40 CFR 61.93 - Emission monitoring and test procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or frequent flow rate measurements shall be made. For relatively constant flow rates only periodic... applicable to batch processes when the unit is in operation. Periodic sampling (grab samples) may be used... have a potential to release radionuclides into the air, periodic confirmatory measurements shall be...

40 CFR 61.93 - Emission monitoring and test procedures.

Code of Federal Regulations, 2011 CFR

2011-07-01

... or frequent flow rate measurements shall be made. For relatively constant flow rates only periodic... applicable to batch processes when the unit is in operation. Periodic sampling (grab samples) may be used... have a potential to release radionuclides into the air, periodic confirmatory measurements shall be...

40 CFR 61.93 - Emission monitoring and test procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

... or frequent flow rate measurements shall be made. For relatively constant flow rates only periodic... applicable to batch processes when the unit is in operation. Periodic sampling (grab samples) may be used... have a potential to release radionuclides into the air, periodic confirmatory measurements shall be...

40 CFR 61.93 - Emission monitoring and test procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... or frequent flow rate measurements shall be made. For relatively constant flow rates only periodic... applicable to batch processes when the unit is in operation. Periodic sampling (grab samples) may be used... have a potential to release radionuclides into the air, periodic confirmatory measurements shall be...

40 CFR 61.93 - Emission monitoring and test procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or frequent flow rate measurements shall be made. For relatively constant flow rates only periodic... applicable to batch processes when the unit is in operation. Periodic sampling (grab samples) may be used... have a potential to release radionuclides into the air, periodic confirmatory measurements shall be...

Effect of Phenol Molecular Structure on Bacterial Transformation Rate Constants in Pond and River Samples

PubMed Central

Paris, Doris F.; Wolfe, N. Lee; Steen, William C.; Baughman, George L.

1983-01-01

Microbial transformation rate constants for a series of phenols were correlated with a property of the substituents, van der Waal's radius. Transformation products were the corresponding catechols, with the exception of p-hydroxybenzoic acid, the product of p-acetylphenol. A different product suggested a different pathway; p-acetylphenol, therefore, was deleted from the data base. PMID:16346236

Distribution of petroleum hydrocarbons and toluene biodegradation, Knox Street fire pits, Fort Bragg, North Carolina

USGS Publications Warehouse

Harden, S.L.; Landmeyer, J.E.

1996-01-01

An investigation was conducted at the Knox Street fire pits, Fort Bragg, North Carolina, to monitor the distribution of toluene, ethylbenzene, and xylene (TEX) in soil vapor, ground water, and ground-water/vapor to evaluate if total concentrations of TEX at the site are decreasing with time, and to quantify biodegradation rates of toluene in the unsaturated and saturated zones. Soil-vapor and ground-water samples were collected around the fire pits and ground-water/vapor samples were collected along the ground-water discharge zone, Beaver Creek, on a monthly basis from June 1994 through June 1995. Concentrations of TEX compounds in these samples were determined with a field gas chro- matograph. Laboratory experiments were performed on aquifer sediment samples to measure rates of toluene biodegradation by in situ micro- organisms. Based on field gas chromatographic analytical results, contamination levels of TEX compounds in both soil vapor and ground water appear to decrease downgradient of the fire-pit source area. During the 1-year study period, the observed temporal and spatial trends in soil vapor TEX concentrations appear to reflect differences in the distribution of TEX among solid, aqueous, and gaseous phases within fuel-contaminated soils in the unsaturated zone. Soil temperature and soil moisture are two important factors which influence the distribution of TEX com- pounds among the different phases. Because of the short period of data collection, it was not possible to distinguish between seasonal fluc- tuations in soil vapor TEX concentrations and an overall net decrease in TEX concentrations at the study site. No seasonal trend was observed in total TEX concentrations for ground- water samples collected at the study site. Although the analytical results could not be used to determine if ground-water TEX concen- trations decreased during the study at a specific location, the data were used to examine rate constants of toluene biodegradation. Based on ground-water toluene concentration data, a maximum rate constant for anaerobic biodegradation of toluene in the saturated zone was estimated to be as low as 0.002 d-1 or as high as 0.026 d-1. Based on analyses of ground-water/vapor samples, toluene was the prin- cipal TEX compound identified in ground water discharging to Beaver Creek. Observed decreases in ground-water/vapor toluene concentrations during the study period may reflect a decrease in source inputs, an increase in dilution caused by higher ground-water flow, and(or) removal by biological or other physical processes. Rate constants of toluene anaerobic biodegradation determined by laboratory measurements illustrate a typical acclimation response of micro-organisms to hydrocarbon contamination in sediments collected from the site. Toluene biodegradation rate constants derived from laboratory microcosm studies ranged from 0.001 to 0.027 d-1, which is similar to the range of 0.002 to 0.026 d-1 for toluene biodegradation rate constants derived from ground-water analytical data. The close agreement of toluene biodegradation rate constants reported using both approaches offer strong evidence that toluene can be degraded at environmentally significant rates at the study site.

Evaluation of procedures for estimating ruminal particle turnover and diet digestibility in ruminant animals

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

Cochran, R.C.

1985-01-01

Procedures used in estimating ruminal particle turnover and diet digestibility were evaluated in a series of independent experiments. Experiment 1 and 2 evaluated the influence of sampling site, mathematical model and intraruminal mixing on estimates of ruminal particle turnover in beef steers grazing crested wheatgrass or offered ad libitum levels of prairie hay once daily, respectively. Particle turnover rate constants were estimated by intraruminal administration (via rumen cannula) of ytterbium (Yb)-labeled forage, followed by serial collection of rumen digesta or fecal samples. Rumen Yb concentrations were transformed to natural logarithms and regressed on time. Influence of sampling site (rectum versusmore » rumen) on turnover estimates was modified by the model used to fit fecal marker excretion curves in the grazing study. In contrast, estimated turnover rate constants from rumen sampling were smaller (P < 0.05) than rectally derived rate constants, regardless of fecal model used, when steers were fed once daily. In Experiment 3, in vitro residues subjected to acid or neutral detergent fiber extraction (IVADF and IVNDF), acid detergent fiber incubated in cellulase (ADFIC) and acid detergent lignin (ADL) were evaluated as internal markers for predicting diet digestibility. Both IVADF and IVNDF displayed variable accuracy for prediction of in vivo digestibility whereas ADL and ADFIC inaccurately predicted digestibility of all diets.« less

Annealed importance sampling with constant cooling rate

NASA Astrophysics Data System (ADS)

Giovannelli, Edoardo; Cardini, Gianni; Gellini, Cristina; Pietraperzia, Giangaetano; Chelli, Riccardo

2015-02-01

Annealed importance sampling is a simulation method devised by Neal [Stat. Comput. 11, 125 (2001)] to assign weights to configurations generated by simulated annealing trajectories. In particular, the equilibrium average of a generic physical quantity can be computed by a weighted average exploiting weights and estimates of this quantity associated to the final configurations of the annealed trajectories. Here, we review annealed importance sampling from the perspective of nonequilibrium path-ensemble averages [G. E. Crooks, Phys. Rev. E 61, 2361 (2000)]. The equivalence of Neal's and Crooks' treatments highlights the generality of the method, which goes beyond the mere thermal-based protocols. Furthermore, we show that a temperature schedule based on a constant cooling rate outperforms stepwise cooling schedules and that, for a given elapsed computer time, performances of annealed importance sampling are, in general, improved by increasing the number of intermediate temperatures.

Crystal Growth Simulations To Establish Physically Relevant Kinetic Parameters from the Empirical Kolmogorov-Johnson-Mehl-Avrami Model

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

Dill, Eric D.; Folmer, Jacob C.W.; Martin, James D.

A series of simulations was performed to enable interpretation of the material and physical significance of the parameters defined in the Kolmogorov, Johnson and Mehl, and Avrami (KJMA) rate expression commonly used to describe phase boundary controlled reactions of condensed matter. The parameters k, n, and t 0 are shown to be highly correlated, which if unaccounted for seriously challenge mechanistic interpretation. It is demonstrated that rate measurements exhibit an intrinsic uncertainty without precise knowledge of the location and orientation of nucleation with respect to the free volume into which it grows. More significantly, it is demonstrated that the KJMAmore » rate constant k is highly dependent on sample size. However, under the simulated conditions of slow nucleation relative to crystal growth, sample volume and sample anisotropy correction affords a means to eliminate the experimental condition dependence of the KJMA rate constant, k, producing the material-specific parameter, the velocity of the phase boundary, v pb.« less

Quantification aspects of constant pressure (ultra) high pressure liquid chromatography using mass-sensitive detectors with a nebulizing interface.

PubMed

Verstraeten, M; Broeckhoven, K; Lynen, F; Choikhet, K; Landt, K; Dittmann, M; Witt, K; Sandra, P; Desmet, G

2013-01-25

The present contribution investigates the quantitation aspects of mass-sensitive detectors with nebulizing interface (ESI-MSD, ELSD, CAD) in the constant pressure gradient elution mode. In this operation mode, the pressure is controlled and maintained at a set value and the liquid flow rate will vary according to the inverse mobile phase viscosity. As the pressure is continuously kept at the allowable maximum during the entire gradient run, the average liquid flow rate is higher compared to that in the conventional constant flow rate operation mode, thus shortening the analysis time. The following three mass-sensitive detectors were investigated: mass spectrometry detector (MS), evaporative light scattering detector (ELSD) and charged aerosol detector (CAD) and a wide variety of samples (phenones, polyaromatic hydrocarbons, wine, cocoa butter) has been considered. It was found that the nebulizing efficiency of the LC-interfaces of the three detectors under consideration changes with the increasing liquid flow rate. For the MS, the increasing flow rate leads to a lower peak area whereas for the ELSD the peak area increases compared to the constant flow rate mode. The peak area obtained with a CAD is rather insensitive to the liquid flow rate. The reproducibility of the peak area remains similar in both modes, although variation in system permeability compromises the 'long-term' reproducibility. This problem can however be overcome by running a flow rate program with an optimized flow rate and composition profile obtained from the constant pressure mode. In this case, the quantification remains reproducibile, despite any occuring variations of the system permeability. Furthermore, the same fragmentation pattern (MS) has been found in the constant pressure mode compared to the customary constant flow rate mode. Copyright © 2012 Elsevier B.V. All rights reserved.

Dose equivalent rate constants and barrier transmission data for nuclear medicine facility dose calculations and shielding design.

PubMed

Kusano, Maggie; Caldwell, Curtis B

2014-07-01

A primary goal of nuclear medicine facility design is to keep public and worker radiation doses As Low As Reasonably Achievable (ALARA). To estimate dose and shielding requirements, one needs to know both the dose equivalent rate constants for soft tissue and barrier transmission factors (TFs) for all radionuclides of interest. Dose equivalent rate constants are most commonly calculated using published air kerma or exposure rate constants, while transmission factors are most commonly calculated using published tenth-value layers (TVLs). Values can be calculated more accurately using the radionuclide's photon emission spectrum and the physical properties of lead, concrete, and/or tissue at these energies. These calculations may be non-trivial due to the polyenergetic nature of the radionuclides used in nuclear medicine. In this paper, the effects of dose equivalent rate constant and transmission factor on nuclear medicine dose and shielding calculations are investigated, and new values based on up-to-date nuclear data and thresholds specific to nuclear medicine are proposed. To facilitate practical use, transmission curves were fitted to the three-parameter Archer equation. Finally, the results of this work were applied to the design of a sample nuclear medicine facility and compared to doses calculated using common methods to investigate the effects of these values on dose estimates and shielding decisions. Dose equivalent rate constants generally agreed well with those derived from the literature with the exception of those from NCRP 124. Depending on the situation, Archer fit TFs could be significantly more accurate than TVL-based TFs. These results were reflected in the sample shielding problem, with unshielded dose estimates agreeing well, with the exception of those based on NCRP 124, and Archer fit TFs providing a more accurate alternative to TVL TFs and a simpler alternative to full spectral-based calculations. The data provided by this paper should assist in improving the accuracy and tractability of dose and shielding calculations for nuclear medicine facility design.

Study of kinetic desorption rate constant in fish muscle and agarose gel model using solid phase microextraction coupled with liquid chromatography with tandem mass spectrometry.

PubMed

Togunde, Oluranti Paul; Oakes, Ken; Servos, Mark; Pawliszyn, Janusz

2012-09-12

This study aims to use solid phase microextraction (SPME), a simple tool to investigate diffusion rate (time) constant of selected pharmaceuticals in gel and fish muscle by comparing desorption rate of diffusion of the drugs in both agarose gel prepared with phosphate-buffered saline (PBS; pH 7.4) and fish muscle. The gel concentration (agarose gel model) that could be used to simulate tissue matrix (fish muscle) for free diffusion of drugs under in vitro and in vivo conditions was determined to model mass transfer phenomena between fibre polymer coating and environmental matrix such that partition coefficients and desorption time constant (diffusion coefficient) can be determined. SPME procedure involves preloading the extraction phase (fibre) with the standards from spiked PBS for 1h via direct extraction. Subsequently, the preloaded fibre is introduced to the sample such fish or agarose gel for specified time ranging from 0.5 to 60 h. Then, fibre is removed at specified time and desorbed in 100 μL of desorption solution (acetonitrile: water 1:1) for 90 min under agitation speed of 1000 rpm. The samples extract were immediately injected to the instrument and analysed using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The limit of detection of the method in gel and fish muscle was 0.01-0.07 ng mL(-1) and 0.07-0.34 ng g(-1), respectively, while the limit quantification was 0.10-0.20 ng mL(-1) in gel samples and 0.40-0.97 ng g(-1) in fish sample. The reproducibility of the method was good (5-15% RSD). The results suggest that kinetics of desorption of the compounds in fish tissue and different viscosity of gel can be determined using desorption time constant. In this study, desorption time constant which is directly related to desorption rate (diffusion kinetics) of selected drugs from the fibre to the gel matrix is faster as the viscosity of the gel matrix reduces from 2% (w/v) to 0.8% (w/v). As the concentration of gel reduces, viscosity of the gel will be reduced therefore allowing faster diffusion which invariably affect desorption time constant. Also, desorption time constant of model drugs in the fish muscle and 0.8-0.9% (w/v) gel model are similar based on free diffusion of studied compounds. In addition, in vitro and in vivo desorption time constant comparison shows that desorption time constant in an in vivo system (live fish muscle) is generally higher than an in vitro system (dead fish muscle) except for sertraline and nordiazepam. This study demonstrates SPME as a simple investigative tool to understand kinetics of desorption in an in vivo system with a goal to measure desorption rate of pharmaceuticals in fish. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

The Oxidation Rate of SiC in High Pressure Water Vapor Environments

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Robinson, R. Craig

1999-01-01

CVD SiC and sintered alpha-SiC samples were exposed at 1316 C in a high pressure burner rig at total pressures of 5.7, 15, and 25 atm for times up to 100h. Variations in sample emittance for the first nine hours of exposure were used to determine the thickness of the silica scale as a function of time. After accounting for volatility of silica in water vapor, the parabolic rate constants for Sic in water vapor pressures of 0.7, 1.8 and 3.1 atm were determined. The dependence of the parabolic rate constant on the water vapor pressure yielded a power law exponent of one. Silica growth on Sic is therefore limited by transport of molecular water vapor through the silica scale.

Experimental Magnetohydrodynamic Energy Extraction from a Pulsed Detonation

DTIC Science & Technology

2015-03-01

experimental data taken in this thesis will follow voltage profiles similar to Fig. 2. Notice the initial section in Fig. 2 shows exponential decay consistent...equal that time constant. The exponential curves in Fig. 2 show how changing the time constant can change the charge and/or discharge rate of the...see Fig. 1), at a sampling rate of 1 MHz. Shielded wire and a common ground were used throughout the DAQ system to avoid capacitive issues in the

Rate constant for the reaction SO + BrO yields SO2 + Br

NASA Technical Reports Server (NTRS)

Brunning, J.; Stief, L.

1986-01-01

The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

Variability in nest survival rates and implications to nesting studies

USGS Publications Warehouse

Klett, A.T.; Johnson, D.H.

1982-01-01

We used four reasonably large samples (83-213) of Mallard (Anas platyrhynchos) and Blue-winged Teal (A. discors) nests on an interstate highway right-of-way in southcentral North Dakota to evaluate potential biases in hatch-rate estimates. Twelve consecutive, weekly searches for nests were conducted with a cable-chain drag in 1976 and 1977. Nests were revisited at weekly intervals. Four methods were used to estimate hatch rates for the four data sets: the Traditional Method, the Mayfield Method, and two modifications of the Mayfield Method that are sometimes appropriate when daily mortality rates of nests are not constant. Hatch rates and the average age of nests at discovery declined as the interval between searches decreased, suggesting that mortality rates were not constant in our samples. An analysis of variance indicated that daily mortality rates varied with the age of nests in all four samples. Mortality was generally highest during the early laying period, moderately high during the late laying period, and lowest during incubation. We speculate that this relationship of mortality to nest age might be due to the presence of hens at nests or to differences in the vulnerability of nest sites to predation. A modification of the Mayfield Method that accounts for age-related variation in nest mortality was most appropriate for our samples. We suggest methods for conducting nesting studies and estimating nest success for species possessing similar nesting habits.

Rheology of welding: experimental constraints

NASA Astrophysics Data System (ADS)

Quane, S. L.; Russell, J. K.; Kennedy, L. A.

2003-04-01

The rheological behavior of pyroclastic deposits during welding is incompletely understood and is based on a surprisingly small number of experimental studies. Previous pioneering experimental studies were done on small (1 cm thick) samples of ash/crystal mixtures under constant load. They established minimum welding temperatures between 600 and 700^oC under loads of 0.7 MPa (˜40 m of ignimbrite) to 3.6 MPa (˜250 m depth of ignimbrite). However, these data are neither sufficiently comprehensive nor coherent enough to fully describe the rheology of pyroclastic mixtures. In addition, previous studies did not examine the microstructural and geometric changes associated with welding compaction. Our goal is to provide accurate and comprehensive constitutive relationships between material properties, temperature, load and strain rate for pyroclastic material undergoing welding. Here we present results from a newly designed experimental apparatus. The experimental apparatus consists of a LoadTrac II fully automated uniaxial compression load frame manufactured by Geocomp Corporation. The load frame has a built in displacement transducer and can run both constant strain rate (10-6 to 0.25 cm/s) and constant load (up to 1150 kg) tests to a maximum displacement of 7.5 cm. The sample assembly comprises 5 cm diameter cylindrical upper and lower pistons (insulating ceramic with steel conductive ends) housed in a copper jacket. Samples are 5 cm diameter cores and can vary in length from 1 to 15 cm depending on experimental needs. A fiber insulated tube furnace capable of reaching temperatures ≈1000^oC surrounds the sample assembly. Temperature is measured using a thermocouple located inside the sample through the bottom piston; the furnace controller is capable of maintaining temperature fluctuations to <5^oC. Deformation experiments are performed on pre-fabricated cylinders of soda-lime glass beads and rhyolitic volcanic ash, as well as, cores of pumiceous rhyodacite. Experimental runs use strain rates of 10-4 and 10-5 cm/s and loads of ˜0 to 4.5 MPa. Experiments are run at temperatures between 400 and 850^oC corresponding to below and above the calorimetric glass transition temperatures of the respective materials. Data deriving from constant load and constant strain rate experiments are being used to constrain rheological models for welding of pyroclastic material.

Longitudinal Evaluation of Myocardial Fatty Acid and Glucose Metabolism in Fasted and Nonfasted Spontaneously Hypertensive Rats Using MicroPET/CT

DOE PAGES

Huber, Jennifer S.; Hernandez, Andrew M.; Janabi, Mustafa; ...

2017-09-06

Using longitudinal micro positron emission tomography (microPET)/computed tomography (CT) studies, we quantified changes in myocardial metabolism and perfusion in spontaneously hypertensive rats (SHRs), a model of left ventricular hypertrophy (LVH). Fatty acid and glucose metabolism were quantified in the hearts of SHRs and Wistar-Kyoto (WKY) normotensive rats using long-chain fatty acid analog 18F-fluoro-6-thia heptadecanoic acid ( 18F-FTHA) and glucose analog 18F-fluorodeoxyglucose ( 18F-FDG) under normal or fasting conditions. We also used 18F-fluorodihydrorotenol ( 18F-FDHROL) to investigate perfusion in their hearts without fasting. Rats were imaged at 4 or 5 times over their life cycle. Compartment modeling was used to estimatemore » the rate constants for the radiotracers. Blood samples were obtained and analyzed for glucose and free fatty acid concentrations. SHRs demonstrated no significant difference in 18F-FDHROL wash-in rate constant (P = .1) and distribution volume (P = .1), significantly higher 18F-FDG myocardial influx rate constant (P = 4×10 –8), and significantly lower 18F-FTHA myocardial influx rate constant (P = .007) than WKYs during the 2009-2010 study without fasting. SHRs demonstrated a significantly higher 18F-FDHROL wash-in rate constant (P = 5×10 –6) and distribution volume (P = 3×10 –8), significantly higher 18F-FDG myocardial influx rate constant (P = 3×10 –8), and a higher trend of 18F-FTHA myocardial influx rate constant (not significant, P = .1) than WKYs during the 2011–2012 study with fasting. Changes in glucose plasma concentrations were generally negatively correlated with corresponding radiotracer influx rate constant changes. The study indicates a switch from preferred fatty acid metabolism to increased glucose metabolism with hypertrophy. Increased perfusion during the 2011-2012 study may be indicative of increased aerobic metabolism in the SHR model of LVH.« less

Longitudinal Evaluation of Myocardial Fatty Acid and Glucose Metabolism in Fasted and Nonfasted Spontaneously Hypertensive Rats Using MicroPET/CT

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

Huber, Jennifer S.; Hernandez, Andrew M.; Janabi, Mustafa

Using longitudinal micro positron emission tomography (microPET)/computed tomography (CT) studies, we quantified changes in myocardial metabolism and perfusion in spontaneously hypertensive rats (SHRs), a model of left ventricular hypertrophy (LVH). Fatty acid and glucose metabolism were quantified in the hearts of SHRs and Wistar-Kyoto (WKY) normotensive rats using long-chain fatty acid analog 18F-fluoro-6-thia heptadecanoic acid ( 18F-FTHA) and glucose analog 18F-fluorodeoxyglucose ( 18F-FDG) under normal or fasting conditions. We also used 18F-fluorodihydrorotenol ( 18F-FDHROL) to investigate perfusion in their hearts without fasting. Rats were imaged at 4 or 5 times over their life cycle. Compartment modeling was used to estimatemore » the rate constants for the radiotracers. Blood samples were obtained and analyzed for glucose and free fatty acid concentrations. SHRs demonstrated no significant difference in 18F-FDHROL wash-in rate constant (P = .1) and distribution volume (P = .1), significantly higher 18F-FDG myocardial influx rate constant (P = 4×10 –8), and significantly lower 18F-FTHA myocardial influx rate constant (P = .007) than WKYs during the 2009-2010 study without fasting. SHRs demonstrated a significantly higher 18F-FDHROL wash-in rate constant (P = 5×10 –6) and distribution volume (P = 3×10 –8), significantly higher 18F-FDG myocardial influx rate constant (P = 3×10 –8), and a higher trend of 18F-FTHA myocardial influx rate constant (not significant, P = .1) than WKYs during the 2011–2012 study with fasting. Changes in glucose plasma concentrations were generally negatively correlated with corresponding radiotracer influx rate constant changes. The study indicates a switch from preferred fatty acid metabolism to increased glucose metabolism with hypertrophy. Increased perfusion during the 2011-2012 study may be indicative of increased aerobic metabolism in the SHR model of LVH.« less

Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

PubMed

Ivanov, Mikhail V; Babikov, Dmitri

2012-05-14

Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

Constant Flux Proxies and Pleistocene Sediment Accumulation Rates on the Juan de Fuca Ridge in the Northeast Pacific

NASA Astrophysics Data System (ADS)

Middleton, J. L.; Mukhopadhyay, S.; Langmuir, C. H.; Costa, K.; McManus, J. F.; d'Almeida, M.; Huybers, P. J.; Winckler, G.

