, viscous water which is strongly hydrogen bonded and selects K+ and univalent anions. These findings are related to the state and properties of cytoplasmic water which is probably held under osmotic stress by the activity of the sodium pump. PMID:19431765

  18. A green method using a micellar system for determination of andrographolide and dehydroandrographolide in human plasma.

    PubMed

    Zhao, Qi; Ding, Jie; Jin, Haiyan; Ding, Lan; Ren, Nanqi

    2013-04-01

    A method based on cloud point extraction (CPE) coupled with high-performance liquid chromatography separation and ultraviolet (UV) detection was developed to determine andrographolide and dehydroandrographolide in human plasma. The nonionic surfactant Triton X-114 was chosen as the extraction medium. Variable parameters affecting the CPE efficiency were evaluated and optimized, such as concentrations of Triton X-114 and NaCl, pH, equilibration temperature and equilibration time. A Zorbax SB C18 column (250 × 4.6 mm i.d., 5 µm) was used for separation of the two analytes at 30°C. The UV detection was performed at 254 nm. Under the optimum conditions, the limits of detection of andrographolide and dehydroandrographolide are 0.032 and 0.019 µg/mL, respectively. The intra-day and inter-day precisions expressed as relative standard deviation ranged from 3.2 to 7.3% and from 2.9 and 8.6%. The recoveries of andrographolide and dehydroandrographolide were in the range of 76.8-98.6% at three fortified concentrations of 0.1, 0.5 and 1.0 µg/mL. This method was efficient, environmentally friendly, rapid and inexpensive for the extraction and determination of andrographolide and dehydroandrographolide in human plasma.

  19. An investigation of long and short range ion motions within the cluster morphology of electrolyte-containing perfluoro-sulfonate ionomer membranes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Su, S.

    1992-01-01

    An equivalent circuit model was postulated for PFSI (perfluoro-sulfanate-ionomer) polymers. It successfully models three different dielectric relaxation mechanisms taking place within long and short sidechain PFSI's in an alternating electric field. The three dielectric processes are long-range ion inter-cluster hopping in the low frequency region, short-range intra-cluster polarization occurred in frequencies at about 10[sup 3] to 10[sup 6] Hz, and Debye-like orientation of water molecules taking place at very high frequencies. When membranes are annealed in the proximity of the glass transition temperature of ionic clusters, the packing of sulfonate groups becomes more efficient. This is by the fact thatmore » the symmetrical parameter of the distribution of relaxation time of the Cole-Cole equation increases with annealing time. The cluster activities of the long and short sidechain polymers act differently in different electrolyte solutions. The sidechains of the long sidechain polymer act like a spring, it contracts while the material was equilibrated in low concentration solutions and it expands as equilibrated in concentrated solutions. The cluster dimension of the long sidechain material does not vary too much. The cluster dimension of short sidechain polymers can vary significantly on different electrolyte solutions.« less

  20. Reversed headspace analysis for characterization, identification, and analysis of solid and liquid matrices: Part I.

    PubMed

    Markelov, M; Bershevits, O

    2006-03-01

    This paper offers a methodology of an experimentally simple reversed headspace (RHS) analysis for measuring of matrix effects and their use for identification and characterization of condensed matrices such as pharmaceuticals, polymers, chromatographic packing, etc. applicable for both quality control monitoring and research and development investigation. In RHS methods, the matrix is spiked and equilibrated with a mixture of volatile chemicals containing various functional groups (molecular sensor array or MSA mixture). Headspace chromatograms of the same spikes of a sample and an empty vial are compared. Examination of basic headspace theory shows that matrix specific constants (M), rather than partition coefficients (K), can be calculated from the headspace chromatograms and M=(K-1)xbeta, where beta is a degree of matrix volume change during equilibration. Matrix specific constants can be plotted against any property of chemicals (polarity, dielectric constant, solubility parameter, vapor pressure, etc.) or just against a set of consecutive numbers, each representing a chemical in MSA. This plot is, in a sense, a molecular affinity spectrum (MAS) specific for a given matrix at a given temperature and is independent of an instrument. Changes in MAS that correspond to chemicals with a particular functional group give an insight to the type of differences between matrices and may quantitatively define them.