2016-12-01

Mass accumulation rates of marine sediments are often employed to constrain deposition rates of important proxies such as terrigenous dust, carbonate, and biogenic opal to quantitatively examine variations in continental aridity, atmospheric transport, and biologic productivity across changing climatic conditions. However, deposition rates that are estimated using traditional mass accumulation rates calculated from sediment core age models can be subject to bias from lateral sediment transport and limited age model resolution. Constant flux proxies, such as extraterrestrial helium-3 (3HeET) and excess thorium-230 (230ThXS), can be used to calculate vertical sediment accumulation rates that are independent of age model uncertainties and the effects of lateral sediment transport. While a short half-life limits analyses of 230ThXS to the past 500 ka, 3HeET is stable and could be used to constrain sedimentary fluxes during much of the Cenozoic. Despite the vast paleoceanographic potential of constant flux proxies, few studies have directly compared the behavior of 230ThXS and 3HeET using measurements from the same samples. Sediment grain size fractionation and local scavenging effects may differentially bias one or both proxy systems and complicate the interpretation of 230ThXS or 3HeET data. We will present a new record of vertical sediment accumulation rates spanning the past 600 ka in the Northeast Pacific constrained using analyses of both 3HeET and 230ThXS in two sediment cores from cruise AT26-19 on the Juan de Fuca Ridge. Such a record allows for intercomparison of both constant flux proxies in the mid-ocean ridge environment and examination of sedimentary behavior across multiple glacial cycles. The 230ThXS-derived accumulation rates typically range from 0.5 to 2 g cm-2 ka-1 over the past 450 ka, with periods of maximum deposition coinciding with glacial maxima. Preliminary results of samples analyzed with both 3HeET and 230ThXS indicate relative consistency between vertical sediment accumulation rates computed from each proxy and encourage the use of these constant flux proxies in other sedimentary records.

Hydro-mechanical properties of calcilutite from an outcrop near the Aigion fault, Gulf of Corinth, Greece

NASA Astrophysics Data System (ADS)

Song, I.; Elphick, S.; Main, I.; Ngwenya, B.

2003-04-01

We present hydraulic and mechanical characteristics of a calcilutite (calcitic mud) sample from an outcrop 4 km south of the Aigion fault zone, on the Southern shore of the Gulf of Corinth, Greece. This fine-grained sediment may provide a top seal for fluid pressure, and is also representative of limestone gouge materials, and hence its properties are important for modelling the hydro-mechanical response of the Aigion fault zone. An X-ray diffraction analysis revealed that the sample consists mostly of calcite (82%), with quartz (10%), and minor clay minerals. An unconsolidated sample was remoulded into a core shape (38 mm diameter by 45 mm length) under slight compaction, and then placed in the centre of an oedometer cell, covered by two porous steel fluid distribution discs on the top and bottom of the sample. The sample was subjected in turn to a constant vertical stress of 16.2, 18.9, 21.6, 24.3, and 27.0 MPa. The vertical load at each level was held constant for 24 hours to measure the compaction/consolidation under passive drained conditions, and then the permeability was measured for the following 24 hours at constant flow rate. Axial deformation was measured by two LVDTs at diagonally-opposite positions on the sample. At the end of the test, we measured the sample dimensions, and its wet and dry weights, obtaining a void ratio of 0.58 and a porosity of 0.37. The axial strain measurements show a consolidation curve with a decelerating strain rate that can be approximated by a power-law function. The permeability is negatively and linearly correlated to the stress, and ranges from 0.9 - 1.5 x 10-17 m2. When fluid is first pumped into the sample at a constant rate, we observed a transient decelerating increase in pore pressure due to swelling in the samples. Conversely on the release of the axial stress a transient reduction in pore pressure was observed, in turn sucking fluid back into the sample. These transient responses to sudden changes in effective stress imply that such fine-grained calcitic mud-like materials may play a crucial role in the time-dependent triggering of fault movement in the Aigion region, especially in faults when the powder has been smeared along the fault surface by repeated movement.

Variable criteria sequential stopping rule: Validity and power with repeated measures ANOVA, multiple correlation, MANOVA and relation to Chi-square distribution.

PubMed

Fitts, Douglas A

2017-09-21

The variable criteria sequential stopping rule (vcSSR) is an efficient way to add sample size to planned ANOVA tests while holding the observed rate of Type I errors, α o , constant. The only difference from regular null hypothesis testing is that criteria for stopping the experiment are obtained from a table based on the desired power, rate of Type I errors, and beginning sample size. The vcSSR was developed using between-subjects ANOVAs, but it should work with p values from any type of F test. In the present study, the α o remained constant at the nominal level when using the previously published table of criteria with repeated measures designs with various numbers of treatments per subject, Type I error rates, values of ρ, and four different sample size models. New power curves allow researchers to select the optimal sample size model for a repeated measures experiment. The criteria held α o constant either when used with a multiple correlation that varied the sample size model and the number of predictor variables, or when used with MANOVA with multiple groups and two levels of a within-subject variable at various levels of ρ. Although not recommended for use with χ 2 tests such as the Friedman rank ANOVA test, the vcSSR produces predictable results based on the relation between F and χ 2 . Together, the data confirm the view that the vcSSR can be used to control Type I errors during sequential sampling with any t- or F-statistic rather than being restricted to certain ANOVA designs.

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents.

PubMed

Fayad, Paul B; Zamyadi, Arash; Broseus, Romain; Prévost, Michèle; Sauvé, Sébastien

2013-01-01

This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens.

A new variable interval schedule with constant hazard rate and finite time range.

PubMed

Bugallo, Mehdi; Machado, Armando; Vasconcelos, Marco

2018-05-27

We propose a new variable interval (VI) schedule that achieves constant probability of reinforcement in time while using a bounded range of intervals. By sampling each trial duration from a uniform distribution ranging from 0 to 2 T seconds, and then applying a reinforcement rule that depends linearly on trial duration, the schedule alternates reinforced and unreinforced trials, each less than 2 T seconds, while preserving a constant hazard function. © 2018 Society for the Experimental Analysis of Behavior.

Portable apparatus for the measurement of environmental radon and thoron

DOEpatents

Negro, Vincent C.

2001-01-01

The radometer is a portable instrument for the measurement of the concentration of atmospheric radon/thoron in a test area. A constant velocity pump pulls the air from the outside at a constant flow rate. If the air is too moist, some or all of the sample is passed through a desiccant filter prior to encountering an electrostatic filter. The electrostatic filter prevents any charged particles from entering the sampling chamber. Once the sample has entered the chamber, the progeny of the decay of radon/thoron are collected on a detector and measured. The measured data is compiled by a computer and displayed.

COMPARISON OF 24H AVERAGE VOC MONITORING RESULTS FOR RESIDENTIAL INDOOR AND OUTDOOR AIR USING CARBOPACK X-FILLED DIFFUSIVE SAMPLERS AND ACTIVE SAMPLING - A PILOT STUDY

EPA Science Inventory

Analytical results obtained by thermal desorption GC/MS for 24h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive samp...

40 CFR 61.107 - Emission determination.

Code of Federal Regulations, 2013 CFR

2013-07-01

... shall be made. For relatively constant flow rates only periodic measurements are necessary. (2... operation. Periodic sampling (grab samples) may be used only with EPA's prior approval. Such approval may be... potential to release radionuclides into the air, periodic confirmatory measurements should be made to verify...

40 CFR 61.107 - Emission determination.

Code of Federal Regulations, 2011 CFR

2011-07-01

... shall be made. For relatively constant flow rates only periodic measurements are necessary. (2... operation. Periodic sampling (grab samples) may be used only with EPA's prior approval. Such approval may be... potential to release radionuclides into the air, periodic confirmatory measurements should be made to verify...

40 CFR 61.107 - Emission determination.

Code of Federal Regulations, 2014 CFR

2014-07-01

... shall be made. For relatively constant flow rates only periodic measurements are necessary. (2... operation. Periodic sampling (grab samples) may be used only with EPA's prior approval. Such approval may be... potential to release radionuclides into the air, periodic confirmatory measurements should be made to verify...

40 CFR 61.107 - Emission determination.

Code of Federal Regulations, 2010 CFR

2010-07-01

... shall be made. For relatively constant flow rates only periodic measurements are necessary. (2... operation. Periodic sampling (grab samples) may be used only with EPA's prior approval. Such approval may be... potential to release radionuclides into the air, periodic confirmatory measurements should be made to verify...

40 CFR 61.107 - Emission determination.

Code of Federal Regulations, 2012 CFR

2012-07-01

... shall be made. For relatively constant flow rates only periodic measurements are necessary. (2... operation. Periodic sampling (grab samples) may be used only with EPA's prior approval. Such approval may be... potential to release radionuclides into the air, periodic confirmatory measurements should be made to verify...

Using Maximum Likelihood Statistical Methods and Pigment Flux Data to Constrain Particle Exchange and Organic Matter Remineralization Rate Constants in the Mediterranean Sea

NASA Astrophysics Data System (ADS)

Wang, W.; Lee, C.; Cochran, K. K.; Armstrong, R. A.

2016-02-01

Sinking particles play a pivotal role transferring material from the surface to the deeper ocean via the "biological pump". To quantify the extent to which these particles aggregate and disaggregate, and thus affect particle settling velocity, we constructed a box model to describe organic matter cycling. The box model was fit to chloropigment data sampled in the 2005 MedFlux project using Indented Rotating Sphere sediment traps operating in Settling Velocity (SV) mode. Because of the very different pigment compositions of phytoplankton and fecal pellets, chloropigments are useful as proxies to record particle exchange. The maximum likelihood statistical method was used to estimate particle aggregation, disaggregation, and organic matter remineralization rate constants. Eleven settling velocity categories collected by SV sediment traps were grouped into two sinking velocity classes (fast- and slow-sinking) to decrease the number of parameters that needed to be estimated. Organic matter degradation rate constants were estimated to be 1.2, 1.6, and 1.1 y^-1, which are equivalent to degradation half-lives of 0.60, 0.45, and 0.62 y^-1, at 313, 524, and 1918 m, respectively. Rate constants of chlorophyll a degradation to pheopigments (pheophorbide, pheophytin, and pyropheophorbide) were estimated to be 0.88, 0.93, and 1.2 y^-1, at 313, 524, and 1918 m, respectively. Aggregation rate constants varied little with depth, with the highest value being 0.07 y^-1 at 524 m. Disaggregation rate constants were highest at 524 m (14 y^-1) and lowest at 1918 m (9.6 y^-1)

Drop-Off Detection with the Long Cane: Effects of Different Cane Techniques on Performance

ERIC Educational Resources Information Center

Kim, Dae Shik; Emerson, Robert Wall; Curtis, Amy

2009-01-01

This study compared the drop-off detection performance with the two-point touch and constant contact cane techniques using a repeated-measures design with a convenience sample of 15 cane users with visual impairments. The constant contact technique was superior to the two-point touch technique in the drop-off detection rate and the 50% detection…

The influence of reagent type on the kinetics of ultrafine coal flotation

USGS Publications Warehouse

Read, R.B.; Camp, L.R.; Summers, M.S.; Rapp, D.M.

1989-01-01

A kinetic study has been conducted to determine the influence of reagent type on flotation rates of ultrafine coal. Two ultrafine coal samples, the Illinois No. 5 (Springfield) and Pittsburgh No. 8, have been evaluated with various reagent types in order to derive the rate constants for coal (kc), ash (ka), and pyrite (kc). The reagents used in the study include anionic surfactants, anionic surfactant-alcohol mixtures, and frothing alcohols. In general, the surfactant-alcohol mixtures tend to float ultrafine coal at a rate three to four times faster than either pure alcohols or pure anionic surfactants. Pine oil, a mixture of terpene alcohols and hydrocarbons, was an exception to this finding; it exhibited higher rate constants than the pure aliphatic alcohols or other pure anionic surfactants studied; this may be explained by the fact that the sample of pine oil used (70% alpha-terpineol) acted as a frother/collector system similar to alcohol/kerosene. The separation efficiencies of ash and pyrite from coal, as evidenced by the ratios of kc/ka or kc/kp, tend to indicate, however, that commercially available surfactant-alcohol mixtures are not as selective as pure alcohols such as 2-ethyl-1-hexanol or methylisobutylcarbinol. Some distinct differences in various rate constants, or their ratios, were noted between the two coals studied, and are possibly attributable to surface chemistry effects. ?? 1989.

Choice with frequently changing food rates and food ratios.

PubMed

Baum, William M; Davison, Michael

2014-03-01

In studies of operant choice, when one schedule of a concurrent pair is varied while the other is held constant, the constancy of the constant schedule may exert discriminative control over performance. In our earlier experiments, schedules varied reciprocally across components within sessions, so that while food ratio varied food rate remained constant. In the present experiment, we held one variable-interval (VI) schedule constant while varying the concurrent VI schedule within sessions. We studied five conditions, each with a different constant left VI schedule. On the right key, seven different VI schedules were presented in seven different unsignaled components. We analyzed performances at several different time scales. At the longest time scale, across conditions, behavior ratios varied with food ratios as would be expected from the generalized matching law. At shorter time scales, effects due to holding the left VI constant became more and more apparent, the shorter the time scale. In choice relations across components, preference for the left key leveled off as the right key became leaner. Interfood choice approximated strict matching for the varied right key, whereas interfood choice hardly varied at all for the constant left key. At the shortest time scale, visit patterns differed for the left and right keys. Much evidence indicated the development of a fix-and-sample pattern. In sum, the procedural difference made a large difference to performance, except for choice at the longest time scale and the fix-and-sample pattern at the shortest time scale. © Society for the Experimental Analysis of Behavior.

The kinetics of the oxidation of ferrous iron in synthetic and natural waters

NASA Astrophysics Data System (ADS)

Davison, W.; Seed, G.

1983-01-01

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six. The present data, together with a comprehensive survey of the literature, are used to suggest a 'universal' rate constant of ca. 2 × 10 13 M -2 atm -1 min -1 (range 1.5-3 × 10 13) in the rate law -d[Fe II]/dt = k[Fe II]pO 2 (OH-) 2 for natural freshwaters in the pH range 6.5-7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander; Hammes-Schiffer, Sharon

2015-11-17

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approachmore » in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (applications to molecular electrocatalysts).« less

Magnetic and structural studies of trivalent Co-substituted Cd-Mn ferrites

NASA Astrophysics Data System (ADS)

Amer, M. A.; Meaz, T. M.; El-Kestawy, M.; Ghoneim, A. I.

2016-05-01

Series of polycrystalline Cd0.4Mn0.6CoxFe2-xO4 ferrites, 0≤x≤1, were prepared by solid state reaction method. The samples were characterized by inductive coupling plasma, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectra and vibrating sample magnetometry. This study proved that all samples have single-phase cubic spinel structure. The true lattice constant, saturation magnetization, magnetic moment and trend of grain size and IR band νA showed decrease against x, whereas the trend of crystallite size, threshold frequency, Debye temperature, IR bands ν1 and ν2 and force constants F1 and F2, coercivity, anisotropy constant and residual magnetization showed increase. The IR analysis proved existence of Fe2+, Co2+, Fe4+, Co4+ and/or Mn4+ ions amongst the crystal sublattices. The characteristic bands ν1 and ν2 and force constants F1 and F2 showed decrease versus the tetrahedral- and octahedral-site bond length, respectively. The strain, specific surface area, refractive index, velocity, jump rate and remnant magnetization proved dependence on Co3+ ion content x.

Constitutive modeling of the human Anterior Cruciate Ligament (ACL) under uniaxial loading using viscoelastic prony series and hyperelastic five parameter Mooney-Rivlin model

NASA Astrophysics Data System (ADS)

Chakraborty, Souvik; Mondal, Debabrata; Motalab, Mohammad

2016-07-01

In this present study, the stress-strain behavior of the Human Anterior Cruciate Ligament (ACL) is studied under uniaxial loads applied with various strain rates. Tensile testing of the human ACL samples requires state of the art test facilities. Furthermore, difficulty in finding human ligament for testing purpose results in very limited archival data. Nominal Stress vs. deformation gradient plots for different strain rates, as found in literature, is used to model the material behavior either as a hyperelastic or as a viscoelastic material. The well-known five parameter Mooney-Rivlin constitutivemodel for hyperelastic material and the Prony Series model for viscoelastic material are used and the objective of the analyses comprises of determining the model constants and their variation-trend with strain rates for the Human Anterior Cruciate Ligament (ACL) material using the non-linear curve fitting tool. The relationship between the model constants and strain rate, using the Hyperelastic Mooney-Rivlin model, has been obtained. The variation of the values of each coefficient with strain rates, obtained using Hyperelastic Mooney-Rivlin model are then plotted and variation of the values with strain rates are obtained for all the model constants. These plots are again fitted using the software package MATLAB and a power law relationship between the model constants and strain rates is obtained for each constant. The obtained material model for Human Anterior Cruciate Ligament (ACL) material can be implemented in any commercial finite element software package for stress analysis.

Estimating site occupancy rates for aquatic plants using spatial sub-sampling designs when detection probabilities are less than one

USGS Publications Warehouse

Nielson, Ryan M.; Gray, Brian R.; McDonald, Lyman L.; Heglund, Patricia J.

2011-01-01

Estimation of site occupancy rates when detection probabilities are <1 is well established in wildlife science. Data from multiple visits to a sample of sites are used to estimate detection probabilities and the proportion of sites occupied by focal species. In this article we describe how site occupancy methods can be applied to estimate occupancy rates of plants and other sessile organisms. We illustrate this approach and the pitfalls of ignoring incomplete detection using spatial data for 2 aquatic vascular plants collected under the Upper Mississippi River's Long Term Resource Monitoring Program (LTRMP). Site occupancy models considered include: a naïve model that ignores incomplete detection, a simple site occupancy model assuming a constant occupancy rate and a constant probability of detection across sites, several models that allow site occupancy rates and probabilities of detection to vary with habitat characteristics, and mixture models that allow for unexplained variation in detection probabilities. We used information theoretic methods to rank competing models and bootstrapping to evaluate the goodness-of-fit of the final models. Results of our analysis confirm that ignoring incomplete detection can result in biased estimates of occupancy rates. Estimates of site occupancy rates for 2 aquatic plant species were 19–36% higher compared to naive estimates that ignored probabilities of detection <1. Simulations indicate that final models have little bias when 50 or more sites are sampled, and little gains in precision could be expected for sample sizes >300. We recommend applying site occupancy methods for monitoring presence of aquatic species.

Estimation of hydrolysis rate constants for carbamates ...

EPA Pesticide Factsheets

Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism. Hydrolysis represents a major environmental degradation pathway; unfortunately, only a small fraction of hydrolysis rates for about 85,000 chemicals on the Toxic Substances Control Act (TSCA) inventory are in public domain, making it critical to develop in silico approaches to estimate hydrolysis rate constants. In this presentation, we compare three complementary approaches to estimate hydrolysis rates for carbamates, an important chemical class widely used in agriculture as pesticides, herbicides and fungicides. Fragment-based Quantitative Structure Activity Relationships (QSARs) using Hammett-Taft sigma constants are widely published and implemented for relatively simple functional groups such as carboxylic acid esters, phthalate esters, and organophosphate esters, and we extend these to carbamates. We also develop a pKa based model and a quantitative structure property relationship (QSPR) model, and evaluate them against measured rate constants using R square and root mean square (RMS) error. Our work shows that for our relatively small sample size of carbamates, a Hammett-Taft based fragment model performs best, followed by a pKa and a QSPR model. This presentation compares three comp

Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

PubMed Central

2013-01-01

Background This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. Results The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M-1 sec-1 in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M-1 sec-1 in ultrapure water and 26 to 149 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M-1 sec-1 in ultrapure water and 180 to 368 M-1 sec-1 in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L-1 after contact times of 10 to 60 min. Conclusion This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens. PMID:23675917

Changes of Photochemical Properties of Dissolved Organic Matter During a Hydrological Year

NASA Astrophysics Data System (ADS)

Porcal, P.; Dillon, P. J.

2009-05-01

The fate of dissolved organic matter (DOM) in lakes and streams is significantly affected by photochemical transformation of DOM. A series of laboratory photochemical experiments has been conducted to describe long term changes in photochemical properties of DOM. The stream samples used in this study originated from three different watersheds in Dorset area (Ontario, Canada), the first watershed has predominantly coniferous cove, the second one is dominated by maple and birch, and a large wetland dominates to the third one. The first order kinetic constant rate was used as a suitable characteristic of photochemical properties of DOM. The higher rates were observed in samples from watershed dominated by coniferous forest while the lower rates were determined in deciduous forest. Kinetic rates from all three watersheds showed sinusoidal pattern during the hydrological year. The rates increased steadily during autumn and winter and decreased during spring and summer. The highest values were observed during the spring melt events when the fresh DOM was flushed out from terrestrial sources. The minimum rate constants were in summer when the discharge was lower. The photochemical properties of DOM changes during the hydrological year and correspond to the seasonal cycles of terrestrial organic matter.

Characterization of solution-phase drug-protein interactions by ultrafast affinity extraction.

PubMed

Beeram, Sandya R; Zheng, Xiwei; Suh, Kyungah; Hage, David S

2018-03-03

A number of tools based on high-performance affinity separations have been developed for studying drug-protein interactions. An example of one recent approach is ultrafast affinity extraction. This method has been employed to examine the free (or non-bound) fractions of drugs and other solutes in simple or complex samples that contain soluble binding agents. These free fractions have also been used to determine the binding constants and rate constants for the interactions of drugs with these soluble agents. This report describes the general principles of ultrafast affinity extraction and the experimental conditions under which it can be used to characterize such interactions. This method will be illustrated by utilizing data that have been obtained when using this approach to measure the binding and dissociation of various drugs with the serum transport proteins human serum albumin and alpha 1 -acid glycoprotein. A number of practical factors will be discussed that should be considered in the design and optimization of this approach for use with single-column or multi-column systems. Techniques will also be described for analyzing the resulting data for the determination of free fractions, rate constants and binding constants. In addition, the extension of this method to complex samples, such as clinical specimens, will be considered. Copyright © 2018 Elsevier Inc. All rights reserved.

The Effect of Sn Orientation on Intermetallic Compound Growth in Idealized Sn-Cu-Ag Interconnects

NASA Astrophysics Data System (ADS)

Kinney, Chris; Linares, Xioranny; Lee, Kyu-Oh; Morris, J. W.

2013-04-01

The work reported here explores the influence of crystal orientation on the growth of the interfacial intermetallic layer during electromigration in Cu||Sn||Cu solder joints. The samples were thin, planar Sn-Ag-Cu (SAC) solder layers between Cu bars subject to a uniaxial current. Electron backscatter diffraction (EBSD) was used to characterize the microstructure before and after testing. The most useful representation of the EBSD data identifies the Sn grain orientation by the angle between the Sn c-axis and the current direction. The tested samples included single-crystal joints with c-axis nearly parallel to the current ("green" samples) and with c-axis perpendicular to the current ("red" samples). At current density of 104 A/cm2 (steady-state temperature of ~150°C), an intermetallic layer grew at an observable rate in the "green" samples, but not in the "red" ones. A current density of 1.15 × 104 A/cm2 (temperature ~160°C) led to measurable intermetallic growth in both samples. The growth fronts were nearly planar and the growth rates constant (after an initial incubation period); the growth rates in the "green" samples were about 10× those in the "red" samples. The Cu concentrations were constant within the joints, showing that the intermetallic growth is dominated by the electromigration flux. The measured growth rates and literature values for the diffusion of Cu in Sn were used to extract values for the effective charge, z *, that governs the electromigration of Cu. The calculated value of z * is significantly larger for current perpendicular to the c-axis than along it.

Effect of antacid on the bioavailabiity of lithium carbonate.

PubMed

Goode, D L; Newton, D W; Ueda, C T; Wilson, J E; Wulf, B G; Kafonek, D

1984-01-01

The effect of an antacid on the bioavailability of lithium carbonate was determined in six healthy men in a crossover study. The volunteers were given single 300-mg doses of lithium carbonate alone and with 30 ml of an antacid containing aluminum and magnesium hydroxides with simethicone. Blood samples were collected at various times for 0-24 hours after each dose. The plasma samples were analyzed for lithium using a spectrophotometer, and bioavailability variables were calculated from plasma lithium concentration-time curves. There were no significant differences in peak plasma lithium concentration, time to peak concentration, area under the concentration-time curve from 0 to 24 hours, first-order absorption rate constant, and first-order elimination rate constant between the two treatments. Concurrent administration of antacids and lithium carbonate should not affect lithium blood concentrations.