  1. The impact of equilibrating hemispheric albedos on tropical performance in the HadGEM2-ES coupled climate model

    DOE PAGES

    Haywood, Jim M.; Jones, Andy; Dunstone, Nick; ...

    2016-01-14

    Despite the fact that the southern hemisphere contains a far greater proportion of dark ocean than the northern hemisphere, the total amount of sunlight reflected from the hemispheres is equal. However, the majority of climate models do not adequately represent this equivalence. Here we examine the impact of equilibrating hemispheric albedos by various idealised methods in a comprehensive coupled climate model and find significant improvements in what have been considered longstanding and apparently intractable model biases. Monsoon precipitation biases almost vanish over all continental land areas, the penetration of monsoon rainfall across the Sahel and the west African monsoon “jump”more » become well represented, and indicators of hurricane frequency are significantly improved. The results appear not to be model specific, implying that hemispheric albedo equivalence may provide a fundamental constraint for climate models that must be satisfied if the dynamics driving these processes, in particular the strength of the Hadley cell, are to be adequately represented. Cross-equatorial energy transport is implicated as a crucial component that must be accurately modelled in coupled general circulation models. The results also suggest that the commonly used practice of prescribing sea-surface temperatures in models provides a less accurate represention of precipitation than constraining the hemispheric albedos.« less

  2. Exploding Pusher Targets for Electron-Ion Coupling Measurements

    NASA Astrophysics Data System (ADS)

    Whitley, Heather D.; Pino, Jesse; Schneider, Marilyn; Shepherd, Ronnie; Benedict, Lorin; Bauer, Joseph; Graziani, Frank; Garbett, Warren

    2015-11-01

    Over the past several years, we have conducted theoretical investigations of electron-ion coupling and electronic transport in plasmas. In the regime of weakly coupled plasmas, we have identified models that we believe describe the physics well, but experimental data is still needed to validate the models. We are currently designing spectroscopic experiments to study electron-ion equilibration and/or electron heat transport using exploding pusher (XP) targets for experiments at the National Ignition Facility. Two platforms are being investigated: an indirect drive XP (IDXP) with a plastic ablator and a polar-direct drive XP (PDXP) with a glass ablator. The fill gas for both designs is D2. We propose to use a higher-Z dopant, such as Ar, as a spectroscopic tracer for time-resolved electron and ion temperature measurements. We perform 1D simulations using the ARES hydrodynamic code, in order to produce the time-resolved plasma conditions, which are then post-processed with CRETIN to assess the feasibility of a spectroscopic measurement. We examine target performance with respect to variations in gas fill pressure, ablator thickness, atom fraction of the Ar dopant, and drive energy, and assess the sensitivity of the predicted spectra to variations in the models for electron-ion equilibration and thermal conductivity. Prepared by LLNL under Contract DE-AC52-07NA27344. LLNL-ABS-675219.

  3. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Roberts, C. D.; Schmidt, S. M.; Physics

    Continuum strong QCD is the application of models and continuum quantum field theory to the study of phenomena in hadronic physics, which includes; e.g., the spectrum of QCD bound states and their interactions; and the transition to, and properties of, a quark gluon plasma. We provide a contemporary perspective, couched primarily in terms of the Dyson-Schwinger equations but also making comparisons with other approaches and models. Our discourse provides a practitioners' guide to features of the Dyson-Schwinger equations [such as confinement and dynamical chiral symmetry breaking] and canvasses phenomenological applications to light meson and baryon properties in cold, sparse QCD.more » These provide the foundation for an extension to hot, dense QCD, which is probed via the introduction of the intensive thermodynamic variables: chemical potential and temperature. We describe order parameters whose evolution signals deconfinement and chiral symmetry restoration, and chronicle their use in demarcating the quark gluon plasma phase boundary and characterizing the plasma's properties. Hadron traits change in an equilibrated plasma. We exemplify this and discuss putative signals of the effects. Finally, since plasma formation is not an equilibrium process, we discuss recent developments in kinetic theory and its application to describing the evolution from a relativistic heavy ion collision to an equilibrated quark gluon plasma.« less