Distribution Development for STORM Ingestion Input Parameters

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

Fulton, John

The Sandia-developed Transport of Radioactive Materials (STORM) code suite is used as part of the Radioisotope Power System Launch Safety (RPSLS) program to perform statistical modeling of the consequences due to release of radioactive material given a launch accident. As part of this modeling, STORM samples input parameters from probability distributions with some parameters treated as constants. This report described the work done to convert four of these constant inputs (Consumption Rate, Average Crop Yield, Cropland to Landuse Database Ratio, and Crop Uptake Factor) to sampled values. Consumption rate changed from a constant value of 557.68 kg / yr tomore » a normal distribution with a mean of 102.96 kg / yr and a standard deviation of 2.65 kg / yr. Meanwhile, Average Crop Yield changed from a constant value of 3.783 kg edible / m 2 to a normal distribution with a mean of 3.23 kg edible / m 2 and a standard deviation of 0.442 kg edible / m 2 . The Cropland to Landuse Database ratio changed from a constant value of 0.0996 (9.96%) to a normal distribution with a mean value of 0.0312 (3.12%) and a standard deviation of 0.00292 (0.29%). Finally the crop uptake factor changed from a constant value of 6.37e -4 (Bq crop /kg)/(Bq soil /kg) to a lognormal distribution with a geometric mean value of 3.38e -4 (Bq crop /kg)/(Bq soil /kg) and a standard deviation value of 3.33 (Bq crop /kg)/(Bq soil /kg)« less

Application of the Zero-Order Reaction Rate Model and Transition State Theory to predict porous Ti6Al4V bending strength.

PubMed

Reig, L; Amigó, V; Busquets, D; Calero, J A; Ortiz, J L

2012-08-01

Porous Ti6Al4V samples were produced by microsphere sintering. The Zero-Order Reaction Rate Model and Transition State Theory were used to model the sintering process and to estimate the bending strength of the porous samples developed. The evolution of the surface area during the sintering process was used to obtain sintering parameters (sintering constant, activation energy, frequency factor, constant of activation and Gibbs energy of activation). These were then correlated with the bending strength in order to obtain a simple model with which to estimate the evolution of the bending strength of the samples when the sintering temperature and time are modified: σY=P+B·[lnT·t-ΔGa/R·T]. Although the sintering parameters were obtained only for the microsphere sizes analysed here, the strength of intermediate sizes could easily be estimated following this model. Copyright © 2012 Elsevier B.V. All rights reserved.

Modeling the effect of laser heating on the strength and failure of 7075-T6 aluminum

DOE PAGES

Florando, J. N.; Margraf, J. D.; Reus, J. F.; ...

2015-06-06

The effect of rapid laser heating on the response of 7075-T6 aluminum has been characterized using 3-D digital image correlation and a series of thermocouples. The experimental results indicate that as the samples are held under a constant load, the heating from the laser profile causes non-uniform temperature and strain fields, and the strain-rate increases dramatically as the sample nears failure. Simulations have been conducted using the LLNL multi-physics code ALE3D, and compared to the experiments. The strength and failure of the material was modeled using the Johnson–Cook strength and damage models. Here, in order to capture the response, amore » dual-condition criterion was utilized which calibrated one set of parameters to low temperature quasi-static strain rate data, while the other parameter set is calibrated to high temperature high strain rate data. The thermal effects were captured using temperature dependent thermal constants and invoking thermal transport with conduction, convection, and thermal radiation.« less

Composite grain size sensitive and grain size insensitive creep of bischofite, carnallite and mixed bischofite-carnallite-halite salt rock

NASA Astrophysics Data System (ADS)

Muhammad, Nawaz; de Bresser, Hans; Peach, Colin; Spiers, Chris

2016-04-01

Deformation experiments have been conducted on rock samples of the valuable magnesium and potassium salts bischofite and carnallite, and on mixed bischofite-carnallite-halite rocks. The samples have been machined from a natural core from the northern part of the Netherlands. Main aim was to produce constitutive flow laws that can be applied at the in situ conditions that hold in the undissolved wall rock of caverns resulting from solution mining. The experiments were triaxial compression tests carried out at true in situ conditions of 70° C temperature and 40 MPa confining pressure. A typical experiment consisted of a few steps at constant strain rate, in the range 10-5 to 10-8 s-1, interrupted by periods of stress relaxation. During the constant strain rate part of the test, the sample was deformed until a steady (or near steady) state of stress was reached. This usually required about 2-4% of shortening. Then the piston was arrested and the stress on the sample was allowed to relax until the diminishing force on the sample reached the limits of the load cell resolution, usually at a strain rate in the order of 10-9 s-1. The duration of each relaxation step was a few days. Carnallite was found to be 4-5 times stronger than bischofite. The bischofite-carnallite-halite mixtures, at their turn, were stronger than carnallite, and hence substantially stronger than pure bischofite. For bischofite as well as carnallite, we observed that during stress relaxation, the stress exponent nof a conventional power law changed from ˜5 at strain rate 10-5 s-1 to ˜1 at 10-9 s-1. The absolute strength of both materials remained higher if relaxation started at a higher stress, i.e. at a faster strain rate. We interpret this as indicating a difference in microstructure at the initiation of the relaxation, notably a smaller grain size related to dynamical recrystallization during the constant strain rate step. The data thus suggest that there is a gradual change in deformation mechanism with decreasing strain rate for both bischofite and carnallite, from grain size insensitive (GSI) dislocation creep at the higher strain rates to grain size sensitive (GSS, i.e. pressure solution) creep at slow strain rate. We can speculate about the composite GSI-GSS nature of the constitutive laws describing the creep of the salt materials.

Study of Creep of Alumina-Forming Austenitic Stainless Steel for High-Temperature Energy Applications

NASA Astrophysics Data System (ADS)

Afonina, Natalie Petrovna

To withstand the high temperature (>700°C) and pressure demands of steam turbines and boilers used for energy applications, metal alloys must be economically viable and have the necessary material properties, such as high-temperature creep strength, oxidation and corrosion resistance, to withstand such conditions. One promising class of alloys potentially capable of withstanding the rigors of aggressive environments, are alumina-forming austenitic stainless steels (AFAs) alloyed with aluminum to improve corrosion and oxidation resistance. The effect of aging on the microstructure, high temperature constant-stress creep behavior and mechanical properties of the AFA-type alloy Fe-20Cr-30Ni-2Nb-5Al (at.%) were investigated in this study. The alloy's microstructural evolution with increased aging time was observed prior to creep testing. As aging time increased, the alloy exhibited increasing quantities of fine Fe2Nb Laves phase dispersions, with a precipitate-free zone appearing in samples with higher aging times. The presence of the L1 2 phase gamma'-Ni3Al precipitate was detected in the alloy's matrix at 760°C. A constant-stress creep rig was designed, built and its operation validated. Constant-stress creep tests were performed at 760°C and 35MPa, and the effects of different aging conditions on creep rate were investigated. Specimens aged for 240 h exhibited the highest creep rate by a factor of 5, with the homogenized sample having the second highest rate. Samples aged for 2.4 h and 24 h exhibited similar low secondary creep rates. Creep tests conducted at 700oC exhibited a significantly lower creep rate compared to those at 760oC. Microstructural analysis was performed on crept samples to explore high temperature straining properties. The quantity and size of Fe2Nb Laves phase and NiAl particles increased in the matrix and on grain boundaries with longer aging time. High temperature tensile tests were performed and compared to room temperature results. The high temperature results were significantly lower when compared to room temperature values. Higher creep rates were correlated with lower yield strengths.

Application of POCIS for exposure assessment of munitions constituents during constant and fluctuating exposure.

PubMed

Belden, Jason B; Lotufo, Guilherme R; Biedenbach, James M; Sieve, Kristal K; Rosen, Gunther

2015-05-01

The present study examined the potential use of polar organic chemical integrative samplers (POCIS) for exposure assessment of munitions constituents, including 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and their breakdown products (aminodinitrotoluenes [ADNTs], diaminonitrotoluenes [DANTs], and hexahydro-1,3,5-trinitroso-1,3,5-triazine [TNX]). Loss of munitions constituents from the sorbent phase after uptake was observed for the "pesticide" POCIS configuration but not for the "pharmaceutical" configuration. Therefore, the latter was selected for further investigation. Under constant exposure conditions, TNT, ADNTs, DANT, RDX, and atrazine (a common environmental contaminant) accumulated at a linear rate for at least 14 d, with sampling rates between 34 mL/d and 215 mL/d. When POCIS were exposed to fluctuating concentrations, analyte accumulation values were similar to values found during constant exposure, indicating that the sampler was indeed integrative. In contrast, caffeine (a common polar contaminant) and TNX did not accumulate at a linear rate and had a reduction in accumulation of greater than 50% on the POCIS during fluctuating exposures, demonstrating that POCIS did not sample those chemicals in an integrative manner. Moreover, in a flow-through microcosm containing the explosive formulation Composition B, TNT and RDX were readily measured using POCIS, despite relatively high turnover rates and thus reduced water concentrations. Mean water concentrations estimated from POCIS were ± 37% of mean water concentrations measured by traditional grab sample collection. Thus, POCIS were found to have high utility for quantifying exposure to most munitions constituents evaluated (TNT, ADNTs, and RDX) and atrazine. © 2014 SETAC.

In situ monitoring of thermal crystallization of ultrathin tris(8-hydroxyquinoline) aluminum films using surface-enhanced Raman scattering.

PubMed

Muraki, Naoki

2014-01-01

Thermal crystallization of 3, 10, and 60 nm-thick tris(8-hydroxyquinoline)aluminum (Alq3) films is studied using surface-enhanced Raman scattering with a constant heating rate. An abrupt higher frequency shift of the quinoline-stretching mode is found to be an indication of a phase transition of Alq3 molecules from amorphous to crystalline. While the 60 nm-thick film shows the same crystallization temperature as a bulk sample, the thinner films were found to have a lower crystallization temperature and slower rate of crystallization. Non-isothermal kinetics analysis is performed to quantify kinetic properties such as the Avrami exponent constants and crystallization rates of ultrathin Alq3 films.

CONTINUOUS GAS ANALYZER

DOEpatents

Katz, S.; Weber, C.W.

1960-02-16

A reagent gas and a sample gas are chemically combined on a continuous basis in a reaction zone maintained at a selected temperature. The reagent gas and the sample gas are introduced to the reaction zone at preselected. constant molar rates of flow. The reagent gas and the selected gas in the sample mixture combine in the reaction zone to form a product gas having a different number of moles from the sum of the moles of the reactants. The difference in the total molar rates of flow into and out of the reaction zone is measured and indicated to determine the concentration of the selected gas.

Simulating and explaining passive air sampling rates for semi-volatile compounds on polyurethane foam passive samplers

PubMed Central

Petrich, Nicholas T.; Spak, Scott N.; Carmichael, Gregory R.; Hu, Dingfei; Martinez, Andres; Hornbuckle, Keri C.

2013-01-01

Passive air samplers (PAS) including polyurethane foam (PUF) are widely deployed as an inexpensive and practical way to sample semi-volatile pollutants. However, concentration estimates from PAS rely on constant empirical mass transfer rates, which add unquantified uncertainties to concentrations. Here we present a method for modeling hourly sampling rates for semi-volatile compounds from hourly meteorology using first-principle chemistry, physics, and fluid dynamics, calibrated from depuration experiments. This approach quantifies and explains observed effects of meteorology on variability in compound-specific sampling rates and analyte concentrations; simulates nonlinear PUF uptake; and recovers synthetic hourly concentrations at a reference temperature. Sampling rates are evaluated for polychlorinated biphenyl congeners at a network of Harner model samplers in Chicago, Illinois during 2008, finding simulated average sampling rates within analytical uncertainty of those determined from loss of depuration compounds, and confirming quasi-linear uptake. Results indicate hourly, daily and interannual variability in sampling rates, sensitivity to temporal resolution in meteorology, and predictable volatility-based relationships between congeners. We quantify importance of each simulated process to sampling rates and mass transfer and assess uncertainty contributed by advection, molecular diffusion, volatilization, and flow regime within the PAS, finding PAS chamber temperature contributes the greatest variability to total process uncertainty (7.3%). PMID:23837599

Crack networks in damaged glass

NASA Astrophysics Data System (ADS)

Mallet, Celine; Fortin, Jerome; Gueguen, Yves

2013-04-01

We investigate how cracks develop and propagate in synthetic glass samples. Cracks are introduced in glass by a thermal shock of 300oC. Crack network is documented from optical and electronic microscopy on these samples that have been submitted to a thermal shock only. Samples are cylinder of 80 mm length and 40 mm diameter. Sections were cut along the cylinder axis and perpendicular to it. Using SEM, crack lengths and apertures can be measured. Optical microscopy allows to get the crack distribution over the entire sample. The sample average crack length is 3 mm. The average aperture is 6 ± 3μm. There is however a clear difference between the sample core, where the crack network has approximatively a transverse isotrope symmetry and the outer ring, where cracks are smaller and more numerous. By measuring before and after the thermal treatment the radial P and S wave velocities in room conditions, we can determine the total crack density which is 0.24. Thermally cracked samples, as described above, were submitted to creep tests. Constant axial stress and lateral stress were applied. Several experiments were performed at different stress values. Samples are saturated for 48 hours (to get an homogeneous pore fluid distribution), the axial stress is increased up to 80% of the sample strength. Stress step tests were performed in order to get creep data. The evolution of strain (axial and radial strain) is measured using strain gages, gap sensors (for the global axial strain) and pore volume change (for the volumetric strain). Creep data are interpreted as evidence of sub-critical crack growth in the cracked glass samples. The above microstructural observations are used, together with a crack propagation model, to account for the creep behavior. Assuming that (i) the observed volumetric strain rate is due to crack propagation and (ii) crack aspect ratio is constant we calculate the creep rate. We obtain some value on the crack propagation during a 24 hours of constant stress test. At each of these test, crack propagate of 0.3 to 0.4 mm. From the initial average crack length of 3 mm, the crack reach the size of 5.8 mm at the end of a complete creep test (with 8 constant stress step of 24 hours).

Effects of pore pressure and mud filtration on drilling rates in a permeable sandstone

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

Black, A.D.; DiBona, B.; Sandstrom, J.

1983-10-01

During laboratory drilling tests in a permeable sandstone, the effects of pore pressure and mud filtration on penetration rates were measured. Four water-base muds were used to drill four saturated sandstone samples. The drilling tests were conducted at constant borehole pressure with different back pressures maintained on the filtrate flowing from the bottom of the sandstone samples. Bit weight was also varied. Filtration rates were measured while drilling and with the bit off bottom and mud circulating. Penetration rates were found to be related to the difference between the filtration rates measured while drilling and circulating. There was no observedmore » correlation between standard API filtration measurements and penetration rate.« less

Effects of pore pressure and mud filtration on drilling rates in a permeable sandstone

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

Black, A.D.; Dearing, H.L.; DiBona, B.G.

1985-09-01

During laboratory drilling tests in a permeable sandstone, the effects of pore pressure and mud filtration on penetration rates were measured. Four water-based muds were used to drill four saturated sandstone samples. The drilling tests were conducted at constant borehole pressure while different backpressures were maintained on the filtrate flowing from the bottom of the sandstone samples. Bit weight was varied also. Filtration rates were measured while circulating mud during drilling and with the bit off bottom. Penetration rates were found to be related qualitatively to the difference between the filtration rates measured while drilling and circulating. There was nomore » observed correlation between standard API filtration measurements and penetration rate.« less

Evaluation of the effect of ammonia on nicotine pharmacokinetics using rapid arterial sampling.

PubMed

McKinney, Diana L; Gogova, Maria; Davies, Bruce D; Ramakrishnan, Viswanathan; Fisher, Kelly; Carter, W Hans; Karnes, H Thomas; Garnett, William R; Iyer, Sunil S; Somani, Amit A; Kobal, Gerd; Barr, William H

2012-05-01

The nicotine bolus theory states that the dependence-producing potential of cigarettes relates to a rapid increase in nicotine at brain receptor sites. It has been suggested that ammonia, a compound typically found in tobacco products, further increases the amount of nicotine absorbed and its absorption rate. The aim of this study was to determine whether different ammonia yields in cigarettes affected the rate or amount of nicotine absorption from the lungs to arterial circulation. 34 adult smokers received 3 separate puffs from each of 2 test cigarettes with different ammonia yields (ammonia in smoke: 10.1 μg per cigarette vs. 18.9 μg per cigarette), followed by rapid radial arterial blood sampling (maximum one sample per second) with 30 min between puffs. Arterial blood samples were assayed for nicotine by liquid chromatography tandem mass spectrometry. Pharmacokinetic modeling was performed and the two test cigarettes were assessed for bioequivalence. No significant differences were found in area under the curve, C(max), or T((max)) and the 2 test cigarettes were found to be bioequivalent based on 2 one-sided tests at a significance level of 5%. In addition, the zero-order rate constant (k(0)) obtained from the initial slope of the curves and the model-dependent first-order rate constant (k(a)) were not significantly different. This study provides strong evidence that the different ammonia yields of the test cigarettes had no impact on nicotine pharmacokinetics; thus, the ammonia did not increase the rate or amount of nicotine absorption from a puff of cigarette smoke.

Thermal reactions of small loblolly pine cubes heated on one face in an air atmosphere

Treesearch

Elizabeth J. Johnson; Peter Koch

1972-01-01

When 1-, 2-, and 3-mm cubes of wood were placed on this sample pan of differential scanning calorimeter and the pan heated at a constant rate from 150 to 513oC. in an air atmosphere, all 144 specimens formed an endothermic peak (all specimen averaged 345oC.) at which the rate of heat dissipation exceeded the rate of heat...

Kinetics of thermal and photo-initiated release of tris (1,3-dichloro-2-propyl) phosphate (TDCP) flame retardant from polyurethane foam materials.

PubMed

Ghanem, Raed A

2015-01-01

Kinetics of thermal and photo-initiated release of Tris (1.3-dichloro-2-propyl) phosphate (TDCP) from the polyurethane foam (PUF) materials were studied using a validated chromatographic method with linear calibration curve in the range of 0.03-400 μg mL(-1). Time dependence of TDCP leaching from foam samples was found to follow first-order kinetics; with rate constants directly dependent on ageing temperatures and intensity of UV radiation, rate constants for the thermally and photo initiated were 3.6 × 10(-3), 1.03 × 10(-2), 3.6 × 10(-2) and 3.94 × 10(-2) day(-1), respectively. Migration of TDCP from foam samples simulating skin or oral exposure were observed from all samples regardless of their ageing history, the presence of biological fluids found to enhance the migration rate. Oral exposure to foam material contains TDCP, which was simulated using the Head-over-Heels test, reveals that an average amount of ∼ 1.7% wt./wt. of the total amount of TDCP was found to leach into biological fluids, and it significantly increased to ∼ 6.0% wt./wt. due to ageing conditions. Direct contact between foam material and skin simulated by using the Contact Blotting test reveals that TDCP is transferred from both aged and un-aged samples at different rates, due to the presence of biological fluids; the transferred amount is increased with ageing conditions.

Nonparametric change point estimation for survival distributions with a partially constant hazard rate.

PubMed

Brazzale, Alessandra R; Küchenhoff, Helmut; Krügel, Stefanie; Schiergens, Tobias S; Trentzsch, Heiko; Hartl, Wolfgang

2018-04-05

We present a new method for estimating a change point in the hazard function of a survival distribution assuming a constant hazard rate after the change point and a decreasing hazard rate before the change point. Our method is based on fitting a stump regression to p values for testing hazard rates in small time intervals. We present three real data examples describing survival patterns of severely ill patients, whose excess mortality rates are known to persist far beyond hospital discharge. For designing survival studies in these patients and for the definition of hospital performance metrics (e.g. mortality), it is essential to define adequate and objective end points. The reliable estimation of a change point will help researchers to identify such end points. By precisely knowing this change point, clinicians can distinguish between the acute phase with high hazard (time elapsed after admission and before the change point was reached), and the chronic phase (time elapsed after the change point) in which hazard is fairly constant. We show in an extensive simulation study that maximum likelihood estimation is not robust in this setting, and we evaluate our new estimation strategy including bootstrap confidence intervals and finite sample bias correction.

Kinetics of patulin degradation in model solution, apple cider and apple juice by ultraviolet radiation.

PubMed

Zhu, Yan; Koutchma, Tatiana; Warriner, Keith; Shao, Suqin; Zhou, Ting

2013-08-01

Patulin is a mycotoxin produced by a wide range of molds involved in fruit spoilage, most commonly by Penicillium expansum and is a health concern for both consumers and manufacturers. The current study evaluated feasibility of monochromatic ultraviolet (UV) radiation at 253.7 nm as a possible commercial application for the reduction of patulin in fresh apple cider and juice. The R-52G MINERALIGHT® UV bench top lamp was used for patulin destruction. It was shown that 56.5%, 87.5%, 94.8% and 98.6% reduction of patulin can be achieved, respectively, in the model solution, apple cider, apple juice without ascorbic acid addition and apple juice with ascorbic acid addition in 2-mm thickness sample initially spiked by 1 mg·L(-1) of patulin after UV exposure for 40 min at UV irradiance of 3.00 mW·cm(-2). A mathematic model to compare the degradation rate and effective UV dose was developed. The effective UV doses that were directly absorbed by patulin for photochemical reaction were 430, 674, 724 and 763 mJ·cm(-3), respectively. The fluence-based decimal reduction time was estimated to 309.3, 31.3, 28.9 and 5.1 mW·cm(-2)·min, respectively, in four media mentioned above. The degradation of patulin followed the first-order reaction model. The time-based and fluence-based reaction rate constants were determined to predict patulin degradation. The time-based reaction rate constant of samples treated in dynamic regime with constant stirring (model solution: 2.95E-4 s(-1), juice: 4.31E-4 s(-1)) were significantly higher than samples treated in static regime (model solution: 2.79E-4 s(-1), juice: 3.49E-4 s(-1), p < 0.05) when applied UV irradiance and sample thickness were consistent. The reaction rate constant of patulin degradation in apple juice was significantly higher than model solution (p < 0.05). Although further investigations are still needed, the results of this study demonstrated that UV radiation may be an effective method for treating patulin-containing apple cider and juice.

Demographic and Psychological Predictors of Panel Attrition: Evidence from the New Zealand Attitudes and Values Study

PubMed Central

Satherley, Nicole; Milojev, Petar; Greaves, Lara M.; Huang, Yanshu; Osborne, Danny; Bulbulia, Joseph; Sibley, Chris G.

2015-01-01

This study examines attrition rates over the first four years of the New Zealand Attitudes and Values Study, a longitudinal national panel sample of New Zealand adults. We report the base rate and covariates for the following four distinct classes of respondents: explicit withdrawals, lost respondents, intermittent respondents and constant respondents. A multinomial logistic regression examined an extensive range of demographic and socio-psychological covariates (among them the Big-Six personality traits) associated with membership in these classes (N = 5,814). Results indicated that men, Māori and Asian peoples were less likely to be constant respondents. Conscientiousness and Honesty-Humility were also positively associated with membership in the constant respondent class. Notably, the effect sizes for the socio-psychological covariates of panel attrition tended to match or exceed those of standard demographic covariates. This investigation broadens the focus of research on panel attrition beyond demographics by including a comprehensive set of socio-psychological covariates. Our findings show that core psychological covariates convey important information about panel attrition, and are practically important to the management of longitudinal panel samples like the New Zealand Attitudes and Values Study. PMID:25793746

DESIGN OF A SIMPLE SLOW COOLING DEVICE FOR CRYOPRESERVATION OF SMALL BIOLOGICAL SAMPLES.

PubMed

de Paz, Leonardo Juan; Robert, Maria Celeste; Graf, Daniel Adolfo; Guibert, Edgardo Elvio; Rodriguez, Joaquin Valentin

2015-01-01

Slow cooling is a cryopreservation methodology where samples are cooled to its storage temperature at controlled cooling rates. Design, construction and evaluation of a simple and low cost device for slow cooling of small biological samples. The device was constructed based on Pye's freezer idea. A Dewar flask filled with liquid nitrogen was used as heat sink and a methanol bath containing the sample was cooled at constant rates using copper bars as heat conductor. Sample temperature may be lowered at controlled cooling rate (ranging from 0.4°C/min to 6.0°C/min) down to ~-60°C, where it could be conserved at lower temperatures. An example involving the cryopreservation of Neuro-2A cell line showed a marked influence of cooling rate over post preservation cell viability with optimal values between 2.6 and 4.6°C/min. The cooling device proved to be a valuable alternative to more expensive systems allowing the assessment of different cooling rates to evaluate the optimal condition for cryopreservation of such samples.

A method to quantify at late imaging a release rate of 18F-FDG in tissues.

PubMed

Laffon, Eric; Allard, Michèle; Marthan, Roger; Ducassou, Dominique

2005-08-01

This theoretical work shows that the rate constant for the (18)F-FDG release in tissues can be assessed without needing any arterial blood sampling. The method requires that the clearance of (18)F-FDG from plasma has occurred, whereas (18)F-FDG is still present in the tissue. This condition can be met dating from 3 h after (18)F-FDG injection, when hydration and/or phlorizin injection are applied after the routine static acquisition. The release rate constant can be obtained from a graphical analysis performed at the later decreasing phase of the tissue tracer activity. A two-compartment and a three-compartment model are developed, both in accordance with one another. To cite this article: E. Laffon et al., C. R. Biologies 328 (2005).

Problems encountered in fluctuating flame temperature measurements by thermocouple.

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

Donaldson, A. Burl; Lucero, Ralph E.; Gill, Walter

2008-11-01

Some thermocouple experiments were carried out in order to obtain sensitivity of thermocouple readings to fluctuations in flames and to determine if the average thermocouple reading was representative of the local volume temperature for fluctuating flames. The thermocouples considered were an exposed junction thermocouple and a fully sheathed thermocouple with comparable time constants. Either the voltage signal or indicated temperature for each test was recorded at sampling rates between 300-4,096 Hz. The trace was then plotted with respect to time or sample number so that time variation in voltage or temperature could be visualized and the average indicated temperature couldmore » be determined. For experiments where high sampling rates were used, the signal was analyzed using Fast Fourier Transforms (FFT) to determine the frequencies present in the thermocouple signal. This provided a basic observable as to whether or not the probe was able to follow flame oscillations. To enhance oscillations, for some experiments, the flame was forced. An analysis based on thermocouple time constant, coupled with the transfer function for a sinusoidal input was tested against the experimental results.« less

Problems Encountered in Fluctuating Flame Temperature Measurements by Thermocouple

PubMed Central

Yilmaz, Nadir; Gill, Walt; Donaldson, A. Burl; Lucero, Ralph E.

2008-01-01

Some thermocouple experiments were carried out in order to obtain sensitivity of thermocouple readings to fluctuations in flames and to determine if the average thermocouple reading was representative of the local volume temperature for fluctuating flames. The thermocouples considered were an exposed junction thermocouple and a fully sheathed thermocouple with comparable time constants. Either the voltage signal or indicated temperature for each test was recorded at sampling rates between 300-4,096 Hz. The trace was then plotted with respect to time or sample number so that time variation in voltage or temperature could be visualized and the average indicated temperature could be determined. For experiments where high sampling rates were used, the signal was analyzed using Fast Fourier Transforms (FFT) to determine the frequencies present in the thermocouple signal. This provided a basic observable as to whether or not the probe was able to follow flame oscillations. To enhance oscillations, for some experiments, the flame was forced. An analysis based on thermocouple time constant, coupled with the transfer function for a sinusoidal input was tested against the experimental results. PMID:27873964

Problems Encountered in Fluctuating Flame Temperature Measurements by Thermocouple.

PubMed

Yilmaz, Nadir; Gill, Walt; Donaldson, A Burl; Lucero, Ralph E

2008-12-04

Some thermocouple experiments were carried out in order to obtain sensitivity of thermocouple readings to fluctuations in flames and to determine if the average thermocouple reading was representative of the local volume temperature for fluctuating flames. The thermocouples considered were an exposed junction thermocouple and a fully sheathed thermocouple with comparable time constants. Either the voltage signal or indicated temperature for each test was recorded at sampling rates between 300-4,096 Hz. The trace was then plotted with respect to time or sample number so that time variation in voltage or temperature could be visualized and the average indicated temperature could be determined. For experiments where high sampling rates were used, the signal was analyzed using Fast Fourier Transforms (FFT) to determine the frequencies present in the thermocouple signal. This provided a basic observable as to whether or not the probe was able to follow flame oscillations. To enhance oscillations, for some experiments, the flame was forced. An analysis based on thermocouple time constant, coupled with the transfer function for a sinusoidal input was tested against the experimental results.

Note: Four-port microfluidic flow-cell with instant sample switching

NASA Astrophysics Data System (ADS)

MacGriff, Christopher A.; Wang, Shaopeng; Tao, Nongjian

2013-10-01

A simple device for high-speed microfluidic delivery of liquid samples to a surface plasmon resonance sensor surface is presented. The delivery platform is comprised of a four-port microfluidic cell, two ports serve as inlets for buffer and sample solutions, respectively, and a high-speed selector valve to control the alternate opening and closing of the two outlet ports. The time scale of buffer/sample switching (or sample injection rise and fall time) is on the order of milliseconds, thereby minimizing the opportunity for sample plug dispersion. The high rates of mass transport to and from the central microfluidic sensing region allow for SPR-based kinetic analysis of binding events with dissociation rate constants (kd) up to 130 s-1. The required sample volume is only 1 μL, allowing for minimal sample consumption during high-speed kinetic binding measurement.

Drop-off Detection with the Long Cane: Effects of Different Cane Techniques on Performance

PubMed Central

Kim, Dae Shik; Emerson, Robert Wall; Curtis, Amy

2010-01-01

This study compared the drop-off detection performance with the two-point touch and constant contact cane techniques using a repeated-measures design with a convenience sample of 15 cane users with visual impairments. The constant contact technique was superior to the two-point touch technique in the drop-off detection rate and the 50% detection threshold. The findings may help an orientation and mobility instructor select an appropriate technique for a particular client or training situation. PMID:21209791

A simple recirculating flow system for the calibration of polar organic chemical integrative samplers (POCIS): effect of flow rate on different water pollutants.

PubMed

Di Carro, Marina; Bono, Luca; Magi, Emanuele

2014-03-01

A calibration system for POCIS was developed and used to calculate the sampling rates of eight analytes belonging to pesticides, non-steroidal anti-inflammatory drugs and perfluorinated compounds: atrazine, propazine, terbutylazine, diclofenac, ibuprofen, ketoprofen, perfluorooctanoic acid and perfluorooctanesulfonate. Experiments with a linear velocity of 2.0, 5.1, 10.2 and 15.3 cm/s were carried out for 96 h using two different analyte concentrations. POCIS extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using multiple reaction monitoring to maximize sensitivity. Results highlighted that the calculated sampling rates are rather constant at the considered concentrations and flow rates. Obtained values of sampling rates were then employed to calculate Time-Weighted Average concentration of the analytes in river and drinking waters. © 2013 Published by Elsevier B.V.

An experimental approach to non - extensive statistical physics and Epidemic Type Aftershock Sequence (ETAS) modeling. The case of triaxially deformed sandstones using acoustic emissions.

NASA Astrophysics Data System (ADS)

Stavrianaki, K.; Vallianatos, F.; Sammonds, P. R.; Ross, G. J.

2014-12-01

Fracturing is the most prevalent deformation mechanism in rocks deformed in the laboratory under simulated upper crustal conditions. Fracturing produces acoustic emissions (AE) at the laboratory scale and earthquakes on a crustal scale. The AE technique provides a means to analyse microcracking activity inside the rock volume and since experiments can be performed under confining pressure to simulate depth of burial, AE can be used as a proxy for natural processes such as earthquakes. Experimental rock deformation provides us with several ways to investigate time-dependent brittle deformation. Two main types of experiments can be distinguished: (1) "constant strain rate" experiments in which stress varies as a result of deformation, and (2) "creep" experiments in which deformation and deformation rate vary over time as a result of an imposed constant stress. We conducted constant strain rate experiments on air-dried Darley Dale sandstone samples in a variety of confining pressures (30MPa, 50MPa, 80MPa) and in water saturated samples with 20 MPa initial pore fluid pressure. The results from these experiments used to determine the initial loading in the creep experiments. Non-extensive statistical physics approach was applied to the AE data in order to investigate the spatio-temporal pattern of cracks close to failure. A more detailed study was performed for the data from the creep experiments. When axial stress is plotted against time we obtain the trimodal creep curve. Calculation of Tsallis entropic index q is performed to each stage of the curve and the results are compared with the ones from the constant strain rate experiments. The Epidemic Type Aftershock Sequence model (ETAS) is also applied to each stage of the creep curve and the ETAS parameters are calculated. We investigate whether these parameters are constant across all stages of the curve, or whether there are interesting patterns of variation. This research has been co-funded by the European Union (European Social Fund) and Greek national resources under the framework of the "THALES Program: SEISMO FEAR HELLARC" project of the "Education & Lifelong Learning" Operational Programme.

High-temperature oxidation kinetics of sponge-based E110 cladding alloy

DOE PAGES

Yan, Yong; Garrison, Benton E.; Howell, Mike; ...

2017-11-03

Two-sided oxidation experiments were recently conducted at 900°C–1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. Atmore » or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100–150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.« less

High-temperature oxidation kinetics of sponge-based E110 cladding alloy

NASA Astrophysics Data System (ADS)

Yan, Yong; Garrison, Benton E.; Howell, Mike; Bell, Gary L.

2018-02-01

Two-sided oxidation experiments were recently conducted at 900°C-1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. At or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100-150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.

Evaluation of selected strapdown inertial instruments and pulse torque loops, volume 1

NASA Technical Reports Server (NTRS)

Sinkiewicz, J. S.; Feldman, J.; Lory, C. B.

1974-01-01

Design, operational and performance variations between ternary, binary and forced-binary pulse torque loops are presented. A fill-in binary loop which combines the constant power advantage of binary with the low sampling error of ternary is also discussed. The effects of different output-axis supports on the performance of a single-degree-of-freedom, floated gyroscope under a strapdown environment are illustrated. Three types of output-axis supports are discussed: pivot-dithered jewel, ball bearing and electromagnetic. A test evaluation on a Kearfott 2544 single-degree-of-freedom, strapdown gyroscope operating with a pulse torque loop, under constant rates and angular oscillatory inputs is described and the results presented. Contributions of the gyroscope's torque generator and the torque-to-balance electronics on scale factor variation with rate are illustrated for a SDF 18 IRIG Mod-B strapdown gyroscope operating with various pulse rebalance loops. Also discussed are methods of reducing this scale factor variation with rate by adjusting the tuning network which shunts the torque coil. A simplified analysis illustrating the principles of operation of the Teledyne two-degree-of-freedom, elastically-supported, tuned gyroscope and the results of a static and constant rate test evaluation of that instrument are presented.

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

Mallow, Anne M; Abdelaziz, Omar; Graham, Samuel

The thermal charging performance of phase change materials, specifically paraffin wax, combined with compressed expanded natural graphite foam is studied under constant heat flux and constant temperature conditions. By varying the heat flux between 0.39 W/cm2 and 1.55 W/cm2 or maintaining a boundary temperature of 60 C for four graphite foam bulk densities, the impact on the rate of thermal energy storage is discussed. Thermal charging experiments indicate that thermal conductivity of the composite is an insufficient metric to compare the influence of graphite foam on the rate of thermal energy storage of the PCM composite. By dividing the latentmore » heat of the composite by the time to melt for various boundary conditions and graphite foam bulk densities, it is determined that bulk density selection is dependent on the applied boundary condition. A greater bulk density is advantageous for samples exposed to a constant temperature near the melting temperature as compared to constant heat flux conditions where a lower bulk density is adequate. Furthermore, the anisotropic nature of graphite foam bulk densities greater than 50 kg/m3 is shown to have an insignificant impact on the rate of thermal charging. These experimental results are used to validate a computational model for future use in the design of thermal batteries for waste heat recovery.« less

Use of pressure in reversed-phase liquid chromatography to study protein conformational changes by differential deuterium exchange.

PubMed

Makarov, Alexey A; Schafer, Wes A; Helmy, Roy

2015-02-17

The market of protein therapeutics is exploding, and characterization methods for proteins are being further developed to understand and explore conformational structures with regards to function and activity. There are several spectroscopic techniques that allow for analyzing protein secondary structure in solution. However, a majority of these techniques need to use purified protein, concentrated enough in the solution to produce a relevant spectrum. In this study, we describe a novel approach which uses ultrahigh pressure liquid chromatography (UHPLC) coupled with mass-spectrometry (MS) to explore compressibility of the secondary structure of proteins under increasing pressure detected by hydrogen-deuterium exchange (HDX). Several model proteins were used for these studies. The studies were conducted with UHPLC in isocratic mode at constant flow rate and temperature. The pressure was modified by a backpressure regulator up to about 1200 bar. It was found that the increase of retention factors upon pressure increase, at constant flow rate and temperature, was based on reduction of the proteins' molecular molar volume. The change in the proteins' molecular molar volume was caused by changes in protein folding, as was revealed by differential deuterium exchange. The degree of protein folding under certain UHPLC conditions can be controlled by pressure, at constant temperature and flow rate. By modifying pressure during UHPLC separation, it was possible to achieve changes in protein folding, which were manifested as changes in the number of labile protons exchanged to deuterons, or vice versa. Moreover, it was demonstrated with bovine insulin that a small difference in the number of protons exchanged to deuterons (based on protein folding under pressure) could be observed between batches obtained from different sources. The use of HDX during UHPLC separation allowed one to examine protein folding by pressure at constant flow rate and temperature in a mixture of sample solution with minimal amounts of sample used for analysis.

Growth rate independence of Mg doping in GaN grown by plasma-assisted MBE

NASA Astrophysics Data System (ADS)

Turski, Henryk; Muzioł, Grzegorz; Siekacz, Marcin; Wolny, Pawel; Szkudlarek, Krzesimir; Feduniewicz-Żmuda, Anna; Dybko, Krzysztof; Skierbiszewski, Czeslaw

2018-01-01

Doping of Ga(Al)N layers by plasma-assisted molecular beam epitaxy in Ga-rich conditions on c-plane bulk GaN substrates was studied. Ga(Al)N samples, doped with Mg or Si, grown using different growth conditions were compared. In contrast to Si doped layers, no change in the Mg concentration was observed for layers grown using different growth rates for a constant Mg flux and constant growth temperature. This effect enables the growth of Ga(Al)N:Mg layers at higher growth rates, leading to shorter growth time and lower residual background doping, without the need of increasing Mg flux. Enhancement of Mg incorporation for Al containing layers was also observed. Change of Al content from 0% to 17% resulted in more than two times higher Mg concentration.

Amino acid geochemistry of fossil bones from the Rancho La Brea asphalt deposit, California

USGS Publications Warehouse

McMenamin, M.A.S.; Blunt, D.J.; Kvenvolden, K.A.; Miller, S.E.; Marcus, L.F.; Pardi, R.R.

1982-01-01

Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 ?? 10-6yr-1. Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 ?? 10-6yr-1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits. ?? 1982.

Estimation of uptake rate constants for PCB congeners accumulated by semipermeable membrane devices and brown treat (Salmo trutta)

USGS Publications Warehouse

Meadows, J.C.; Echols, K.R.; Huckins, J.N.; Borsuk, F.A.; Carline, R.F.; Tillitt, D.E.

1998-01-01

The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMD to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB- contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/ g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMDs was also similar. The rates of uptake generally increased or decreased with increasing K(ow), depending on the assumption of presence or absence of TOC.The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMB to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB-contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMBs was also similar. The rates of uptake generally increased or decreased with increasing KOW, depending on the assumption of presence or absence of TOC.

The Hydroxyl Radical Reaction Rate Constant and Products of Dimethyl Succinate

DTIC Science & Technology

2008-03-01

phase reaction of OH + DMS, 10 liters of chamber content were flowed over 2,4- dinitrophenylhydrazine (DNPH) impregnated cartridges. Hydrazones formed... dinitrophenylhydrazine (DNPH) derivatization (method described in experimental methods), and GC/MS/MS (where samples were directly introduced into the mass

FORMAL UNCERTAINTY ANALYSIS OF A LAGRANGIAN PHOTOCHEMICAL AIR POLLUTION MODEL. (R824792)

EPA Science Inventory

This study applied Monte Carlo analysis with Latin
hypercube sampling to evaluate the effects of uncertainty
in air parcel trajectory paths, emissions, rate constants,
deposition affinities, mixing heights, and atmospheric stability
on predictions from a vertically...

Combined techniques for characterising pasta structure reveals how the gluten network slows enzymic digestion rate.

PubMed

Zou, Wei; Sissons, Mike; Gidley, Michael J; Gilbert, Robert G; Warren, Frederick J

2015-12-01

The aim of the present study is to characterise the influence of gluten structure on the kinetics of starch hydrolysis in pasta. Spaghetti and powdered pasta were prepared from three different cultivars of durum semolina, and starch was also purified from each cultivar. Digestion kinetic parameters were obtained through logarithm-of-slope analysis, allowing identification of sequential digestion steps. Purified starch and semolina were digested following a single first-order rate constant, while pasta and powdered pasta followed two sequential first-order rate constants. Rate coefficients were altered by pepsin hydrolysis. Confocal microscopy revealed that, following cooking, starch granules were completely swollen for starch, semolina and pasta powder samples. In pasta, they were completely swollen in the external regions, partially swollen in the intermediate region and almost intact in the pasta strand centre. Gluten entrapment accounts for sequential kinetic steps in starch digestion of pasta; the compact microstructure of pasta also reduces digestion rates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ozone measurements

NASA Technical Reports Server (NTRS)

Randhawa, J.

1978-01-01

The chemiluminescent ozonesonde to be flown with the STRATCOM balloon flight consisted of two main parts: (1) A constant-volume sampling pump made from TEFLON was used for the intake of the air sample. Sample was drawn at a rate of 200 millimeters per minute. (2) Ozone was detected by the chemiluminescent process (Rhodamine - B). Ozone molecules in the air sample flowed over the detector and the photons produced by the destruction of ozone molecules on the chemiluminescent material were monitored by the photomultiplier tube, the output signal from which was transmitted to the ground receiver.

Slowdowns in diversification rates from real phylogenies may not be real.

PubMed

Cusimano, Natalie; Renner, Susanne S

2010-07-01

Studies of diversification patterns often find a slowing in lineage accumulation toward the present. This seemingly pervasive pattern of rate downturns has been taken as evidence for adaptive radiations, density-dependent regulation, and metacommunity species interactions. The significance of rate downturns is evaluated with statistical tests (the gamma statistic and Monte Carlo constant rates (MCCR) test; birth-death likelihood models and Akaike Information Criterion [AIC] scores) that rely on null distributions, which assume that the included species are a random sample of the entire clade. Sampling in real phylogenies, however, often is nonrandom because systematists try to include early-diverging species or representatives of previous intrataxon classifications. We studied the effects of biased sampling, structured sampling, and random sampling by experimentally pruning simulated trees (60 and 150 species) as well as a completely sampled empirical tree (58 species) and then applying the gamma statistic/MCCR test and birth-death likelihood models/AIC scores to assess rate changes. For trees with random species sampling, the true model (i.e., the one fitting the complete phylogenies) could be inferred in most cases. Oversampling deep nodes, however, strongly biases inferences toward downturns, with simulations of structured and biased sampling suggesting that this occurs when sampling percentages drop below 80%. The magnitude of the effect and the sensitivity of diversification rate models is such that a useful rule of thumb may be not to infer rate downturns from real trees unless they have >80% species sampling.

Herbal dryer: drying of ginger (zingiber officinale) using tray dryer

NASA Astrophysics Data System (ADS)

Haryanto, B.; Hasibuan, R.; Alexander; Ashari, M.; Ridha, M.

2018-02-01

Drying is widely used as a method to preserve food because of its convenience and affordability. Drying of ginger using tray dryer were carried out at various drying conditions, such as air-drying flow, air-drying temperature, and sample dimensions, to achieve the highest drying rate. Samples with various dimensions were placed in the tray dryer and dried using various air-drying flow and temperatures. The weights of samples were observed every 3 minutes interval. Drying was stopped after three times of constant weighing. Data of drying was collected to make the drying curves. Drying curves show that the highest drying rate is achieved using highest air flow and temperature.

Investigation of New Semiinsulating Behavior of III-V Compounds.

DTIC Science & Technology

1990-02-23

load (I 10) directions, respectively. Open circles correspond to p-type samples cell . The sample with the length Io of 7 mm, was placed deformed in the...DISCUSSION at a constant rate dl /dt of 0.05 mm/min. The load cell was used to monitor the applied force. All samples used in this A. Free-carrier...the growth of epitaxial quality GaAs bulk crystals (Bryskiewicz et al 1987b). A schematic diagram of the growth cell used in our growth experi- S-nts

Constant strain rate experiments and constitutive modeling for a class of bitumen

NASA Astrophysics Data System (ADS)

Reddy, Kommidi Santosh; Umakanthan, S.; Krishnan, J. Murali

2012-08-01

The mechanical properties of bitumen vary with the nature of the crude source and the processing methods employed. To understand the role of the processing conditions played in the mechanical properties, bitumen samples derived from the same crude source but processed differently (blown and blended) are investigated. The samples are subjected to constant strain rate experiments in a parallel plate rheometer. The torque applied to realize the prescribed angular velocity for the top plate and the normal force applied to maintain the gap between the top and bottom plate are measured. It is found that when the top plate is held stationary, the time taken by the torque to be reduced by a certain percentage of its maximum value is different from the time taken by the normal force to decrease by the same percentage of its maximum value. Further, the time at which the maximum torque occurs is different from the time at which the maximum normal force occurs. Since the existing constitutive relations for bitumen cannot capture the difference in the relaxation times for the torque and normal force, a new rate type constitutive model, incorporating this response, is proposed. Although the blended and blown bitumen samples used in this study correspond to the same grade, the mechanical responses of the two samples are not the same. This is also reflected in the difference in the values of the material parameters in the model proposed. The differences in the mechanical properties between the differently processed bitumen samples increase further with aging. This has implications for the long-term performance of the pavement.

The Hydroxyl Radical Reaction Rate Constant and Products of Cyclohexanol

DTIC Science & Technology

2007-10-01

Analysis Samples from kinetic studies were quantitativelymon- itored using a Hewlett-Packard (HP) gas chromato- graph (GC) 5890 with a flame ionization...excluded from the reaction mixture and the COL concentration was approximately doubled (4.9–9 ppm). Product Study Analysis Reactant mixtures and standards...from product identi- fication experiments were sampled by exposing a 100% polydimethylsiloxane solid phase microextrac- tion fiber (SPME) in the

Fabrication of copper decorated tungsten oxide-titanium oxide nanotubes by photochemical deposition technique and their photocatalytic application under visible light

NASA Astrophysics Data System (ADS)

Momeni, Mohamad Mohsen

2015-12-01

Copper decorated WO3-TiO2 nanotubes (Cu/WTNs) with a high photocatalytic activity were prepared by anodizing and photochemical deposition. Highly ordered WO3-TiO2 nanotubes (WTNs) on pure titanium foils were successfully fabricated by electrochemical anodizing and copper deposited on these nanotubes (Cu/WTNs) by photoreduction method. The resulting samples were characterized by various methods. Only the anatase phase was detected by X-ray diffraction analysis. The presence of copper in the structure of thin films was confirmed by energy dispersive X-ray spectrometry and X-ray diffraction. The extension of optical absorption into the visible region of as-prepared films was indicated by UV/Vis spectroscopy. The degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of the obtained samples. Results showed that the photocatalytic activity of Cu/WTNs samples is higher than bare WTNs sample. Kinetic research showed that the reaction rate constant of Cu/WTNs is approximately 2.5 times higher than the apparent reaction rate constant of bare WTNs. These results not only offer an economical method for constructing Cu/WTNs photocatalysts, but also shed new insight on the rational design of a low cost and high-efficiency photocatalyst for environmental remediation.