  4. X-ray diffraction measurement of cosolvent accessible volume in rhombohedral insulin crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Soares, Alexei S.; Caspar, Donald L. D.

    We report x-ray crystallographic measurement of the number of solvent electrons in the unit cell of a protein crystal equilibrated with aqueous solutions of different densities provides information about preferential hydration in the crystalline state. Room temperature and cryo-cooled rhombohedral insulin crystals were equilibrated with 1.2 M trehalose to study the effect of lowered water activity. The native and trehalose soaked crystals were isomorphous and had similar structures. Including all the low resolution data, the amplitudes of the structure factors were put on an absolute scale (in units of electrons per asymmetric unit) by constraining the integrated number of electronsmore » inside the envelope of the calculated protein density map to equal the number deduced from the atomic model. This procedure defines the value of F(0 0 0), the amplitude at the origin of the Fourier transform, which is equal to the total number of electrons in the asymmetric unit (i.e. protein plus solvent). Comparison of the F(0 0 0) values for three isomorphous pairs of room temperature insulin crystals, three with trehalose and three without trehalose, indicates that 75 ± 12 electrons per asymmetric unit were added to the crystal solvent when soaked in 1.2 M trehalose. If all the water in the crystal were available as solvent for the trehalose, 304 electrons would have been added. Thus, the co-solvent accessible volume is one quarter of the total water in the crystal. Finally, determination of the total number of electrons in a protein crystal is an essential first step for mapping the average density distribution of the disordered solvent.« less

  5. Development of new method of δ13C measurement for trace hydrocarbons in natural gas using solid phase micro-extraction coupled to gas chromatography isotope ratio mass spectrometry.

    PubMed

    Li, Zhongping; Wang, Xibin; Li, Liwu; Zhang, Mingjie; Tao, Mingxin; Xing, Lantian; Cao, Chunhui; Xia, Yanqing

    2014-11-01

    Compound specific isotope analysis (CSIA) of normal-level hydrocarbons (C 1 -C 4 ) in natural gas is often successfully used in natural gas origin identification and classification, but little progress so far has been made for trace level hydrocarbons (C 5 -C 14 ) in natural gas. In this study, we developed a method for rapid analysis of carbon isotopic ratios for trace hydrocarbons in natural gas samples. This method can be described as a combined approach characterized by solid phase micro-extraction (SPME) technique coupled to gas chromatography isotope ratio mass spectrometry (GC/IRMS). In this study, the CAR-PDMS fiber was chosen as the SPME adsorptive material after comparative experiments with other four fibers, and the parameters, including equilibration time, extraction temperature and desorption time, for efficient extraction of trace hydrocarbons were systematically optimized. The results showed the carbon isotopic fractionation was not observed as a function of equilibration time and extraction temperature. And the δ 13 C signatures determined by SPME-GC/IRMS were in good agreement with the known δ 13 C values of C 5 -C 14 measured by GC-IRMS, and the accuracy is generally within ±0.5‰. Five natural gas samples were analyzed using this method, and the δ 13 C values for C 5 -C 14 components were obtained with satisfied repeatability. The SPME-GC/IRMS approach fitted with CAR-PDMS fiber is well suited for the preconcentration of trace hydrocarbons and provides so far the most reliable carbon isotopic analysis for trace compounds in natural gas. Published by Elsevier B.V.