Design of a blood-freezing system for leukemia research

NASA Technical Reports Server (NTRS)

Williams, T. E.; Cygnarowicz, T. A.

1978-01-01

Leukemia research involves the use of cryogenic freezing and storage equipment. In a program being carried out at the National Cancer Institute (NCI), bone marrow (white blood cells) was frozen using a standard cryogenic biological freezer. With this system, it is difficult to maintain the desired rate of freezing and repeatability from sample to sample. A freezing system was developed that satisfies the requirements for a repeatable, constant freezing rate. The system was delivered to NIC and is now operational. This report describes the design of the major subsystems, the analyses, the operating procedure, and final system test results.

Ultraviolet radiation effects on the infrared damage rate of a thermal control coating

NASA Technical Reports Server (NTRS)

Bass, J. A.

1972-01-01

The effects of ultraviolet radiation on the infrared reflectance of ZnO silicone white thermal coatings were investigated. Narrow band ultraviolet radiation for wavelengths in the 2200A to 3500A range by a monochromator and a high pressure, 150-W Eimac xenon lamp. The sample was irradiated while in a vacuum of at least 0.000001 torr, and infrared reflectance was measured in situ with a spectroreflectometer at 19,500A. Reflectance degradation was studied as a function of wavelength, time, intensity, and dose. Damage was wavelength dependent at constant exposure, but no maximum was evident above the shortest wavelength investigated here. The degradation rate at constant intensity was an exponential function of time and varies with intensity.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Exploratory Study on VO2 On-kinetics During Treadmill Walking in Women With Systemic Lupus Erythematosus

PubMed Central

Keyser, Randall E.; Rus, Violeta; Mikdashi, Jamal A.; Handwerger, Barry S.

2010-01-01

Objective To determine if oxygen consumption (VO2) on-kinetics differed between groups of women with systemic lupus erythematosus (SLE) and sedentary but otherwise healthy controls. Design Exploratory case control study. Setting Medical school exercise physiology laboratory. Participants Convenience samples of 12 women with SLE and 10 sedentary but otherwise healthy controls. Intervention None. Main Outcome Measurements VO2 on-kinetics indices including time to steady state, rate constant, mean response time (MRT), transition constant, and oxygen deficit measured during bouts of treadmill walking at intensities of 3-METS and 5-METS. Results Time to steady state and oxygen deficit were increased and rate constant was decreased in the women with SLE compared to controls. At the 5-MET energy demand, the transition constant was lower and MRT was longer in the women with SLE than in the controls. For a comparable, relative energy expenditure that was slightly lower than the anaerobic threshold, the transition constant was higher in the controls than in the women with SLE. Conclusion VO2 on-kinetics was prolonged in the women with SLE. The prolongation was concomitant with an increase in oxygen deficit and may underlie performance fatigability in women with SLE. PMID:20801259

Control of the Protein Turnover Rates in Lemna minor

PubMed Central

Trewavas, A.

1972-01-01

The control of protein turnover in Lemna minor has been examined using a method described in the previous paper for determining the rate constants of synthesis and degradation of protein. If Lemna is placed on water, there is a reduction in the rate constants of synthesis of protein and an increase (3- to 6-fold) in the rate constant of degradation. The net effect is a loss of protein from the tissue. Omission of nitrate, phosphate, sulfate, magnesium, or calcium results in increases in the rate constant of degradation of protein. An unusual dual effect of benzyladenine on the turnover constants has been observed. Treatment of Lemna grown on sucrose-mineral salts with benzyladenine results in alterations only in the rate constant of synthesis. Treatment of Lemna grown on water with benzyladenine alters only the rate constant of degradation. Abscisic acid on the other hand alters both rate constants of synthesis and degradation of protein together. Inclusion of growth-inhibiting amino acids in the medium results in a reduction in the rate constants of synthesis and increases in the rate constant of degradation of protein. It is concluded that the rate of turnover of protein in Lemna is very dependent on the composition of the growth medium. Conditions which reduce growth rates also reduce the rates of synthesis of protein and increase those of degradation. PMID:16657895

Monitoring bald eagles using lists of nests: Response to Watts and Duerr

USGS Publications Warehouse

Sauer, John R.; Otto, Mark C.; Kendall, William L.; Zimmerman, Guthrie S.

2011-01-01

The post-delisting monitoring plan for bald eagles (Haliaeetus leucocephalus) roposed use of a dual-frame sample design, in which sampling of known nest sites in combination with additional area-based sampling is used to estimate total number of nesting bald eagle pairs. Watts and Duerr (2010) used data from repeated observations of bald eagle nests in Virginia, USA to estimate a nest turnover rate and used this rate to simulate decline in number of occupied nests in list nests over time. Results of Watts and Duerr suggest that, given the rates of loss of nests from the list of known nest sites in Virginia, the list information will be of little value to sampling unless lists are constantly updated. Those authors criticize the plan for not placing sufficient emphasis on updating and maintaining lists of bald eagle nests. Watts and Duerr's metric of turnover rate does not distinguish detectability or temporary nonuse of nests from permanent loss of nests and likely overestimates turnover rate. We describe a multi-state capture–recapture model that allows appropriate estimation of rates of loss of nests, and we use the model to estimate rates of loss from a sample of nests from Maine, USA. The post-delisting monitoring plan addresses the need to maintain and update the lists of nests, and we show that dual frame sampling is an effective approach for sampling nesting bald eagle populations.

Modeling Hybridization Kinetics of Gene Probes in a DNA Biochip Using FEMLAB

PubMed Central

Munir, Ahsan; Waseem, Hassan; Williams, Maggie R.; Stedtfeld, Robert D.; Gulari, Erdogan; Tiedje, James M.; Hashsham, Syed A.

2017-01-01

Microfluidic DNA biochips capable of detecting specific DNA sequences are useful in medical diagnostics, drug discovery, food safety monitoring and agriculture. They are used as miniaturized platforms for analysis of nucleic acids-based biomarkers. Binding kinetics between immobilized single stranded DNA on the surface and its complementary strand present in the sample are of interest. To achieve optimal sensitivity with minimum sample size and rapid hybridization, ability to predict the kinetics of hybridization based on the thermodynamic characteristics of the probe is crucial. In this study, a computer aided numerical model for the design and optimization of a flow-through biochip was developed using a finite element technique packaged software tool (FEMLAB; package included in COMSOL Multiphysics) to simulate the transport of DNA through a microfluidic chamber to the reaction surface. The model accounts for fluid flow, convection and diffusion in the channel and on the reaction surface. Concentration, association rate constant, dissociation rate constant, recirculation flow rate, and temperature were key parameters affecting the rate of hybridization. The model predicted the kinetic profile and signal intensities of eighteen 20-mer probes targeting vancomycin resistance genes (VRGs). Predicted signal intensities and hybridization kinetics strongly correlated with experimental data in the biochip (R2 = 0.8131). PMID:28555058

Modeling Hybridization Kinetics of Gene Probes in a DNA Biochip Using FEMLAB.

PubMed

Munir, Ahsan; Waseem, Hassan; Williams, Maggie R; Stedtfeld, Robert D; Gulari, Erdogan; Tiedje, James M; Hashsham, Syed A

2017-05-29

Microfluidic DNA biochips capable of detecting specific DNA sequences are useful in medical diagnostics, drug discovery, food safety monitoring and agriculture. They are used as miniaturized platforms for analysis of nucleic acids-based biomarkers. Binding kinetics between immobilized single stranded DNA on the surface and its complementary strand present in the sample are of interest. To achieve optimal sensitivity with minimum sample size and rapid hybridization, ability to predict the kinetics of hybridization based on the thermodynamic characteristics of the probe is crucial. In this study, a computer aided numerical model for the design and optimization of a flow-through biochip was developed using a finite element technique packaged software tool (FEMLAB; package included in COMSOL Multiphysics) to simulate the transport of DNA through a microfluidic chamber to the reaction surface. The model accounts for fluid flow, convection and diffusion in the channel and on the reaction surface. Concentration, association rate constant, dissociation rate constant, recirculation flow rate, and temperature were key parameters affecting the rate of hybridization. The model predicted the kinetic profile and signal intensities of eighteen 20-mer probes targeting vancomycin resistance genes (VRGs). Predicted signal intensities and hybridization kinetics strongly correlated with experimental data in the biochip (R² = 0.8131).

Measuring star formation rates in blue galaxies

NASA Technical Reports Server (NTRS)

Gallagher, John S., III; Hunter, Deidre A.

1987-01-01

The problems associated with measurements of star formation rates in galaxies are briefly reviewed, and specific models are presented for determinations of current star formation rates from H alpha and Far Infrared (FIR) luminosities. The models are applied to a sample of optically blue irregular galaxies, and the results are discussed in terms of star forming histories. It appears likely that typical irregular galaxies are forming stars at nearly constant rates, although a few examples of systems with enhanced star forming activity are found among HII regions and luminous irregular galaxies.

Artificial neural networks for processing fluorescence spectroscopy data in skin cancer diagnostics

NASA Astrophysics Data System (ADS)

Lenhardt, L.; Zeković, I.; Dramićanin, T.; Dramićanin, M. D.

2013-11-01

Over the years various optical spectroscopic techniques have been widely used as diagnostic tools in the discrimination of many types of malignant diseases. Recently, synchronous fluorescent spectroscopy (SFS) coupled with chemometrics has been applied in cancer diagnostics. The SFS method involves simultaneous scanning of both emission and excitation wavelengths while keeping the interval of wavelengths (constant-wavelength mode) or frequencies (constant-energy mode) between them constant. This method is fast, relatively inexpensive, sensitive and non-invasive. Total synchronous fluorescence spectra of normal skin, nevus and melanoma samples were used as input for training of artificial neural networks. Two different types of artificial neural networks were trained, the self-organizing map and the feed-forward neural network. Histopathology results of investigated skin samples were used as the gold standard for network output. Based on the obtained classification success rate of neural networks, we concluded that both networks provided high sensitivity with classification errors between 2 and 4%.

In Situ X-ray Diffraction Studies of Li(sub x)Mn(sub 2)O(sub 4) Cathode Materials by Synchrotron X-ray Radiation

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

Yang, X. Q.; Sun, X.; Lee, S. J.

In Situ x-ray diffraction studies on Li{sub x}Mn{sub 2}O{sub 4} spinel cathode materials during charge-discharge cycles were carried out by using a synchrotron as x-ray source. Lithium rich (x = 1.03-1.06) spinel materials obtained from two different sources were studied. Three cubic phases with different lattice constants were observed during charge-discharge cycles in all the samples when a Sufficiently low charge-discharge rate (C/10) was used. There are two regions of two-phase coexistence between these three phases, indicating that both phase transitions are first order. The separation of the Bragg peaks representing these three phases varies from sample to sample andmore » also depends on the charge-discharge rate. These results show that the de-intercalation of lithium in lithium-rich spinel cathode materials proceeds through a series of phase transitions from a lithium-rich phase to a lithium-poor phase and finally to a {lambda}-MnO{sub 2} like cubic phase, rather than through a continuous lattice constant contraction in a single phase.« less

Geographic and temporal differences in band reporting rates for American black ducks

USGS Publications Warehouse

Conroy, M.J.; Blandin, W.W.

1984-01-01

Recoveries of reward- and standard-banded American black ducks (Anas rubripes) were used to estimate band reporting rates and to investigate geographic and temporal variability in reporting rate for 1978-80. Reporting rates were higher close ( 20 km) to the parent banding site in 3 of 42 samples and were higher close to the nearest black duck banding site in 3 of 35 samples., Reporting rates were higher P 0.05) in Canada than in the Atlantic Flyway for the pre-huntIng season 1980-banded sample, but were otherwise similar among regions. Temporal differences over the duration of the study occured, but there were no consistent trends over time. The small number of rejections suggests that there is little evidence of differences in band reporting rate by proximity to banding sites, geographic location, or over time. Thus, the best estimate of band reporting rate for black ducks is a constant 0.43. This estimate should be used with caution, because we believe that it overestimates reporting rate due to the unknown proportion of reward bands found that were not reported.

Elementary Energy Transfer Pathways in Allochromatium vinosum Photosynthetic Membranes

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

Lüer, Larry; Carey, Anne-Marie; Henry, Sarah

2015-11-01

Allochromatium vinosum (formerly Chromatium vinosum) purple bacteria are known to adapt their light-harvesting strategy during growth according to environmental factors such as temperature and average light intensity. Under low light illumination or low ambient temperature conditions, most of the LH2 complexes in the photosynthetic membranes form a B820 exciton with reduced spectral overlap with LH1. To elucidate the reason for this light and temperature adaptation of the LH2 electronic structure, we performed broadband femtosecond transient absorption spectroscopy as a function of excitation wavelength in A. vinosum membranes. A target analysis of the acquired data yielded individual rate constants for allmore » relevant elementary energy transfer (ET) processes. We found that the ET dynamics in high-light-grown membranes was well described by a homogeneous model, with forward and backward rate constants independent of the pump wavelength. Thus, the overall B800→B850→B890→ Reaction Center ET cascade is well described by simple triexponential kinetics. In the low-light-grown membranes, we found that the elementary backward transfer rate constant from B890 to B820 was strongly reduced compared with the corresponding constant from B890 to B850 in high-light-grown samples. The ET dynamics of low-light-grown membranes was strongly dependent on the pump wavelength, clearly showing that the excitation memory is not lost throughout the exciton lifetime. The observed pump energy dependence of the forward and backward ET rate constants suggests exciton diffusion via B850→ B850 transfer steps, making the overall ET dynamics nonexponential. Our results show that disorder plays a crucial role in our understanding of low-light adaptation in A. vinosum.« less

Elementary Energy Transfer Pathways in Allochromatium vinosum Photosynthetic Membranes

PubMed Central

Lüer, Larry; Carey, Anne-Marie; Henry, Sarah; Maiuri, Margherita; Hacking, Kirsty; Polli, Dario; Cerullo, Giulio; Cogdell, Richard J.

2015-01-01

Allochromatium vinosum (formerly Chromatium vinosum) purple bacteria are known to adapt their light-harvesting strategy during growth according to environmental factors such as temperature and average light intensity. Under low light illumination or low ambient temperature conditions, most of the LH2 complexes in the photosynthetic membranes form a B820 exciton with reduced spectral overlap with LH1. To elucidate the reason for this light and temperature adaptation of the LH2 electronic structure, we performed broadband femtosecond transient absorption spectroscopy as a function of excitation wavelength in A. vinosum membranes. A target analysis of the acquired data yielded individual rate constants for all relevant elementary energy transfer (ET) processes. We found that the ET dynamics in high-light-grown membranes was well described by a homogeneous model, with forward and backward rate constants independent of the pump wavelength. Thus, the overall B800→B850→B890→ Reaction Center ET cascade is well described by simple triexponential kinetics. In the low-light-grown membranes, we found that the elementary backward transfer rate constant from B890 to B820 was strongly reduced compared with the corresponding constant from B890 to B850 in high-light-grown samples. The ET dynamics of low-light-grown membranes was strongly dependent on the pump wavelength, clearly showing that the excitation memory is not lost throughout the exciton lifetime. The observed pump energy dependence of the forward and backward ET rate constants suggests exciton diffusion via B850→ B850 transfer steps, making the overall ET dynamics nonexponential. Our results show that disorder plays a crucial role in our understanding of low-light adaptation in A. vinosum. PMID:26536265

Elementary Energy Transfer Pathways in Allochromatium vinosum Photosynthetic Membranes.

PubMed

Lüer, Larry; Carey, Anne-Marie; Henry, Sarah; Maiuri, Margherita; Hacking, Kirsty; Polli, Dario; Cerullo, Giulio; Cogdell, Richard J

2015-11-03

Allochromatium vinosum (formerly Chromatium vinosum) purple bacteria are known to adapt their light-harvesting strategy during growth according to environmental factors such as temperature and average light intensity. Under low light illumination or low ambient temperature conditions, most of the LH2 complexes in the photosynthetic membranes form a B820 exciton with reduced spectral overlap with LH1. To elucidate the reason for this light and temperature adaptation of the LH2 electronic structure, we performed broadband femtosecond transient absorption spectroscopy as a function of excitation wavelength in A. vinosum membranes. A target analysis of the acquired data yielded individual rate constants for all relevant elementary energy transfer (ET) processes. We found that the ET dynamics in high-light-grown membranes was well described by a homogeneous model, with forward and backward rate constants independent of the pump wavelength. Thus, the overall B800→B850→B890→ Reaction Center ET cascade is well described by simple triexponential kinetics. In the low-light-grown membranes, we found that the elementary backward transfer rate constant from B890 to B820 was strongly reduced compared with the corresponding constant from B890 to B850 in high-light-grown samples. The ET dynamics of low-light-grown membranes was strongly dependent on the pump wavelength, clearly showing that the excitation memory is not lost throughout the exciton lifetime. The observed pump energy dependence of the forward and backward ET rate constants suggests exciton diffusion via B850→ B850 transfer steps, making the overall ET dynamics nonexponential. Our results show that disorder plays a crucial role in our understanding of low-light adaptation in A. vinosum. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Fracture in Westerly granite under AE feedback and constant strain rate loading: Nucleation, quasi-static propagation, and the transition to unstable fracture propagation

USGS Publications Warehouse

Thompson, B.D.; Young, R.P.; Lockner, D.A.

2006-01-01

New observations of fracture nucleation are presented from three triaxial compression experiments on intact samples of Westerly granite, using Acoustic Emission (AE) monitoring. By conducting the tests under different loading conditions, the fracture process is demonstrated for quasi-static fracture (under AE Feedback load), a slowly developing unstable fracture (loaded at a 'slow' constant strain rate of 2.5 ?? 10-6/s) and an unstable fracture that develops near instantaneously (loaded at a 'fast' constant strain rate of 5 ?? 10-5/s). By recording a continuous ultrasonic waveform during the critical period of fracture, the entire AE catalogue can be captured and the exact time of fracture defined. Under constant strain loading, three stages are observed: (1) An initial nucleation or stable growth phase at a rate of ??? 1.3 mm/s, (2) a sudden increase to a constant or slowly accelerating propagation speed of ??? 18 mm/s, and (3) unstable, accelerating propagation. In the ??? 100 ms before rupture, the high level of AE activity (as seen on the continuous record) prevented the location of discrete AE events. A lower bound estimate of the average propagation velocity (using the time-to-rupture and the existing fracture length) suggests values of a few m/s. However from a low gain acoustic record, we infer that in the final few ms, the fracture propagation speed increased to 175 m/s. These results demonstrate similarities between fracture nucleation in intact rock and the nucleation of dynamic instabilities in stick slip experiments. It is suggested that the ability to constrain the size of an evolving fracture provides a crucial tool in further understanding the controls on fracture nucleation. ?? Birkha??user Verlag, Basel, 2006.

Charge displacement in bacteriorhodopsin during the forward and reverse bR-K phototransition.

PubMed Central

Groma, G I; Hebling, J; Ludwig, C; Kuhl, J

1995-01-01

Dried oriented purple membrane samples of Halobacterium salinarium were excited by 150 fs laser pulses of 620 nm with a 7 kHz repetition rate. An unusual complex picosecond electric response signal consisting of a positive and a negative peak was detected by a sampling oscilloscope. The ratio of the two peaks was changed by 1) reducing the repetition rate, 2) varying the intensity of the excitation beam, and 3) applying background illumination by light of 647 nm or 511 nm. All of these features can be explained by the simultaneous excitation of the bacteriorhodopsin ground form and the K intermediate. The latter was populated by the (quasi)continuous excitation attributable to its prolonged lifetime in a dehydrated state. Least-square analysis resulted in a 5 ps upper and 2.5 ps lower limit for the time constant of the charge displacement process, corresponding to the forward reaction. That is in good agreement with the formation time of K. The charge separation driven by the reverse phototransition was faster, having a time constant of a 3.5 ps upper limit. The difference in the rates indicates the existence of different routes for the forward and the reverse photoreactions. PMID:8580349

Diffusive sampling of methylene chloride with solid phase microextraction.

PubMed

Chen, Cheng-Yao; Hsiech, Chunming; Lin, Jia-Ming

2006-12-29

This study examined the characteristics of a solid phase microextraction (SPME) assembly as a passive sampler to determine the short-term exposure level (STEL) of methylene chloride. Two types of SPME fibers and six sampling-related factors were chosen and nested in an L(18) Taguchi's orthogonal array. Samples were thermally desorpted and analyzed by gas chromatograph equipped with an electron capture detector (GC/ECD). The use of 85-mum Carboxen/polydimethylsiloxane (Car/PDMS) fibers resulted in greater adsorbed mass, which was highly correlated with the product of concentration and sampling time (r>0.99, p<0.0001), than 85-microm polyacrylate fibers. The sampling rate (SR) of the 85-microm Carboxen/polydimethylsiloxane fibers was not significantly affected by variations in relative humidity (0-80%) and coexistent toluene (none to 100 ppm). Variance of sampling rate was predominantly attributed to the diffusive path length (86.4%) and sampling time (5.7%). With diffusive paths of 3, 10 and 15 mm, the sampling rates of 85-microm Carboxen/polydimethylsiloxane fibers for methylene chloride were 1.4 x 10(-2), 7.7 x 10(-3) and 5.1 x1 0(-3)mL min(-1), respectively. The measured sampling rates were greater than the theoretical values, and decreased with increment of sampling time until they came to constant.

Thermoluminscence of irradiated herbs and spices

NASA Astrophysics Data System (ADS)

Mamoon, A.; Abdul-Fattah, A. A.; Abulfaraj, W. H.

1994-07-01

Several types of herbs and spices from the local market were irradiated with different doses of γ radiations. Doses varied from a few kilograys to 10 kilograys. Thermoluminescence of the irradiated samples and their controls was investigated. For the same type of herb or spice glow curves of different magnitudes, corresponding somewhat to the doses given, were obtained from the irradiated samples. Most control samples gave little or insignificant glow. Glow curves from different herbs and spices irradiated with the same doses were not similar in the strength of the glow signal given. Samples of the black pepper obtained from different packages sometimes give glow curves of very different intensities. Samples from irradiated black pepper were found to show little fading of their glow curves even at 9 months postirradiation. All irradiations were done under the same experimental conditions and at a dose rate of approximately 1 kGy h-1. The glow curves were obtained using a heating rate of about 9°C s-1 and a constant nitrogen flow rate.

The vibrational dependence of dissociative recombination: Rate constants for N{sub 2}{sup +}

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

Guberman, Steven L., E-mail: slg@sci.org

Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N{sub 2}{sup +} ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller thanmore » 2.0 × 10{sup −7} cm{sup 3}/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N{sub 2}{sup +} ionospheric densities.« less

Calculation of kinetic rate constants from thermodynamic data

NASA Technical Reports Server (NTRS)

Marek, C. John

1995-01-01

A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rate constants computed from thermodynamics compare well with the current kinetic rate constants. This method is self consistent and does not have extensive rules. It is first demonstrated and calibrated by computing the HBr reaction from H2 and Br2. This method then is used on other reactions.

Fabrication of barium titanate doped strontium using co-precipitation method

NASA Astrophysics Data System (ADS)

Iriani, Y.; Yasin, M. A.; Suryana, R.

2018-03-01

Fabrication of barium titanate (BaTiO3/BT) doped strontium (Sr) using co-precipitation method has been successfully conducted. The research aim is to get the best of mole variation of Sr doping to ferroelectric material properties. Doping Sr was varied at 1%, 2%, 3%, 4% and 5% in BaTiO3. Each sample was sintered at temperature of 1100°C with holding time for 6 h and temperature rate at 10°C/min. They were then characterized by XRD instrument to investigate the crystal structure, LCR meter to measure the dielectric constant, and Sawyer Tower circuit to reveal the hysteresis curve. The peaks of XRD shift towards larger angle when mole doping Sr increase. The crystallinity of all samples is above 90% and the crystallite size is in the range of 27 nm to 34 nm. Hysteresis curve from Sawyer Tower testing confirms that all samples are ferroelectric material. The RLC measurement results reveal that the less frequency leads to the higher dielectric constant while the highest dielectric constant belongs to the BT doped 3% of Sr. Therefore, it is the best variation obtained in this research.