  6. Seed storage at elevated partial pressure of oxygen, a fast method for analysing seed ageing under dry conditions.

    PubMed

    Groot, S P C; Surki, A A; de Vos, R C H; Kodde, J

    2012-11-01

    Despite differences in physiology between dry and relative moist seeds, seed ageing tests most often use a temperature and seed moisture level that are higher than during dry storage used in commercial practice and gene banks. This study aimed to test whether seed ageing under dry conditions can be accelerated by storing under high-pressure oxygen. methods: Dry barley (Hordeum vulgare), cabbage (Brassica oleracea), lettuce (Lactuca sativa) and soybean (Glycine max) seeds were stored between 2 and 7 weeks in steel tanks under 18 MPa partial pressure of oxygen. Storage under high-pressure nitrogen gas or under ambient air pressure served as controls. The method was compared with storage at 45 °C after equilibration at 85 % relative humidity and long-term storage at the laboratory bench. Germination behaviour, seedling morphology and tocopherol levels were assessed. The ageing of the dry seeds was indeed accelerated by storing under high-pressure oxygen. The morphological ageing symptoms of the stored seeds resembled those observed after ageing under long-term dry storage conditions. Barley appeared more tolerant of this storage treatment compared with lettuce and soybean. Less-mature harvested cabbage seeds were more sensitive, as was the case for primed compared with non-primed lettuce seeds. Under high-pressure oxygen storage the tocopherol levels of dry seeds decreased, in a linear way with the decline in seed germination, but remained unchanged in seeds deteriorated during storage at 45 °C after equilibration at 85 % RH. Seed storage under high-pressure oxygen offers a novel and relatively fast method to study the physiology and biochemistry of seed ageing at different seed moisture levels and temperatures, including those that are representative of the dry storage conditions as used in gene banks and commercial practice.

  7. X-ray diffraction measurement of cosolvent accessible volume in rhombohedral insulin crystals

    DOE PAGES

    Soares, Alexei S.; Caspar, Donald L. D.

    2017-08-31

    We report x-ray crystallographic measurement of the number of solvent electrons in the unit cell of a protein crystal equilibrated with aqueous solutions of different densities provides information about preferential hydration in the crystalline state. Room temperature and cryo-cooled rhombohedral insulin crystals were equilibrated with 1.2 M trehalose to study the effect of lowered water activity. The native and trehalose soaked crystals were isomorphous and had similar structures. Including all the low resolution data, the amplitudes of the structure factors were put on an absolute scale (in units of electrons per asymmetric unit) by constraining the integrated number of electronsmore » inside the envelope of the calculated protein density map to equal the number deduced from the atomic model. This procedure defines the value of F(0 0 0), the amplitude at the origin of the Fourier transform, which is equal to the total number of electrons in the asymmetric unit (i.e. protein plus solvent). Comparison of the F(0 0 0) values for three isomorphous pairs of room temperature insulin crystals, three with trehalose and three without trehalose, indicates that 75 ± 12 electrons per asymmetric unit were added to the crystal solvent when soaked in 1.2 M trehalose. If all the water in the crystal were available as solvent for the trehalose, 304 electrons would have been added. Thus, the co-solvent accessible volume is one quarter of the total water in the crystal. Finally, determination of the total number of electrons in a protein crystal is an essential first step for mapping the average density distribution of the disordered solvent.« less

  8. Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

    NASA Astrophysics Data System (ADS)

    O'Rourke, J. G.; Stevenson, D. J.

    2015-12-01

    Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer might inhibit the initialization of the dynamo.

  9. Average structure and M2 site configurations in C2/c clinopyroxenes along the Di-En join

    NASA Astrophysics Data System (ADS)

    Tribaudino, M.; Benna, P.; Bruno, E.