Stress evolution and associated microstructure during transient creep of olivine at 1000-1200 °C

NASA Astrophysics Data System (ADS)

Thieme, M.; Demouchy, S.; Mainprice, D.; Barou, F.; Cordier, P.

2018-05-01

We study the mechanical response and correlated microstructure of axial deformed fine-grained olivine aggregates as a function of incremental finite strains. Deformation experiments were conducted in uniaxial compression in an internally heated gas-medium deformation apparatus at temperatures of 1000 and 1200 °C, at strain rates of 10-6 s-1 to 10-5 s-1 and at confining pressure of 300 MPa. Sample volumes are around 1.2 cm3. Finite strains range from 0.1 to 8.6% and corresponding maximal (final) differential stresses range from 80 to 1073 MPa for deformation at 1000 °C and from 71 to 322 MPa for deformation at 1200 °C. At 1200 °C, samples approach steady state deformation after about 8% of strain. At 1000 °C, significant strain hardening leads to stresses exceeding the confining pressure by a factor of 3.5 with brittle deformation after 3% of strain. Deformed samples were characterized by electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). EBSD maps with step sizes as low as 50 nm were acquired without introducing analytical artifacts for the first time. The grain size of deformed samples ranges from 2.1 to 2.6 μm. Despite clear strain hardening, texture or microstructure do not change as a function of stress or finite strain. This observation is supported by a constant texture strength (J-index) and symmetry (BA-index), constant grain shape and aspect ratio, constant density of geometrically necessary dislocations, grain orientation spread, and constant subgrain boundary spacing and misorientation in between samples. TEM shows that all samples exhibit unambiguous dislocation activity but with a highly heterogeneous dislocation distribution. Olivine grains display evidence of [1 0 0] and [0 0 1] slip activity, but there is no evidence of interaction between the dislocations from the different slip systems. Several observations of grain boundaries acting as dislocation sources have been found. We find no confirmation of increasing dislocation densities as the cause for strain hardening during transient creep. This suggests other, yet not fully understood mechanisms affecting the strength of deformed olivine. These mechanisms could possibly involve grain boundaries. Such mechanisms are relevant for the deformation of uppermost mantle rocks, where the Si diffusion rate is too slow and dislocation glide must be accommodated in another way to fulfill the von Mises criterion.

Molten salt synthesis of nanocrystalline phase of high dielectric constant material CaCu3Ti4O12.

PubMed

Prakash, B Shri; Varma, K B R

2008-11-01

Nanocrystalline powders of giant dielectric constant material, CaCu3Ti4O12 (CCTO), have been prepared successfully by the molten salt synthesis (MSS) using KCl at 750 degrees C/10 h, which is significantly lower than the calcination temperature (approximately 1000 degrees C) that is employed to obtain phase pure CCTO in the conventional solid-state reaction route. The water washed molten salt synthesized powder, characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) confirmed to be a phase pure CCTO associated with approximately 150 nm sized crystallites of nearly spherical shape. The decrease in the formation temperature/duration of CCTO in MSS method was attributed to an increase in the diffusion rate or a decrease in the diffusion length of reacting ions in the molten salt medium. As a consequence of liquid phase sintering, pellets of as-synthesized KCl containing CCTO powder exhibited higher sinterability and grain size than that of KCl free CCTO samples prepared by both MSS method and conventional solid-state reaction route. The grain size and the dielectric constant of KCl containing CCTO ceramics increased with increasing sintering temperature (900 degrees C-1050 degrees C). Indeed the dielectric constants of these ceramics were higher than that of KCl free CCTO samples prepared by both MSS method and those obtained via the solid-state reaction route and sintered at the same temperature. Internal barrier layer capacitance (IBLC) model was invoked to correlate the observed dielectric constant with the grain size in these samples.

Effect of surface modification on hydration kinetics of carbamazepine anhydrate using isothermal microcalorimetry.

PubMed

Otsuka, Makoto; Ishii, Mika; Matsuda, Yoshihisa

2003-01-01

The purpose of this research was to improve the stability of carbamazepine (CBZ) bulk powder under high humidity by surface modification. The surface-modified anhydrates of CBZ were obtained in a specially designed surface modification apparatus at 60 degrees C via the adsorption of n-butanol, and powder x-ray diffraction, Fourier-Transformed Infrared spectra, and differential scanning calorimetry were used to determine the crystalline characteristics of the samples. The hydration process of intact and surface-modified CBZ anhydrate at 97% relative humidity (RH) and 40 +/-C 1 degrees C was automatically monitored by using isothermal microcalorimetry (IMC). The dissolution test for surface-modified samples (20 mg) was performed in 900 mL of distilled water at 37 +/-C 0.5 degrees C with stirring by a paddle at 100 rpm as in the Japanese Pharmacopoeia XIII. The heat flow profiles of hydration of intact and surface-modified CBZ anhydrates at 97% RH by using IMC profiles showed a maximum peak at around 10 hours and 45 hours after 0 and 10 hours of induction, respectively. The result indicated that hydration of CBZ anhydrate was completely inhibited at the initial stage by surface modification of n-butanol and thereafter transformed into dihydrate. The hydration of surface-modified samples followed a 2-dimensional phase boundary process with an induction period (IP). The IP of intact and surface-modified samples decreased with increase of the reaction temperature, and the hydration rate constant (k) increased with increase of the temperature. The crystal growth rate constants of nuclei of the intact sample were significantly larger than the surface-modified sample's at each temperature. The activation energy (E) of nuclei formation and crystal growth process for hydration of surface-modified CBZ anhydrate were evaluated to be 20.1 and 32.5 kJ/mol, respectively, from Arrhenius plots, but the Es of intact anhydrate were 56.3 and 26.8 kJ/mol, respectively. The dissolution profiles showed that the surface-modified sample dissolved faster than the intact sample at the initial stage. The dissolution kinetics were analyzed based on the Hixon-Crowell equation, and the dissolution rate constants for intact and surface-modified anhydrates were found to be 0.0102 +/-C 0.008 mg(1/3) x min(-1) and 0.1442 +/-C 0.0482 mg(1/3) x min(-1). The surface-modified anhydrate powders were more stable than the nonmodified samples under high humidity and showed resistance against moisture. However, surface modification induced rapid dissolution in water compared to the control.

Carbonyls in the metropolitan area of Mexico City: calculation of the total photolytic rate constants Kp(s(-1)) and photolytic lifetime (tau) of ambient formaldehyde and acetaldehyde.

PubMed

Báez, Armando P; Torres, Ma del Carmen B; García, Rocío M; Padilla, Hugo G

2002-01-01

A great number of studies on the ambient levels of formaldehyde and other carbonyls in the urban rural and maritime atmospheres have been published because of their chemical and toxicological characteristics, and adverse health effects. Due to their toxicological effects, it was considered necessary to measure these compounds at different sites in the metropolitan area of Mexico City, and to calculate the total rate of photolytic constants and the photolytic lifetime of formaldehyde and acetaldehyde. Four sites were chosen. Sampling was carried out at different seasons and atmospheric conditions. The results indicated that formaldehyde was the most abundant carbonyl, followed by acetone and acetaldehyde. Data sets obtained from the 4 sites were chosen to calculate the total rate of photolysis and the photolytic lifetime for formaldehyde and acetaldehyde. Maximum photolytic rate values were obtained at the maximum actinic fluxes, as was to be expected.

Photosynthesis and Ribulose 1,5-Bisphosphate Concentrations in Intact Leaves of Xanthium strumarium L. 1

PubMed Central

Mott, Keith A.; Jensen, Richard G.; O'Leary, James W.; Berry, Joseph A.

1984-01-01

The interacting effects of the rate of ribulose 1,5-bisphosphate (RuBP) regeneration and the rate of RuBP utilization as influenced by the amount and activation of RuBP carboxylase on photosynthesis and RuBP concentrations were resolved in experiments which examined the kinetics of the response of photosynthesis and RuBP concentrations after step changes from a rate-saturating to a rate-limiting light intensity in Xanthium strumarium. Because RuBP carboxylase requires several minutes to deactivate in vivo, it was possible to observe the effect of reducing the rate of RuBP regeneration on the RuBP concentration at constant enzyme activation state by sampling very soon after reducing the light intensity. Samples taken over longer time periods showed the effect of changes in enzyme activation at constant RuBP regeneration rate on RuBP concentration and photosynthetic rate. Within 15 s of lowering the light intensity from 1500 to 600 microEinsteins per square meter per second the RuBP concentration in the leaves dropped below the enzyme active site concentration, indicating that RuBP regeneration rate was limiting for photosynthesis. After longer intervals of time, the RuBP concentration in the leaf increased as the RuBP carboxylase assumed a new steady state activation level. No change in the rate of photosynthesis was observed during the interval that RuBP concentration increased. It is concluded that the rate of photosynthesis at the lower light intensity was limited by the rate of RuBP regeneration and that parallel changes in the activation of RuBP carboxylase occurred such that concentrations of RuBP at steady state were not altered by changes in light intensity. PMID:16663982

Photosynthesis and Ribulose 1,5-Bisphosphate Concentrations in Intact Leaves of Xanthium strumarium L.

PubMed

Mott, K A; Jensen, R G; O'leary, J W; Berry, J A

1984-12-01

The interacting effects of the rate of ribulose 1,5-bisphosphate (RuBP) regeneration and the rate of RuBP utilization as influenced by the amount and activation of RuBP carboxylase on photosynthesis and RuBP concentrations were resolved in experiments which examined the kinetics of the response of photosynthesis and RuBP concentrations after step changes from a rate-saturating to a rate-limiting light intensity in Xanthium strumarium. Because RuBP carboxylase requires several minutes to deactivate in vivo, it was possible to observe the effect of reducing the rate of RuBP regeneration on the RuBP concentration at constant enzyme activation state by sampling very soon after reducing the light intensity. Samples taken over longer time periods showed the effect of changes in enzyme activation at constant RuBP regeneration rate on RuBP concentration and photosynthetic rate. Within 15 s of lowering the light intensity from 1500 to 600 microEinsteins per square meter per second the RuBP concentration in the leaves dropped below the enzyme active site concentration, indicating that RuBP regeneration rate was limiting for photosynthesis. After longer intervals of time, the RuBP concentration in the leaf increased as the RuBP carboxylase assumed a new steady state activation level. No change in the rate of photosynthesis was observed during the interval that RuBP concentration increased. It is concluded that the rate of photosynthesis at the lower light intensity was limited by the rate of RuBP regeneration and that parallel changes in the activation of RuBP carboxylase occurred such that concentrations of RuBP at steady state were not altered by changes in light intensity.

A multi-purpose readout electronics for CdTe and CZT detectors for x-ray imaging applications

NASA Astrophysics Data System (ADS)

Yue, X. B.; Deng, Z.; Xing, Y. X.; Liu, Y. N.

2017-09-01

A multi-purpose readout electronics based on the DPLMS digital filter has been developed for CdTe and CZT detectors for X-ray imaging applications. Different filter coefficients can be synthesized optimized either for high energy resolution at relatively low counting rate or for high rate photon-counting with reduced energy resolution. The effects of signal width constraints, sampling rate and length were numerical studied by Mento Carlo simulation with simple CRRC shaper input signals. The signal width constraint had minor effect and the ENC was only increased by 6.5% when the signal width was shortened down to 2 τc. The sampling rate and length depended on the characteristic time constants of both input and output signals. For simple CR-RC input signals, the minimum number of the filter coefficients was 12 with 10% increase in ENC when the output time constant was close to the input shaping time. A prototype readout electronics was developed for demonstration, using a previously designed analog front ASIC and a commercial ADC card. Two different DPLMS filters were successfully synthesized and applied for high resolution and high counting rate applications respectively. The readout electronics was also tested with a linear array CdTe detector. The energy resolutions of Am-241 59.5 keV peak were measured to be 6.41% in FWHM for the high resolution filter and to be 13.58% in FWHM for the high counting rate filter with 160 ns signal width constraint.

Fast backprojection-based reconstruction of spectral-spatial EPR images from projections with the constant sweep of a magnetic field.

PubMed

Komarov, Denis A; Hirata, Hiroshi

2017-08-01

In this paper, we introduce a procedure for the reconstruction of spectral-spatial EPR images using projections acquired with the constant sweep of a magnetic field. The application of a constant field-sweep and a predetermined data sampling rate simplifies the requirements for EPR imaging instrumentation and facilitates the backprojection-based reconstruction of spectral-spatial images. The proposed approach was applied to the reconstruction of a four-dimensional numerical phantom and to actual spectral-spatial EPR measurements. Image reconstruction using projections with a constant field-sweep was three times faster than the conventional approach with the application of a pseudo-angle and a scan range that depends on the applied field gradient. Spectral-spatial EPR imaging with a constant field-sweep for data acquisition only slightly reduces the signal-to-noise ratio or functional resolution of the resultant images and can be applied together with any common backprojection-based reconstruction algorithm. Copyright © 2017 Elsevier Inc. All rights reserved.

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

DOE PAGES

Song, Bo; Sanborn, Brett

2018-05-07

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

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

Song, Bo; Sanborn, Brett

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Comparison of TID Effects in Space-Like Variable Dose Rates and Constant Dose Rates

NASA Technical Reports Server (NTRS)

Harris, Richard D.; McClure, Steven S.; Rax, Bernard G.; Evans, Robin W.; Jun, Insoo

2008-01-01

The degradation of the LM193 dual voltage comparator has been studied at different TID dose rate profiles, including several different constant dose rates and a variable dose rate that simulates the behavior of a solar flare. A comparison of results following constant dose rate vs. variable dose rates is made to explore how well the constant dose rates used for typical part testing predict the performance during a simulated space-like mission. Testing at a constant dose rate equal to the lowest dose rate seen during the simulated flare provides an extremely conservative estimate of the overall amount of degradation. A constant dose rate equal to the average dose rate is also more conservative than the variable rate. It appears that, for this part, weighting the dose rates by the amount of total dose received at each rate (rather than the amount of time at each dose rate) results in an average rate that produces an amount of degradation that is a reasonable approximation to that received by the variable rate.

Modeling Systematic Change in Stopover Duration Does Not Improve Bias in Trends Estimated from Migration Counts.

PubMed

Crewe, Tara L; Taylor, Philip D; Lepage, Denis

2015-01-01

The use of counts of unmarked migrating animals to monitor long term population trends assumes independence of daily counts and a constant rate of detection. However, migratory stopovers often last days or weeks, violating the assumption of count independence. Further, a systematic change in stopover duration will result in a change in the probability of detecting individuals once, but also in the probability of detecting individuals on more than one sampling occasion. We tested how variation in stopover duration influenced accuracy and precision of population trends by simulating migration count data with known constant rate of population change and by allowing daily probability of survival (an index of stopover duration) to remain constant, or to vary randomly, cyclically, or increase linearly over time by various levels. Using simulated datasets with a systematic increase in stopover duration, we also tested whether any resulting bias in population trend could be reduced by modeling the underlying source of variation in detection, or by subsampling data to every three or five days to reduce the incidence of recounting. Mean bias in population trend did not differ significantly from zero when stopover duration remained constant or varied randomly over time, but bias and the detection of false trends increased significantly with a systematic increase in stopover duration. Importantly, an increase in stopover duration over time resulted in a compounding effect on counts due to the increased probability of detection and of recounting on subsequent sampling occasions. Under this scenario, bias in population trend could not be modeled using a covariate for stopover duration alone. Rather, to improve inference drawn about long term population change using counts of unmarked migrants, analyses must include a covariate for stopover duration, as well as incorporate sampling modifications (e.g., subsampling) to reduce the probability that individuals will be detected on more than one occasion.

MERCURY REACTIONS IN THE PRESENCE OF CHLORINE SPECIES: HOMOGENOUS GAS PHASE AND HETEROGENOUS GAS-SOLID PHASE

EPA Science Inventory

The kinetics of mercury chlorination (with HC1) were studied using a flow reactor system with an on-line Hg analyzer and spciation sampling using a set of impingers. Kinetic parameters, such as reaction order (a), activation energy (Eu) and the overall rate constant (k') were es...

Near-Slope changes in the Eurasian and Makarov Basins from Glider Surveys

DTIC Science & Technology

2015-09-30

vibration and vehicle orientation. The Microrider samples all channels at a constant 512 Hz rate, and is neutrally buoyant in seawater , which allows for...efficient and precise ballasting of the glider vehicle. The lithium- battery powered G2 gliders will also be equipped with a pumped Seabird GPCTD, a

Evaluation of photostability of solid-state nicardipine hydrochloride polymorphs by using Fourier-transformed reflection-absorption infrared spectroscopy - effect of grinding on the photostability of crystal form.

PubMed

Teraoka, Reiko; Otsuka, Makoto; Matsuda, Yoshihisa

2004-11-22

Photostability and physicochemical properties of nicardipine hydrochloride polymorphs (alpha- and beta-form) were studied by using Fourier-transformed reflection-absorption infrared spectroscopy (FT-IR-RAS) of the tablets, X-ray powder diffraction analysis, differential scanning calorimetry (DSC), and color difference measurement. It was clear from the results of FT-IR-RAS spectra after irradiation that nicardipine hydrochloride in the solid state decomposed to its pyridine derivative when exposed to light. The photostability of the ground samples of two forms was also measured in the same manner. The two crystalline forms of the drug changed to nearly amorphous form after 150 min grinding in a mixer mill. X-ray powder diffraction patterns of those ground samples showed almost halo patterns. The nicardipine hydrochloride content on the surface of the tablet was determined based on the absorbance at 1700 cm(-1) attributable to the C=O stretch vibration in FT-IR-RAS spectra before and after irradiation by fluorescent lamp (3500 lx). The photodegradation followed apparently the first-order kinetics for any sample. The apparent photodegradation rate constant of beta-form was greater than that of alpha-form. The ground samples decomposed rapidly under the same light irradiation as compared with the intact crystalline forms. The photodegradation rate constant decreased with increase of the heat of fusion. copyright 2004 Elsevier B.V.

Relationship of nonreturn rates of dairy bulls to binding affinity of heparin to sperm

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

Marks, J.L.; Ax, R.L.

1985-08-01

The binding of the glycosaminoglycan (3H) heparin to bull spermatozoa was compared with nonreturn rates of dairy bulls. Semen samples from five bulls above and five below an average 71% nonreturn rate were used. Samples consisted of first and second ejaculates on a single day collected 1 d/wk for up to 5 consecutive wk. Saturation binding assays using (TH) heparin were performed to quantitate the binding characteristics of each sample. Scatchard plot analyses indicated a significant difference in the binding affinity for (TH) heparin between bulls of high and low fertility. Dissociation constants were 69.0 and 119.3 pmol for bullsmore » of high and low fertility, respectively. In contrast, the number of binding sites for (TH) heparin did not differ significantly among bulls. Differences in binding affinity of (TH) heparin to bull sperm might be used to predict relative fertility of dairy bulls.« less

Biased Brownian dynamics for rate constant calculation.

PubMed

Zou, G; Skeel, R D; Subramaniam, S

2000-08-01

An enhanced sampling method-biased Brownian dynamics-is developed for the calculation of diffusion-limited biomolecular association reaction rates with high energy or entropy barriers. Biased Brownian dynamics introduces a biasing force in addition to the electrostatic force between the reactants, and it associates a probability weight with each trajectory. A simulation loses weight when movement is along the biasing force and gains weight when movement is against the biasing force. The sampling of trajectories is then biased, but the sampling is unbiased when the trajectory outcomes are multiplied by their weights. With a suitable choice of the biasing force, more reacted trajectories are sampled. As a consequence, the variance of the estimate is reduced. In our test case, biased Brownian dynamics gives a sevenfold improvement in central processing unit (CPU) time with the choice of a simple centripetal biasing force.

Solvation and Acid Strength Effects on Catalysis by Faujasite Zeolites

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

Gounder, Rajamani P.; Jones, Andrew J.; Carr, Robert T.

2012-02-01

Kinetic, spectroscopic, and chemical titration data indicate that differences in monomolecular isobutane cracking and dehydrogenation and methanol dehydration turnover rates (per H+) among FAU zeolites treated thermally with steam (H-USY) and then chemically with ammonium hexafluorosilicate (CDHUSY) predominantly reflect differences in the size and solvating properties of their supercage voids rather than differences in acid strength. The number of protons on a given sample was measured consistently by titrations with Na+, with CH3 groups via reactions of dimethyl ether, and with 2,6-di-tert-butylpyridine during methanol dehydration catalysis; these titration values were also supported by commensurate changes in acidic OH infrared bandmore » areas upon exposure to titrant molecules. The number of protons, taken as the average of the three titration methods, was significantly smaller than the number of framework Al atoms (Alf) obtained from X-ray diffraction and 27Al magic angle spinning nuclear magnetic resonance spectroscopy on H-USY (0.35 H+/Alf) and CD-HUSY (0.69 H+/Alf). These data demonstrate that the ubiquitous use of Alf sites as structural proxies for active H+ sites in zeolites can be imprecise, apparently because distorted Al structures that are not associated with acidic protons are sometimes detected as Alf sites. Monomolecular isobutane cracking and dehydrogenation rate constants, normalized non-rigorously by the number of Alf species, decreased with increasing Na+ content on both H-USY and CD-HUSY samples and became undetectable at sub-stoichiometric exchange levels (0.32 and 0.72 Na+/Alf ratios, respectively), an unexpected finding attributed incorrectly in previous studies to the presence of minority ‘‘super-acidic’’ sites. These rate constants, when normalized rigorously by the number of residual H+ sites were independent of Na+ content on both H-USY and CD-HUSY samples, reflecting the stoichiometric replacement of protons that are uniform in reactivity by Na+ cations. Monomolecular isobutane cracking and dehydrogenation rate constants (per H+; 763 K), however, were higher on H-USY than CD-HUSY (by a factor of 1.4). Equilibrium constants for the formation of protonated methanol dimers via adsorption of gaseous methanol onto adsorbed methanol monomers, determined from kinetic studies of methanol dehydration to dimethyl ether (433 K), were also higher on H-USY than CD-HUSY (by a factor of 2.1). These larger constants predominantly reflect stronger dispersive interactions in H-USY, consistent with its smaller supercage voids that result from the occlusion of void space by extraframework Al (Alex) residues. These findings appear to clarify enduring controversies about the mechanistic interpretation of the effects of Na+ and Alex species on the catalytic reactivity of FAU zeolites. They also illustrate the need to normalize rates by the number of active sites instead of more convenient but less accurate structural proxies for such sites.« less

Deducing growth mechanisms for minerals from the shapes of crystal size distributions

USGS Publications Warehouse

Eberl, D.D.; Drits, V.A.; Srodon, J.

1998-01-01

Crystal size distributions (CSDs) of natural and synthetic samples are observed to have several distinct and different shapes. We have simulated these CSDs using three simple equations: the Law of Proportionate Effect (LPE), a mass balance equation, and equations for Ostwald ripening. The following crystal growth mechanisms are simulated using these equations and their modifications: (1) continuous nucleation and growth in an open system, during which crystals nucleate at either a constant, decaying, or accelerating nucleation rate, and then grow according to the LPE; (2) surface-controlled growth in an open system, during which crystals grow with an essentially unlimited supply of nutrients according to the LPE; (3) supply-controlled growth in an open system, during which crystals grow with a specified, limited supply of nutrients according to the LPE; (4) supply- or surface-controlled Ostwald ripening in a closed system, during which the relative rate of crystal dissolution and growth is controlled by differences in specific surface area and by diffusion rate; and (5) supply-controlled random ripening in a closed system, during which the rate of crystal dissolution and growth is random with respect to specific surface area. Each of these mechanisms affects the shapes of CSDs. For example, mechanism (1) above with a constant nucleation rate yields asymptotically-shaped CSDs for which the variance of the natural logarithms of the crystal sizes (??2) increases exponentially with the mean of the natural logarithms of the sizes (??). Mechanism (2) yields lognormally-shaped CSDs, for which ??2 increases linearly with ??, whereas mechanisms (3) and (5) do not change the shapes of CSDs, with ??2 remaining constant with increasing ??. During supply-controlled Ostwald ripening (4), initial lognormally-shaped CSDs become more symmetric, with ??2 decreasing with increasing ??. Thus, crystal growth mechanisms often can be deduced by noting trends in ?? versus ??2 of CSDs for a series of related samples.

Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Effect of Different Loading Conditions on the Nucleation and Development of Shear Zones Around Material Heterogeneities

NASA Astrophysics Data System (ADS)

Rybacki, E.; Nardini, L.; Morales, L. F.; Dresen, G.

2017-12-01

Rock deformation at depths in the Earth's crust is often localized in high temperature shear zones, which occur in the field at different scales and in a variety of lithologies. The presence of material heterogeneities has long been recognized to be an important cause for shear zones evolution, but the mechanisms controlling initiation and development of localization are not fully understood, and the question of which loading conditions (constant stress or constant deformation rate) are most favourable is still open. To better understand the effect of boundary conditions on shear zone nucleation around heterogeneities, we performed a series of torsion experiments under constant twist rate (CTR) and constant torque (CT) conditions in a Paterson-type deformation apparatus. The sample assemblage consisted of copper-jacketed Carrara marble hollow cylinders with one weak inclusion of Solnhofen limestone. The CTR experiments were performed at maximum bulk strain rates of 1.8-1.9*10-4 s-1, yielding shear stresses of 19-20 MPa. CT tests were conducted at shear stresses between 18.4 and 19.8 MPa resulting in shear strain rates of 1-2*10-4 s-1. All experiments were run at 900 °C temperature and 400 MPa confining pressure. Maximum bulk shear strains (γ) were ca. 0.3 and 1. Strain localized within the host marble in front of the inclusion in an area termed process zone. Here grain size reduction is intense and local shear strain (estimated from markers on the jackets) is up to 8 times higher than the applied bulk strain, rapidly dropping to 2 times higher at larger distance from the inclusion. The evolution of key microstructural parameters such as average grain size and average grain orientation spread (GOS, a measure of lattice distortion) within the process zone, determined by electron backscatter diffraction analysis, differs significantly as a function of loading conditions. Both parameters indicate that, independent of bulk strain and distance from the inclusion, the contribution of small strain-free recrystallized grains is larger in CTR than in CT samples. Our results suggest that loading conditions substantially affect material heterogeneity-induced localization in its nucleation and transient stages.

Sample-interpolation timing: an optimized technique for the digital measurement of time of flight for γ rays and neutrons at relatively low sampling rates

NASA Astrophysics Data System (ADS)

Aspinall, M. D.; Joyce, M. J.; Mackin, R. O.; Jarrah, Z.; Boston, A. J.; Nolan, P. J.; Peyton, A. J.; Hawkes, N. P.

2009-01-01

A unique, digital time pick-off method, known as sample-interpolation timing (SIT) is described. This method demonstrates the possibility of improved timing resolution for the digital measurement of time of flight compared with digital replica-analogue time pick-off methods for signals sampled at relatively low rates. Three analogue timing methods have been replicated in the digital domain (leading-edge, crossover and constant-fraction timing) for pulse data sampled at 8 GSa s-1. Events arising from the 7Li(p, n)7Be reaction have been detected with an EJ-301 organic liquid scintillator and recorded with a fast digital sampling oscilloscope. Sample-interpolation timing was developed solely for the digital domain and thus performs more efficiently on digital signals compared with analogue time pick-off methods replicated digitally, especially for fast signals that are sampled at rates that current affordable and portable devices can achieve. Sample interpolation can be applied to any analogue timing method replicated digitally and thus also has the potential to exploit the generic capabilities of analogue techniques with the benefits of operating in the digital domain. A threshold in sampling rate with respect to the signal pulse width is observed beyond which further improvements in timing resolution are not attained. This advance is relevant to many applications in which time-of-flight measurement is essential.

Radioimmunoassay for pyridostigmine

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

Meyer, H.G.; Lukey, B.J.; Gepp, R.T.

1988-01-01

Pyridostigmine is a cholinergic drug used for the treatment of myasthenia gravis and for antagonizing the effects of non-depolarizing muscle relaxants. In addition, military organizations in several countries have an active interest in pyridostigmine as a pretreatment compound for nerve agent poisoning. Anti-pyridostigmine antibodies were produced in rabbits using a pyridostigmine analog conjugated to keyhole limpet hemocyanin. These antibodies were used for development of a radioimmunoassay that has a linear standard curve (r2=0.986) ranging from 0.5 to 10.0 ng/ml of pyridostigmine bromide in a 0.1-ml plasma sample. This assay measures pyridostigmine in plasma with better sensitivity and much greater through-putmore » than do current state-of-the-art high-performance liquid chromatography techniques. In addition, only small volumes (100ml) of the plasma samples are required. Plasma levels of pyridostigmine were determined in the rat after intramuscular administration (0.056mg/kg) of pyridostigmine bromide. Estimates of the various pharmacokinetic parameters were calculated using the computer program NONLIN84. The results were as follows: apparent volume of distribution = 1.97 1/kg, absorption rate constant = 0.277 min-1, elimination rate constant = 0.0273 min-1, area under the curve = 1010 ng x min/ml, absorption rate half-life = 2.41 min, elimination rate half-life = 24.8 min, maximal plasma concentration (Cmax) = 21.3 ng/ml and time to Cmax = 9.02 min.« less

Innovative flow controller for time integrated passive sampling using SUMMA canisters

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

Simon, P.; Farant, J.P.; Cole, H.

1996-12-31

To restrict the entry of gaseous contaminants inside evacuated vessels such as SUMMA canisters, mechanical flow controllers are used to collect integrated atmospheric samples. From the passive force generated by the pressure gradient, the motion of gas can be controlled to obtain a constant flow rate. Presently, devices based on the principle of critical orifices are used and they are all limited to an upper integrated sampling time. A novel flow controller which can be designed to achieve any desired sampling time when used on evacuated vessels was recently developed. It can extend the sampling time for hours, days, weeksmore » or even months for the benefits of environmental, engineering and toxicological professionals. The design of the controller is obtained from computer simulations done with an original set of equations derived from fluid mechanic and gas kinetic laws. To date, the experimental results have shown excellent agreement, with predictions obtained from the mathematical model. This new controller has already found numerous applications. Units able to deliver a constant sampling rate between vacuum and approximately -10 inches Hg during continuous long term duration have been used with SUMMA canisters of different volumes (500 ml, 1 litre and 61). Essentially, any combination of sampling time and sampler volume is possible. The innovative flow controller has contributed to an air quality assessment around a sanitary landfill (indoor/outdoor), and inside domestic wastewater and pulpmill sludge treatment facilities. It is presently being used as an alternative methodology for atmospheric sampling in the Russian orbital station Mir. This device affords true long term passive monitoring of selected gaseous air pollutants for environmental studies. 14 refs., 3 figs.« less

Rate constants measured for hydrated electron reactions with peptides and proteins

NASA Technical Reports Server (NTRS)

Braams, R.

1968-01-01

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Predicting sample lifetimes in creep fracture of heterogeneous materials

NASA Astrophysics Data System (ADS)

Koivisto, Juha; Ovaska, Markus; Miksic, Amandine; Laurson, Lasse; Alava, Mikko J.

2016-08-01

Materials flow—under creep or constant loads—and, finally, fail. The prediction of sample lifetimes is an important and highly challenging problem because of the inherently heterogeneous nature of most materials that results in large sample-to-sample lifetime fluctuations, even under the same conditions. We study creep deformation of paper sheets as one heterogeneous material and thus show how to predict lifetimes of individual samples by exploiting the "universal" features in the sample-inherent creep curves, particularly the passage to an accelerating creep rate. Using simulations of a viscoelastic fiber bundle model, we illustrate how deformation localization controls the shape of the creep curve and thus the degree of lifetime predictability.

Characterizing full matrix constants of piezoelectric single crystals with strong anisotropy using two samples

NASA Astrophysics Data System (ADS)

Tang, Liguo; Zhang, Yang; Cao, Wenwu

2016-10-01

Although the self-consistency of the full matrix material constants of a piezoelectric sample obtained by the resonant ultrasonic spectroscopy technique can be guaranteed because all constants come from the same sample, it is a great challenge to determine the constants of a piezoelectric sample with strong anisotropy because it might not be possible to identify enough resonance modes from the resonance spectrum. To overcome this difficulty, we developed a strategy to use two samples of similar geometries to increase the number of easy identifiable modes. Unlike the IEEE resonance methods, sample-to-sample variation here is negligible because the two samples have almost the same dimensions, cut from the same specimen and poled under the same conditions. Using this method, we have measured the full matrix constants of a [011]c poled 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 single crystal, which has 17 independent constants. The self-consistency of the obtained results is checked by comparing the calculated elastic stiffness constants c33 D , c44 D , and c55 D with those directly measured ones using the ultrasonic pulse-echo method.

Comparative in vitro flow study of 3 different Ex-PRESS miniature glaucoma device models.

PubMed

Estermann, Stephan; Yuttitham, Kanokwan; Chen, Julie A; Lee, On-Tat; Stamper, Robert L

2013-03-01

To determine the flow characteristics of the 3 different models of the Ex-PRESS miniature glaucoma device in a controlled laboratory study. The 3 different Ex-PRESS models (P-50, R-50, and P-200; Optonol Ltd; now Alcon Lab) were tested using a gravity-driven flow test. Three samples of each of the 3 Ex-PRESS models were subjected to a constant gravitational force of fluid at 5 different pressure levels (5 to 25 mm Hg). Four measurements per sample were taken at each pressure level. The main outcome measure was flow rate (Q) (µL/min). Resistance (R) was calculated by dividing pressure (P) by the measured flow (Q). The flow rate was primarily pressure dependent. The P-200 model (internal diameter 200 µm) showed a statistically significant higher flow rate and lower resistance compared with both the P-50 and R-50 models (internal diameter 50 µm) (P<0.0001). The P-50 and R-50 models demonstrated similar flow rates (P=0.08) despite their difference in tube length (2.64 vs. 2.94 mm). The 3 models of the Ex-PRESS mini shunt behaved in vitro as simple flow resistors by creating a relatively constant resistance to flow. Tube diameter was the only parameter with significant impact on flow and resistance. All models demonstrated flow rates per unit of pressure much higher than the outflow facility of a healthy human eye.

Interaction of abiotic and microbial processes in hexachloroethane reduction in groundwater

USGS Publications Warehouse

Roberts, A. Lynn; Gschwend, Philip M.

1994-01-01

In order to gain insight into mechanisms of hexachloroethane reduction, hexa- and pentachloroethane transformation rates were measured in anaerobic groundwater samples. For samples spiked with pentachloroethane, disappearance of pentachloroethane was accompanied by tetrachloroethylene production. Transformation rates were similar in unpoisoned and in HgCl2-poisoned samples, and rates were within ±20% of predictions based on measured pH and second-order dehydrochlorination rate constants determined in clean laboratory systems, indicating that the fate of pentachloroethane in this system is dominated by abiotic reactions. No hexachloroethane transformation was observed in HgCl2-poisoned samples, whereas in unpoisoned samples, hexachloroethane disappearance was accompanied by production of tetrachloroethylene as well as traces of pentachloroethane. Although only minor amounts of pentachloroethane accumulated, as much as 30% of the hexachloroethane transformation pathway proceeds via a pentachloroethane intermediate. This suggests that the microbial reduction of hexachloroethane proceeds at least in part through a free-radical mechanism. To the extent that hexachloroethane reduction to tetrachloroethylene occurs through a pentachloroethane intermediate, the first step in the sequence, the microbially-mediated step, is the slow step; the subsequent abiotic dehydrohalogenation step occurs much more rapidly.

Design of Edible Oil Degradation Tool by Using Electromagnetic Field Absorbtion Principle which was Characterized to Peroxide Number

NASA Astrophysics Data System (ADS)

Isnen, M.; Nasution, T. I.; Perangin-angin, B.

2016-08-01

The identification of changes in oil quality has been conducted by indicating the change of dielectric constant which was showed by sensor voltage. Sensor was formed from two parallel flats that worked by electromagnetic wave propagation principle. By measuring its amplitude of electromagnetic wave attenuation caused by interaction between edible oil samples and the sensor, dielectric constant could be identified and estimated as well as peroxide number. In this case, the parallel flats were connected to an electric oscillator 700 kHz. Furthermore, sensor system could showed measurable voltage differences for each different samples. The testing carried out to five oil samples after undergoing an oxidation treatment at fix temperature of 235oC for 0, 5, 10, 15 and 20 minutes. Iodometry method testing showed peroxide values about 1.99, 9.95, 5.96, 11.86, and 15.92 meq/kg respectively with rising trend. Besides that, the testing result by sensor system showed voltages values 1.139, 1.147, 1.165, 1.173, and 1.176 volts with rising trend, respectively. It means that the higher sensor voltages showed the higher damage rate of edible oil when the change in sensor voltage was caused by the change in oil dielectric constant in which heating process caused damage in edible oil molecules structure. The more damage of oil structure caused the more difficulties of oil molecules to polarize and it is indicated by smaller dielectric constant. Therefore electric current would be smaller when sensor voltage was higher. On the other side, the higher sensor voltage means the smaller dielectric constant and the higher peroxide number.

Spin relaxation measurements of electrostatic bias in intermolecular exploration

NASA Astrophysics Data System (ADS)

Teng, Ching-Ling; Bryant, Robert G.

2006-04-01

We utilize the paramagnetic contribution to proton spin-lattice relaxation rate constants induced by freely diffusing charged paramagnetic centers to investigate the effect of charge on the intermolecular exploration of a protein by the small molecule. The proton NMR spectrum provided 255 resolved resonances that report how the explorer molecule local concentration varies with position on the surface. The measurements integrate over local dielectric constant variations, and, in principle, provide an experimental characterization of the surface free energy sampling biases introduced by the charge distribution on the protein. The experimental results for ribonuclease A obtained using positive, neutral, and negatively charged small nitroxide radicals are qualitatively similar to those expected from electrostatic calculations. However, while systematic electrostatic trends are apparent, the three different combinations of the data sets do not yield internally consistent values for the electrostatic contribution to the intermolecular free energy. We attribute this failure to the weakness of the electrostatic sampling bias for charged nitroxides in water and local variations in effective translational diffusion constant at the water-protein interface, which enters the nuclear spin relaxation equations for the nitroxide-proton dipolar coupling.

Agarose electrophoresis of DNA in discontinuous buffers, using a horizontal slab apparatus and a buffer system with improved properties.

PubMed

Zsolnai, A; Orbán, L; Chrambach, A

1993-03-01

Using a horizontal slab apparatus with a buffer in the reservoirs at the level of the gel ("sea-level electrophoresis"), the retrograde discontinuous buffer system reported by Wiltfang et al. for sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) of proteins was applied to DNA electrophoresis. This application yielded the advantages of an increased displacement rate of the moving boundary front and a decrease in the concentration of the counterion base in the resolving phase, which yielded reduced relative mobility values at equivalent gel concentrations and practicable low buffer concentrations. The change of relative mobilities (Rf) with a variation of field strength is decreased compared to that of the migration rate in the continuous Tris-boric-acid-EDTA (TBE) buffer and thus the robustness of the system is improved, as well as the efficiency of separation. The system of Wiltfang et al. has in common with previously described discontinuous DNA system, that it is able to stack DNA from dilute samples and is insensitive to sample components with lower net mobilities than DNA, such as acetate. However, the variance of Rf at constant current density in the discontinuous buffer system is not improved over that of the migration rate at constant field strength in the continuous TBE buffer.

Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery

NASA Astrophysics Data System (ADS)

Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F.

2014-02-01

Lithium-ion batteries suffer from inherent thermal limitations (i.e., capacity fade and thermal runaway); thus, it is critical to understand heat generation experienced in the batteries under normal operation. In the current study, reversible and irreversible electrochemical heat generation rates were measured experimentally on a small commercially available C/LiFePO4 lithium-ion battery designed for high-rate applications. The battery was tested over a wide range of temperatures (10-60 °C) and discharge and charge rates (∼C/4-5C) to elucidate their effects. Two samples were tested in a specially designed wind tunnel to maintain constant battery surface temperature within a maximum variation of ±0.88 °C. A data normalization technique was employed to account for the observed capacity fade, which was largest at the highest rates. The heat rate was shown to increase with both increasing rate and decreasing temperature, and the reversible heat rate was shown to be significant even at the highest rate and temperature (7.4% at 5C and 55 °C). Results from cycling the battery using a dynamic power profile also showed that constant-current data predict the dynamic performance data well. In addition, the reversible heat rate in the dynamic simulation was shown to be significant, especially for charge-depleting HEV applications.

Rare behavior of growth processes via umbrella sampling of trajectories

NASA Astrophysics Data System (ADS)

Klymko, Katherine; Geissler, Phillip L.; Garrahan, Juan P.; Whitelam, Stephen

2018-03-01

We compute probability distributions of trajectory observables for reversible and irreversible growth processes. These results reveal a correspondence between reversible and irreversible processes, at particular points in parameter space, in terms of their typical and atypical trajectories. Thus key features of growth processes can be insensitive to the precise form of the rate constants used to generate them, recalling the insensitivity to microscopic details of certain equilibrium behavior. We obtained these results using a sampling method, inspired by the "s -ensemble" large-deviation formalism, that amounts to umbrella sampling in trajectory space. The method is a simple variant of existing approaches, and applies to ensembles of trajectories controlled by the total number of events. It can be used to determine large-deviation rate functions for trajectory observables in or out of equilibrium.

Landfill gas generation after mechanical biological treatment of municipal solid waste. Estimation of gas generation rate constants.

PubMed

Gioannis, G De; Muntoni, A; Cappai, G; Milia, S

2009-03-01

Mechanical biological treatment (MBT) of residual municipal solid waste (RMSW) was investigated with respect to landfill gas generation. Mechanically treated RMSW was sampled at a full-scale plant and aerobically stabilized for 8 and 15 weeks. Anaerobic tests were performed on the aerobically treated waste (MBTW) in order to estimate the gas generation rate constants (k,y(-1)), the potential gas generation capacity (L(o), Nl/kg) and the amount of gasifiable organic carbon. Experimental results show how MBT allowed for a reduction of the non-methanogenic phase and of the landfill gas generation potential by, respectively, 67% and 83% (8 weeks treatment), 82% and 91% (15 weeks treatment), compared to the raw waste. The amount of gasified organic carbon after 8 weeks and 15 weeks of treatment was equal to 11.01+/-1.25kgC/t(MBTW) and 4.54+/-0.87kgC/t(MBTW), respectively, that is 81% and 93% less than the amount gasified from the raw waste. The values of gas generation rate constants obtained for MBTW anaerobic degradation (0.0347-0.0803y(-1)) resemble those usually reported for the slowly and moderately degradable fractions of raw MSW. Simulations performed using a prediction model support the hypothesis that due to the low production rate, gas production from MBTW landfills is well-suited to a passive management strategy.

Dynamic nuclear polarization using frequency modulation at 3.34 T.

PubMed

Hovav, Y; Feintuch, A; Vega, S; Goldfarb, D

2014-01-01

During dynamic nuclear polarization (DNP) experiments polarization is transferred from unpaired electrons to their neighboring nuclear spins, resulting in dramatic enhancement of the NMR signals. While in most cases this is achieved by continuous wave (cw) irradiation applied to samples in fixed external magnetic fields, here we show that DNP enhancement of static samples can improve by modulating the microwave (MW) frequency at a constant field of 3.34 T. The efficiency of triangular shaped modulation is explored by monitoring the (1)H signal enhancement in frozen solutions containing different TEMPOL radical concentrations at different temperatures. The optimal modulation parameters are examined experimentally and under the most favorable conditions a threefold enhancement is obtained with respect to constant frequency DNP in samples with low radical concentrations. The results are interpreted using numerical simulations on small spin systems. In particular, it is shown experimentally and explained theoretically that: (i) The optimal modulation frequency is higher than the electron spin-lattice relaxation rate. (ii) The optimal modulation amplitude must be smaller than the nuclear Larmor frequency and the EPR line-width, as expected. (iii) The MW frequencies corresponding to the enhancement maxima and minima are shifted away from one another when using frequency modulation, relative to the constant frequency experiments. Copyright © 2013 Elsevier Inc. All rights reserved.

Higher success rate with transcranial electrical stimulation of motor-evoked potentials using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery.

PubMed

Shigematsu, Hideki; Kawaguchi, Masahiko; Hayashi, Hironobu; Takatani, Tsunenori; Iwata, Eiichiro; Tanaka, Masato; Okuda, Akinori; Morimoto, Yasuhiko; Masuda, Keisuke; Tanaka, Yuu; Tanaka, Yasuhito

2017-10-01

During spine surgery, the spinal cord is electrophysiologically monitored via transcranial electrical stimulation of motor-evoked potentials (TES-MEPs) to prevent injury. Transcranial electrical stimulation of motor-evoked potential involves the use of either constant-current or constant-voltage stimulation; however, there are few comparative data available regarding their ability to adequately elicit compound motor action potentials. We hypothesized that the success rates of TES-MEP recordings would be similar between constant-current and constant-voltage stimulations in patients undergoing spine surgery. The objective of this study was to compare the success rates of TES-MEP recordings between constant-current and constant-voltage stimulation. This is a prospective, within-subject study. Data from 100 patients undergoing spinal surgery at the cervical, thoracic, or lumbar level were analyzed. The success rates of the TES-MEP recordings from each muscle were examined. Transcranial electrical stimulation with constant-current and constant-voltage stimulations at the C3 and C4 electrode positions (international "10-20" system) was applied to each patient. Compound muscle action potentials were bilaterally recorded from the abductor pollicis brevis (APB), deltoid (Del), abductor hallucis (AH), tibialis anterior (TA), gastrocnemius (GC), and quadriceps (Quad) muscles. The success rates of the TES-MEP recordings from the right Del, right APB, bilateral Quad, right TA, right GC, and bilateral AH muscles were significantly higher using constant-voltage stimulation than those using constant-current stimulation. The overall success rates with constant-voltage and constant-current stimulations were 86.3% and 68.8%, respectively (risk ratio 1.25 [95% confidence interval: 1.20-1.31]). The success rates of TES-MEP recordings were higher using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery. Copyright © 2017 Elsevier Inc. All rights reserved.

Elongational flow of polymer melts at constant strain rate, constant stress and constant force

NASA Astrophysics Data System (ADS)

Wagner, Manfred H.; Rolón-Garrido, Víctor H.

2013-04-01

Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

The Henry's constant of monochloramine.

PubMed

Garcia, Miguel A; Anderson, Michael A

2018-02-01

Monochloramine is a secondary disinfectant used in drinking water and is also formed in chlorinated wastewater. While known to hydrolyze over time and react with dissolved organic matter, its partitioning between the aqueous and gas phase has not been extensively studied. Preliminary experiments demonstrated that monochloramine concentrations in solutions open to the atmosphere or actively aerated decreased more rapidly than in sealed solutions, indicating significant losses to the atmosphere. For example, a monochloramine solution open to the atmosphere yielded a loss rate constant of 0.08 d -1 , a value twice that for sealed samples without headspace (0.04 d -1 ) where loss occurs exclusively as a result of hydrolysis. A solution aerated at 10 mL s -1 had a loss rate constant nearly 10× greater than that for hydrolysis alone (0.35 d -1 ). To better understand partitioning of monochloramine to the gas phase and potential for volatilization, the dimensionless Henry's law constants of monochloramine (K H ) were determined using an equilibrium headspace technique at five different temperatures (11, 16, 21, 27, and 32 °C). The resulting values ranged from 8 × 10 -3 to 4 × 10 -2 , indicating a semi-volatile compound, and were found to be consistent with quantitative structure activity relationship predictions. At 20 °C, monochloramine exhibits a dimensionless Henry's constant of about 1.7 × 10 -2 which is 35 times greater than ammonia but comparable to the Henry's constant of inorganic semi-volatile compounds such sulfur dioxide. The Henry's constant values for monochloramine suggests that volatilization could be a relevant loss process in open systems such as rivers receiving chlorinated wastewater effluent, swimming pools and cooling towers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Instanton rate constant calculations close to and above the crossover temperature.