    1989-12-01

    In order to clarify the structural configurations observed in Diss in the Ca-rich region of the Di-En join (in which TEM observations show neither exsolution microstructures nor evidence of spinodal decomposition) single crystals large enough for X-ray diffraction analyses, with composition (Ca0.66Mg0.34)MgSi2O6, have been equilibrated close to the solvus at T=1350° C for 317 h, and quenched at room temperature. The refinement in C2/c space group shows that in the M2 site Ca and Mg are fully ‘ordered’ in two split positions (M2occ: 0.66 Ca; M2'occ: 0.34 Mg). Since the average structure shows a relevant elongation of anisotropic thermal ellipsoids of the O2 and O3 oxygen atoms, the refinement has been carried out according to a split model for O2 and O3 atoms: Ca appears 8-coordinated (as in diopside) and Mg shows a sixfold coordination similar to that of high-pigeonite. This coordination for Mg is significantly different from the fourfold coordination (Zn-like in Zn-cpx) proposed previously and it is a more probable coordination for Mg from a crystalchemical point of view. The same results were obtained refining a Di80En20 cpx, equilibrated at T=1230° C, according to the same O-split model. The data support the coexistence of a Di-like configuration for Ca and of a highPig-like configuration for Mg away from the solvus also. At T very near to T solidus the different configurations, observed at room temperature in the quenched samples, should converge and Ca and Mg should retain a single disordered configuration in the M2 site.

  10. Mercury Methylation by Desulfovibrio desulfuricans ND132 in the Presence of Polysulfides

    PubMed Central

    Jay, Jenny Ayla; Murray, Karen J.; Gilmour, Cynthia C.; Mason, Robert P.; Morel, François M. M.; Roberts, A. Lynn; Hemond, Harold F.

    2002-01-01

    The extracellular speciation of mercury may control bacterial uptake and methylation. Mercury-polysulfide complexes have recently been shown to be prevalent in sulfidic waters containing zero-valent sulfur. Despite substantial increases in total dissolved mercury concentration, methylation rates in cultures of Desulfovibrio desulfuricans ND132 equilibrated with cinnabar did not increase in the presence of polysulfides, as expected due to the large size and charged nature of most of the complexes. In natural waters not at saturation with cinnabar, mercury-polysulfide complexes would be expected to shift the speciation of mercury from HgS0(aq) toward charged complexes, thereby decreasing methylation rates. PMID:12406773

  11. Column temperature programming in enantioseparation of dihydropyrimidinone compounds using derivatized cellulose and amylose chiral stationary phases.

    PubMed

    Wang, Fang; Yeung, David; Han, Jun; Semin, David; McElvain, James S; Cheetham, Janet

    2008-03-01

    We report the application of column temperature programs as a tool to examine unusual temperature-induced behaviors of polysaccharide chiral stationary phases (CSPs). Using dihydropyrimidinone (DHP) compounds as probes we observed the heating (10-50 degrees C) and cooling (50-10 degrees C) van't Hoff plots of retention factors and/or selectivities of DHP compounds were not superimposable on AD, IA, and AS-H columns solvated with ethanol (EtOH)/n-hexane (n-Hex) mobile phases. The plots were not superimposable on AD, IB, and AS-H columns solvated with 2-propanol (2-PrOH)/n-Hex mobile phases. The thermally induced path-dependant behaviors were caused by slow equilibration as evidenced by the disappearance of the hysteresis in the second heating to cooling cycle and in a cooling to heating cycle. From the step-temperature program (10-50-10 degrees C), only EtOH solvated AD and AS-H phases showed the change of retention factors and/or selectivities with time while only 2-PrOH solvated AS-H phase showed similar behaviors.

  12. Correlated Time-Variation of Asphalt Rheology and Bulk Microstructure

    NASA Astrophysics Data System (ADS)

    Ramm, Adam; Nazmus, Sakib; Bhasin, Amit; Downer, Michael

    We use noncontact optical microscopy and optical scattering in the visible and near-infrared spectrum on Performance Grade (PG) asphalt binder to confirm the existence of microstructures in the bulk. The number of visible microstructures increases linearly as penetration depth of the incident radiation increases, which verifies a uniform volume distribution of microstructures. We use dark field optical scatter in the near-infrared to measure the temperature dependent behavior of the bulk microstructures and compare this behavior with Dynamic Shear Rheometer (DSR) measurements of the bulk complex shear modulus | G* (T) | . The main findings are: (1) After reaching thermal equilibrium, both temperature dependent optical scatter intensity (I (T)) and bulk shear modulus (| G* (T) |) continue to change appreciably for times much greater than thermal equilibration times. (2) The hysteresis behavior during a complete temperature cycle seen in previous work derives from a larger time dependence in the cooling step compared with the heating step. (3) Different binder aging conditions show different thermal time-variations for both I (T) and | G* (T) | .

  13. Critical fluid thermal equilibration experiment (19-IML-1)

    NASA Technical Reports Server (NTRS)

    Wilkinson, R. Allen

    1992-01-01

    Gravity sometimes blocks all experimental techniques of making a desired measurement. Any pure fluid possesses a liquid-vapor critical point. It is defined by a temperature, pressure, and density state in thermodynamics. The critical issue that this experiment attempts to understand is the time it takes for a sample to reach temperature and density equilibrium as the critical point is approached; is it infinity due to mass and thermal diffusion, or do pressure waves speed up energy transport while mass is still under diffusion control. The objectives are to observe: (1) large phase domain homogenization without and with stirring; (2) time evolution of heat and mass after temperature step is applied to a one phase equilibrium sample; (3) phase evolution and configuration upon going two phase from a one phase equilibrium state; (4) effects of stirring on a low g two phase configuration; (5) two phase to one phase healing dynamics starting from a two phase low g configuration; and (6) effects of shuttle acceleration events on spatially and temporally varying compressible critical fluid dynamics.

  14. Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

    NASA Astrophysics Data System (ADS)

    Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

    2018-03-01

    Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

  15. Impurity ion flow and temperature measured in a detached divertor with externally applied non-axisymmetric fields on DIII-D

    DOE PAGES

    Briesemeister, A. R.; Isler, R. C.; Allen, S. L.; ...

    2014-11-15

    In this study, externally applied non-axisymmetric magnetic fields are shown to have little effect on the impurity ion flow velocity and temperature as measured by the multichord divertor spectrometer in the DIII-D divertor for both attached and detached conditions. These experiments were performed in H-mode plasmas with the grad-B drift toward the target plates, with and without n = 3 resonant magnetic perturbations (RMPs). The flow velocity in the divertor is shown to change by as much as 30% when deuterium gas puffing is used to create detachment of the divertor plasma. No measurable changes in the C III flowmore » were observed in response to the RMP fields for the conditions used in this work. Images of the C III emission are used along with divertor Thomson scattering to show that the local electron and C III temperatures are equilibrated for the conditions shown.« less

  16. Oxygen potential of (U 0.88Pu 0.12)O 2±x and (U 0.7Pu 0.3)O 2±x at high temperatures of 1673-1873 K

    NASA Astrophysics Data System (ADS)

    Kato, M.; Takeuchi, K.; Uchida, T.; Sunaoshi, T.; Konashi, K.

    2011-07-01

    The oxygen potential of (U 0.88Pu 0.12)O 2±x (-0.0119 < x < 0.0408) and (U 0.7Pu 0.3)O 2±x (-0.0363 < x < 0.0288) was measured at high temperatures of 1673-1873 K using gas equilibrium method with thermo gravimeter. The measured data were analyzed by a defect chemistry model. Expressions were derived to represent the oxygen potential based on defect chemistry as functions of temperature and oxygen-to-metal ratio. The thermodynamic data, ΔG, ΔH and ΔS, at stoichiometric composition were obtained. The expressions can be used for in situ determination of the oxygen-to-metal ratio by the gas-equilibration method. The calculation results were consistent with measured data. It was estimated that addition of 1 wt.% Pu content increased oxygen potential of uranium and plutonium mixed oxide by 2-5 kJ/mol.

  17. Ion-Ion Equilibration and Particle Distributions in a 3000 km s-1 Shock in SN 1006

    NASA Astrophysics Data System (ADS)

    Raymond, J. C.; Winkler, P. F.; Blair, W. P.; Laming, J. M.

    2017-12-01

    SN 1006 is the most attractive target for investigating the physics of collisionless shock waves faster than 2000 {km} {{{s}}}-1. We obtained UV and optical spectra and an Hα image of a 3000 {km} {{{s}}}-1 shock driven by a clump of ejecta that has overtaken the blast wave. It is 500 km s-1 faster than the filament studied earlier. We find kinetic temperatures of H, He, C, and N that are consistent with being mass proportional, suggesting little or no energy transfer among species. We also find evidence that the electron temperature is less than 10% of the proton temperature and that the velocity distribution of H atoms is non-Maxwellian. We measure a proper motion of 0.″34 ± 0.″01 yr-1 for the bow shock, which implies a distance to SN 1006 of 1.85 ± 0.25 kpc, and we discuss the role of plasma turbulence in determining the shape of the velocity distribution.

  18. Quest for postdialysis urea rebound-equilibrated Kt/V with only intradialytic urea samples.

    PubMed

    Jean, G; Charra, B; Chazot, C; Laurent, G

    1999-09-01

    Postdialysis urea rebound (PDUR) is a cause of Kt/V overestimation when it is calculated from predialysis and the immediate postdialysis blood urea collections. Measuring PDUR requires a 30- or 60-minute postdialysis sampling, which is inconvenient. Several methods had been devised for a reasonable approach to determine PDUR-equilibrated Kt/V in short dialysis without the need for a delayed sample. The aim of our study was to compare these different Kt/V methods during the longer eight-hour hemodialysis sessions, and to determine the optimum intradialytic urea sample time that fits best with PDUR. The study included 21 patients (mean age 71.9 years) who were hemodialyzed for 60+/-60 months at three times eight hours weekly, using bicarbonate dialysate and cellulosic membranes. Blood urea samples were obtained at onset, and then at 17, 33, 50, 66, 75, 80, 85, and 100% of the dialysis session times, after 30 seconds of low flow, and then at 60-minutes postdialysis. All patients had a meal during dialysis. We compared four different formulas of Kt/V [(a) Kt/V-Smye with a 33% dialysis time urea sample, (b) two-pool equilibrated eKt/V, (c) Kt/V-std (Daugirdas-2) obtained with an immediate postdialytic sample, and (d) the different intradialytic urea samples for Kt/V (50, 66, 75, 80, and 85% of dialysis time)] with the equilibrated 60-minute PDUR Kt/V (Kt/V-r-60) formula as the reference method. The mean PDUR was 17.2+/-9%, leading to an overestimation of Kt/V-std by 12.2%. Kt/V-r-60 was 1.68+/-0.34. Kt/V-std was 1.88+/-0.36 (Delta = 12.2+/-4.8%, r = 0.8). eKt/V was 1.77+/-0.3 (Delta = 5+/-5%, r = 0.96), and Kt/V-Smye was 1.79+/-0.47 (Delta = 5.2+/-14%, r = 0.9). The best time for the intradialytic sampling was 80% (that is, at 6 hr and 24 min). The Kt/V-80 was 1.64+/-0.3 and was best fitted with Kt/V-r-60 (Delta = -1.8+/-8%, r = 0.91). The mean intradialytic urea evolution showed a three-exponential rate, in discrepancy with the two-exponential rate theoretical model. These results confirm that a significant postdialysis rebound exists in an eight-hour dialysis. An intradialytic urea sample taken at 80% of the total session time permits an estimation of the 60-minute Kt/V-rebound without the necessity of taking a delayed sample, with better accuracy than eKt/V or especially Kt/V-Smye. This may be related to a particular urea kinetics curve on the longer dialysis duration, which needs to be studied further.

  19. Comparison of methods for nutrient measurement in calcareous soils: Ion-exchange resin bag, capsule, membrane, and chemical extractions

    USGS Publications Warehouse

    Sherrod, S.K.; Belnap, J.; Miller, M.E.

    2002-01-01

    Four methods for measuring quantities of 12 plant-available nutrients were compared using three sandy soils in a series of three experiments. Three of the methods use different ion-exchange resin forms—bags, capsules, and membranes—and the fourth was conventional chemical extraction. The first experiment compared nutrient extraction data from a medium of sand saturated with a nutrient solution. The second and third experiments used Nakai and Sheppard series soils from Canyonlands National Park, which are relatively high in soil carbonates. The second experiment compared nutrient extraction data provided by the four methods from soils equilibrated at two temperatures, “warm” and “cold.” The third experiment extracted nutrients from the same soils in a field equilibration. Our results show that the four extraction techniques are not comparable. This conclusion is due to differences among the methods in the net quantities of nutrients extracted from equivalent soil volumes, in the proportional representation of nutrients within similar soils and treatments, in the measurement of nutrients that were added in known quantities, and even in the order of nutrients ranked by net abundance. We attribute the disparities in nutrient measurement among the different resin forms to interacting effects of the inherent differences in resin exchange capacity, differences among nutrients in their resin affinities, and possibly the relatively short equilibration time for laboratory trials. One constraint for measuring carbonate-related nutrients in high-carbonate soils is the conventional ammonium acetate extraction method, which we suspect of dissolving fine CaCO3 particles that are more abundant in Nakai series soils, resulting in erroneously high Ca2+ estimates. For study of plant-available nutrients, it is important to identify the nutrients of foremost interest and understand differences in their resin sorption dynamics to determine the most appropriate extraction method.

  20. Abiotic vs biological sources and fates of organic compounds in a low temperature continental serpentinizing system

    NASA Astrophysics Data System (ADS)

    Robinson, K.; Noble, S. M.; Shock, E.

    2016-12-01

    Serpentinization is likely the most common water-rock reaction in our solar system. During this process ultramafic silicates are hydrated, a calcium hydroxide solution is formed, and H2O is reduced to H2 coupled to the oxidation of Fe2+ to Fe3+. The resulting hyper-alkaline, reduced conditions generate thermodynamic drives for numerous carbon compound reactions, including the precipitation of various carbonate minerals and the reduction of inorganic carbonate to organic carbon. Testing the extent to which these thermodynamic drives lead to observable results led to the present study of the flow and transformations of carbon through the active continental serpentinizing system at the Samail Ophiolite in the Sultanate of Oman. Water samples were collected from shallow groundwater (representing system input), hyper-alkaline seeps (system output), boreholes (system intermediate), and surface fluid mixing zones, and analyzed for concentrations of dissolved inorganic carbon (DIC + δ13C), organic carbon (+ δ13C), formate, acetate, H2, methane (+ δ13C), ethane, and an accompanying suite of other geochemical solutes. These analyses indicate that the vast majority of DIC in these serpentinizing fluids precipitates in the subsurface as carbonate minerals; however, a significant amount of DIC is converted into organic acids and light hydrocarbons and expelled at the surface in hyper-alkaline seeps. Based on thermodynamic calculations, it seems most likely that formate last equilibrated with dolomite (CaMg[CO3]2) in the subsurface, acetate last equilibrated with calcite (CaCO3) near the surface, and methane and ethane last equilibrated in a distinct carbon-limited region of the subsurface. As for the fates of these compounds, energetic calculations reveal that a combination of oxidative, reductive, and fermentative metabolisms are thermodynamically favorable. Indeed, δ13C trends record microbial methane oxidation at the surface and cannot rule out methane as biologically sourced from the subsurface.

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