PubMed

McConnell, Sean; Kästner, Johannes

2017-11-15

Canonical instanton theory is known to overestimate the rate constant close to a system-dependent crossover temperature and is inapplicable above that temperature. We compare the accuracy of the reaction rate constants calculated using recent semi-classical rate expressions to those from canonical instanton theory. We show that rate constants calculated purely from solving the stability matrix for the action in degrees of freedom orthogonal to the instanton path is not applicable at arbitrarily low temperatures and use two methods to overcome this. Furthermore, as a by-product of the developed methods, we derive a simple correction to canonical instanton theory that can alleviate this known overestimation of rate constants close to the crossover temperature. The combined methods accurately reproduce the rate constants of the canonical theory along the whole temperature range without the spurious overestimation near the crossover temperature. We calculate and compare rate constants on three different reactions: H in the Müller-Brown potential, methylhydroxycarbene → acetaldehyde and H 2  + OH → H + H 2 O. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Semi-automated in vivo solid-phase microextraction sampling and the diffusion-based interface calibration model to determine the pharmacokinetics of methoxyfenoterol and fenoterol in rats.

PubMed

Yeung, Joanne Chung Yan; de Lannoy, Inés; Gien, Brad; Vuckovic, Dajana; Yang, Yingbo; Bojko, Barbara; Pawliszyn, Janusz

2012-09-12

In vivo solid-phase microextraction (SPME) can be used to sample the circulating blood of animals without the need to withdraw a representative blood sample. In this study, in vivo SPME in combination with liquid-chromatography tandem mass spectrometry (LC-MS/MS) was used to determine the pharmacokinetics of two drug analytes, R,R-fenoterol and R,R-methoxyfenoterol, administered as 5 mg kg(-1) i.v. bolus doses to groups of 5 rats. This research illustrates, for the first time, the feasibility of the diffusion-based calibration interface model for in vivo SPME studies. To provide a constant sampling rate as required for the diffusion-based interface model, partial automation of the SPME sampling of the analytes from the circulating blood was accomplished using an automated blood sampling system. The use of the blood sampling system allowed automation of all SPME sampling steps in vivo, except for the insertion and removal of the SPME probe from the sampling interface. The results from in vivo SPME were compared to the conventional method based on blood withdrawal and sample clean up by plasma protein precipitation. Both whole blood and plasma concentrations were determined by the conventional method. The concentrations of methoxyfenoterol and fenoterol obtained by SPME generally concur with the whole blood concentrations determined by the conventional method indicating the utility of the proposed method. The proposed diffusion-based interface model has several advantages over other kinetic calibration models for in vivo SPME sampling including (i) it does not require the addition of a standard into the sample matrix during in vivo studies, (ii) it is simple and rapid and eliminates the need to pre-load appropriate standard onto the SPME extraction phase and (iii) the calibration constant for SPME can be calculated based on the diffusion coefficient, extraction time, fiber length and radius, and size of the boundary layer. In the current study, the experimental calibration constants of 338.9±30 mm(-3) and 298.5±25 mm(-3) are in excellent agreement with the theoretical calibration constants of 307.9 mm(-3) and 316.0 mm(-3) for fenoterol and methoxyfenoterol respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Aerobic batch degradation of 17-beta estradiol (E2) by activated sludge: effects of spiking E2 concentrations, MLVSS and temperatures.

PubMed

Li, Fusheng; Yuasa, Akira; Obara, Aya; Mathews, Alexander P

2005-05-01

Aerobic batch degradation of 17beta estradiol (E2) spiked into the activated sludge liquor from a sewage treatment plant was studied; and the likely impacts of E2's initial concentrations (C0), microbial population densities (MLVSS) and temperatures (TEMPT) were examined for a variety of combinations of these three factors: C0 = 10, 30 and 50 microgl(-1); MLVSS = 1750, 875 and 435 mgl(-1); and TEMPT = 5, 20 and 35 degrees C. The results, together with those obtained through two control runs performed using a killed sludge sample, demonstrated clearly that E2 was eliminated from the aqueous phase readily under appropriate MLVSS and temperature levels, with the role of sorption by biomass being less significant. By fitting observed concentration data with a first-order rate expression, the degradation rate constants (k) under all experimental conditions were estimated. The magnitude of k changed markedly in the range of 0.23-4.79 h(-1), following a general order that the higher the MLVSS was, the higher the rate constant, and that the higher the temperature, the higher the rate constant. An obvious increasing trend of the biomass-modified average rate constant (k') with increases in the temperature was also presented: the k' values at 5, 20 and 35 degrees C were 0.79, 1.77 and 3.29l MLVSS g(-1)h(-1), respectively. Furthermore, based upon the estimated k values, the temperature coefficients (theta) over the ranges of 5-20 and 20-35 degrees C were determined. In similarity with the magnitude of theta reported for ordinary BOD-based organic matrices in domestic wastewater, the theta values of E2 varied in the range of 1.026-1.09, suggesting that the temperature impacts on the degradation rates of E2 and BOD constituents are probably similar.

Kinetic aspects of the coil-stretch transition of polymer chains in dilute solution under extensional flow

NASA Astrophysics Data System (ADS)

Hernández Cifre, J. G.; García de la Torre, J.

2001-11-01

When linear polymer chains in dilute solution are subject to extensional flow, each chain in the sample experiences the coil-stretch transition at a different time. Using Brownian dynamics simulation, we have studied the distribution of transition times in terms of the extensional rate and the length of the chains. If instead of time one characterizes the effect of the flow by the accumulated strain, then the distribution and its moments seem to take general forms, independent of molecular weight and flow rate, containing some numerical, universal constants that have been evaluated from the dynamical simulation. The kinetics of the transition, expressed by the time-dependence of the fraction of remaining coils, has also been simulated, and the results for the kinetic rate constant has been rationalized in a manner similar to that used for the transition time. The molecular individualism, characterized in this work by the distribution of transition times, is related to the excess of the applied extensional rate over its critical value, which will determine the transition time and other features of the coil-stretch transition.

The nano-epsilon dot method for strain rate viscoelastic characterisation of soft biomaterials by spherical nano-indentation.

PubMed

Mattei, G; Gruca, G; Rijnveld, N; Ahluwalia, A

2015-10-01

Nano-indentation is widely used for probing the micromechanical properties of materials. Based on the indentation of surfaces using probes with a well-defined geometry, the elastic and viscoelastic constants of materials can be determined by relating indenter geometry and measured load and displacement to parameters which represent stress and deformation. Here we describe a method to derive the viscoelastic properties of soft hydrated materials at the micro-scale using constant strain rates and stress-free initial conditions. Using a new self-consistent definition of indentation stress and strain and corresponding unique depth-independent expression for indentation strain rate, the epsilon dot method, which is suitable for bulk compression testing, is transformed to nano-indentation. We demonstrate how two materials can be tested with a displacement controlled commercial nano-indentor using the nano-espilon dot method (nano-ε̇M) to give values of instantaneous and equilibrium elastic moduli and time constants with high precision. As samples are tested in stress-free initial conditions, the nano-ε̇M could be useful for characterising the micro-mechanical behaviour of soft materials such as hydrogels and biological tissues at cell length scales. Copyright © 2015 Elsevier Ltd. All rights reserved.

Improved waste water treatment by bio-synthesized Graphene Sand Composite.

PubMed

Poornima Parvathi, V; Umadevi, M; Bhaviya Raj, R

2015-10-01

The photocatalytic and antibacterial properties of graphene biosynthesized from sugar and anchored on sand particles has been focused here. The morphology and composition of the synthesized Graphene Sand Composite (GSC) was investigated by means of X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDAX), Fourier Transform Infra-red Spectroscopy (FTIR) and UV-Visible spectroscopy. SEM images show wrinkly edges. This is characteristic of graphenic morphology. Three types of waste water samples namely, textile waste (TW), sugarcane industrial waste water (SW) and domestic waste water from a local purification center at Kodaikanal (KWW) were collected and treated. Adsorption experiments showed effective removal of impurities at 0.2 g of GSC. Photocatalytic activity was analyzed under visible and ultraviolet irradiation. The rate constant for TW increased to 0.0032/min for visible light irradiation from 0.0029/min under UV irradiation. SW showed similar improved activity with rate constant as 0.0023/min in visible irradiation compared to 0.0016/min under UV irradiation. For KWW enhanced activity was seen only in visible light irradiation with rate constant 0.0025/min. GSC showed an inhibition zone of 20 mm against the bacterium Escherichia coli. Results suggest development of economic and effective waste water management systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

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

PubMed

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

2014-01-17

Five methods for controlling the mobile phase flow rate for gradient elution analyses using very high pressure liquid chromatography (VHPLC) were tested to determine thermal stability of the column during rapid gradient separations. To obtain rapid separations, instruments are operated at high flow rates and high inlet pressure leading to uneven thermal effects across columns and additional time needed to restore thermal equilibrium between successive analyses. The purpose of this study is to investigate means to minimize thermal instability and obtain reliable results by measuring the reproducibility of the results of six replicate gradient separations of a nine component RPLC standard mixture under various experimental conditions with no post-run times. Gradient separations under different conditions were performed: constant flow rates, two sets of constant pressure operation, programmed flow constant pressure operation, and conditions which theoretically should yield a constant net heat loss at the column's wall. The results show that using constant flow rates, programmed flow constant pressures, and constant heat loss at the column's wall all provide reproducible separations. However, performing separations using a high constant pressure with programmed flow reduces the analysis time by 16% compared to constant flow rate methods. For the constant flow rate, programmed flow constant pressure, and constant wall heat experiments no equilibration time (post-run time) was required to obtain highly reproducible data. Copyright © 2013 Elsevier B.V. All rights reserved.

A chlorophyll fluorescence-based method for the integrated characterization of the photophysiological response to light stress.

PubMed

Serôdio, João; Schmidt, William; Frankenbach, Silja

2017-02-01

This work introduces a new experimental method for the comprehensive description of the physiological responses to light of photosynthetic organisms. It allows the integration in a single experiment of the main established manipulative chlorophyll fluorescence-based protocols. It enables the integrated characterization of the photophysiology of samples regarding photoacclimation state (generating non-sequential light-response curves of effective PSII quantum yield, electron transport rate or non-photochemical quenching), photoprotection capacity (running light stress-recovery experiments, quantifying non-photochemical quenching components) and the operation of photoinactivation and photorepair processes (measuring rate constants of photoinactivation and repair for different light levels and the relative quantum yield of photoinactivation). The new method is based on a previously introduced technique, combining the illumination of a set of replicated samples with spatially separated actinic light beams of different intensity, and the simultaneous measurement of the fluorescence emitted by all samples using an imaging fluorometer. The main novelty described here is the independent manipulation of light intensity and duration of exposure for each sample, and the control of the cumulative light dose applied. The results demonstrate the proof of concept for the method, by comparing the responses of cultures of Chlorella vulgaris acclimated to low and high light regimes, highlighting the mapping of light stress responses over a wide range of light intensity and exposure conditions, and the rapid generation of paired light-response curves of photoinactivation and repair rate constants. This approach represents a chlorophyll fluorescence 'protocol of everything', contributing towards the high throughput characterization of the photophysiology of photosynthetic organisms. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Acid-base regulation during heating and cooling in the lizard, Varanus exanthematicus.

PubMed

Wood, S C; Johansen, K; Glass, M L; Hoyt, R W

1981-04-01

Current concepts of acid-base balance in ectothermic animals require that arterial pH vary inversely with body temperature in order to maintain a constant OH-/H+ and constant net charge on proteins. The present study evaluates acid-base regulation in Varanus exanthematicus under various regimes of heating and cooling between 15 and 38 degrees C. Arterial blood was sampled during heating and cooling at various rates, using restrained and unrestrained animals with and without face masks. Arterial pH was found to have a small temperature dependence, i.e., pH = 7.66--0.005 (T). The slope (dpH/dT = -0.005), while significantly greater than zero (P less than 0.05), is much less than that required for a constant OH-/H+ or a constant imidazole alphastat (dpH/dT congruent to 0.018). The physiological mechanism that distinguishes this species from most other ectotherms is the presence of a ventilatory response to temperature-induced changes in CO2 production and O2 uptake, i.e., VE/VO2 is constant. This results in a constant O2 extraction and arterial saturation (approx. 90%), which is adaptive to the high aerobic requirements of this species.

Importance of allochthonous and autochthonous dissolved organic matter in Fe(II) oxidation: A case study in Shizugawa Bay watershed, Japan.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro

2017-08-01

Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1  s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reduction of hexavalent chromium by fasted and fed human gastric fluid. II. Ex vivo gastric reduction modeling

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

Kirman, Christopher R., E-mail: ckirman@summittoxi

To extend previous models of hexavalent chromium [Cr(VI)] reduction by gastric fluid (GF), ex vivo experiments were conducted to address data gaps and limitations identified with respect to (1) GF dilution in the model; (2) reduction of Cr(VI) in fed human GF samples; (3) the number of Cr(VI) reduction pools present in human GF under fed, fasted, and proton pump inhibitor (PPI)-use conditions; and (4) an appropriate form for the pH-dependence of Cr(VI) reduction rate constants. Rates and capacities of Cr(VI) reduction were characterized in gastric contents from fed and fasted volunteers, and from fasted pre-operative patients treated with PPIs.more » Reduction capacities were first estimated over a 4-h reduction period. Once reduction capacity was established, a dual-spike approach was used in speciated isotope dilution mass spectrometry analyses to characterize the concentration-dependence of the 2nd order reduction rate constants. These data, when combined with previously collected data, were well described by a three-pool model (pool 1 = fast reaction with low capacity; pool 2 = slow reaction with higher capacity; pool 3 = very slow reaction with higher capacity) using pH-dependent rate constants characterized by a piecewise, log-linear relationship. These data indicate that human gastric samples, like those collected from rats and mice, contain multiple pools of reducing agents, and low concentrations of Cr(VI) (< 0.7 mg/L) are reduced more rapidly than high concentrations. The data and revised modeling results herein provide improved characterization of Cr(VI) gastric reduction kinetics, critical for Cr(VI) pharmacokinetic modeling and human health risk assessment. - Highlights: • SIDMS allows for measurement of Cr(VI) reduction rate in gastric fluid ex vivo • Human gastric fluid has three reducing pools • Cr(VI) in drinking water at < 0.7 mg/L is rapidly reduced in human gastric fluid • Reduction rate is concentration- and pH-dependent • A refined PK model is used to characterize inter-individual variability in Cr(VI) gastric reduction capacity.« less

An example of slip instability resulting from displacement-varying strength

USGS Publications Warehouse

Lockner, D.; Byerlee, J.

1990-01-01

A rock cylinder, containing a clay-filled sawcut making an angle of 30?? to the sample axis, was deformed at constant confining and pore pressures and constant remote shortening rate. The sawcut surfaces contained a series of regularly spaced ridges and grooves oriented perpendicular to the direction of shear. The interaction of these grooved surfaces resulted in a sliding strength which varied periodically with displacement. By varying the effective machine stiffness through the use of an electronic feedback circuit, a range of stable and unstable slip behavior was achieved. In this way, we examined fault slip behavior which was dominated by displacement-dependent strength. ?? 1990 Birkha??user Verlag.

Photocatalytic removal of doxycycline from aqueous solution using ZnO nano-particles: a comparison between UV-C and visible light.

PubMed

Pourmoslemi, Shabnam; Mohammadi, Ali; Kobarfard, Farzad; Amini, Mohsen

2016-10-01

Zinc oxide nano-particles were synthesized, characterized and used for photocatalytic degradation of doxycycline using UV-C and visible light. Effects of several operational factors including initial pH of antibiotic solution, initial antibiotic concentration and ZnO nano-particles loading amount were investigated. Comparing photocatalytic degradation and mineralization of doxycycline under UV-C and visible light showed successful application of the method under both light sources. However, reaction rate was higher under UV-C irradiation, which degraded doxycycline almost completely in 5 hours, and 68% mineralization was achieved. Synthesized ZnO nano-particles were successfully applied for photocatalytic degradation of doxycycline in a pharmaceutical wastewater sample. The process was fitted to the pseudo first order kinetic model with rate constants in the range of 6-22(×10 -3 ) mg L -1 min -1 with respect to initial concentration of doxycycline under UV-C irradiation. The Langmuir-Hinshelwood model was also employed for describing the photocatalytic reaction with surface reaction kinetic constant k c and equilibrium adsorption constant K LH values calculated as 0.12 mg L -1 min -1 and 2.2 L mg -1 , respectively. Degradation of doxycycline was followed by UV-visible spectroscopy and a validated stability indicating high-performance liquid chromatography method that was developed using stressed samples of doxycycline and could selectively determine doxycycline in the presence of its degradation products. Mass spectrometry was used for determining final degradation products.

Dielectric studies on PEG-LTMS based polymer composites

NASA Astrophysics Data System (ADS)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-02-01

PEG LTMS based polymer composites were prepared and studied for dielectric constant variation with frequency and temperature as a potential candidate with better dielectric properties. Solution cast technique is used for the preparation of polymer composite with five different compositions. Samples show variation in dielectric constant with frequency and temperature. Dielectric constant is large at low frequencies and higher temperatures. Samples with larger space charges have shown larger dielectric constant. The highest dielectric constant observed was about 29244 for PEG25LTMS sample at 100Hz and 312 K.

Sequential CFAR detectors using a dead-zone limiter

NASA Astrophysics Data System (ADS)

Tantaratana, Sawasd

1990-09-01

The performances of some proposed sequential constant-false-alarm-rate (CFAR) detectors are evaluated. The observations are passed through a dead-zone limiter, the output of which is -1, 0, or +1, depending on whether the input is less than -c, between -c and c, or greater than c, where c is a constant. The test statistic is the sum of the outputs. The test is performed on a reduced set of data (those with absolute value larger than c), with the test statistic being the sum of the signs of the reduced set of data. Both constant and linear boundaries are considered. Numerical results show a significant reduction of the average number of observations needed to achieve the same false alarm and detection probabilities as a fixed-sample-size CFAR detector using the same kind of test statistic.

Esterification of palm fatty acid distillate with epychlorohydrin using cation exchange resin catalyst

NASA Astrophysics Data System (ADS)

Budhijanto, Budhijanto; Subagyo, Albertus F. P. H.

2017-05-01

Palm Fatty Acid Distillate (PFAD) is one of the wastes from the conversion of crude palm oil (CPO) into cooking oil. The PFAD is currently only utilized as the raw material for low grade soap and biofuel. To improve the economic value of PFAD, it was converted into monoglyceride by esterification process. Furthermore, the monoglyceride could be polymerized to form alkyd resin, which is a commodity of increasing importance. This study aimed to propose a kinetics model for esterification of PFAD with epichlorohydrin using cation exchange resin catalyst. The reaction was the first step from a series of reactions to produce the monoglyceride. In this study, the reaction between PFAD and epichlorohydirne was run in a stirred batch reactor. The stirrer was operated at a constant speed of 400 RPM. The reaction was carried out for 180 minutes on varied temperatures of 60°C, 70°C, 80°C, dan 90°C. Cation exchange resin was applied as solid catalysts. Analysis was conducted periodically by measuring the acid number of the samples, which was further used to calculate PFAD conversion. The data were used to determine the rate constants and the equilibrium constants of the kinetics model. The kinetics constants implied that the reaction was reversible and controlled by the intrinsic surface reaction. Despite the complication of the heterogeneous nature of the reaction, the kinetics data well fitted the elementary rate law. The effect of temperature on the equilibrium constants indicated that the reaction is exothermic.

Mobilisation kinetics of hazardous elements in marine plastics subject to an avian physiologically-based extraction test.

PubMed

Turner, Andrew

2018-05-01

Samples of plastic collected from two beaches in southwest England (n = 185) have been analysed by XRF spectrometry for elements that are hazardous or restricted in synthetic polymers (namely, As, Ba, Br, Cd, Cr, Hg, Pb, Sb and Se). Overall, one or more restricted element was detected in 151 samples, with 15 cases exhibiting non-compliance with respect to the Restriction of Hazardous Substances (RoHS) Directive. Twelve plastics that were RoHS-non-compliant were subsequently processed into microplastic-sized fragments and subjected to an avian physiologically-based extraction test (PBET) that simulates the chemical conditions in the gizzard-proventriculus of the northern fulmar. Kinetic profiles of metal and metalloid mobilisation in the PBET were fitted using a pseudo-first-order diffusion model with rate constants ranging from ∼0.02 to 0.5 h -1 , while profiles for Br were better fitted with a parabolic diffusion model and rate constants of 7.4-9.5 (μg L -1 ) -1 h -1/2 . Bioaccessibilities, based on maximum or equilibrium concentrations mobilised relative to total (XRF) concentrations, ranged from <1% for Cd and Se in polyethylene and polypropylene to over 10% for Br in a sample of expanded polystyrene and Pb in a sample of PVC. Calculations suggest that ingested plastic could contribute about 6% and 30% of a seabird's exposure to and accumulation of Pb and brominated compounds, respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Rate Constants and Mechanisms of Protein–Ligand Binding

PubMed Central

Pang, Xiaodong; Zhou, Huan-Xiang

2017-01-01

Whereas protein–ligand binding affinities have long-established prominence, binding rate constants and binding mechanisms have gained increasing attention in recent years. Both new computational methods and new experimental techniques have been developed to characterize the latter properties. It is now realized that binding mechanisms, like binding rate constants, can and should be quantitatively determined. In this review, we summarize studies and synthesize ideas on several topics in the hope of providing a coherent picture of and physical insight into binding kinetics. The topics include microscopic formulation of the kinetic problem and its reduction to simple rate equations; computation of binding rate constants; quantitative determination of binding mechanisms; and elucidation of physical factors that control binding rate constants and mechanisms. PMID:28375732

OXIDATION OF INCONEL 718 IN AIR AT TEMPERATURES FROM 973K TO 1620K.

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

GREENE,G.A.; FINFROCK,C.C.

2000-10-01

As part of the APT project, it was necessary to quantify the release of tungsten from the APT spallation target during postulated accident conditions in order to develop accident source terms for accident consequence characterization. Experiments with tungsten rods at high temperatures in a flowing steam environment characteristic of postulated accidents revealed that considerable vaporization of the tungsten occurred as a result of reactions with the steam and that the aerosols which formed were readily transported away from the tungsten surfaces, thus exposing fresh tungsten to react with more steam. The resulting tungsten release fractions and source terms were undesirablemore » and it was decided to clad the tungsten target with Inconel 718 in order to protect it from contact with steam during an accident and mitigate the accident source term and the consequences. As part of the material selection criteria, experiments were conducted with Inconel 718 at high temperatures to evaluate the rate of oxidation of the proposed clad material over as wide a temperature range as possible, as well as to determine the high-temperature failure limit of the material. Samples of Inconel 718 were inserted into a preheated furnace at temperatures ranging from 973 K to 1620 K and oxidized in air for varying periods of time. After oxidizing in air at a constant temperature for the prescribed time and then being allowed to cool, the samples would be reweighed to determine their weight gain due to the uptake of oxygen. From these weight gain measurements, it was possible to identify three regimes of oxidation for Inconel 718: a low-temperature regime in which the samples became passivated after the initial oxidation, an intermediate-temperature regime in which the rate of oxidation was limited by diffusion and exhibited a constant parabolic rate dependence, and a high-temperature regime in which material deformation and damage accompanied an accelerated oxidation rate above the parabolic regime. At temperatures below 1173 K, the rate of oxidation of the Inconel 718 surface was found to decrease markedly with time; the parabolic oxidation rate coefficient was not a constant but decreased with time. This was taken to indicate that the oxide film on the surface was having a passivating effect on oxygen transport through the oxide to the underlying metal. For temperatures in the range 1173 K to 1573 K, the time-dependent rate of oxidation as determined once again by weight-gain measurements was found to display the classical parabolic rate behavior, indicating that the rate of transport of reactants through the oxide was controlled by diffusion through the growing oxide layer. Parabolic rate coefficients were determined by least-squares analysis of time-dependent mass-gain data at 1173 K, 1273 K, 1373 K, 1473 K and 1573 K. At temperatures above 1540 K, post test examination of the oxidized samples revealed that the Inconel 718 began to lose strength and to deform. At 1540 K, samples which were suspended from their ends during testing began to demonstrate axial curvature as they lost strength and bowed under their own weight. As the temperatures of the tests were increased, rivulets were seen to appear on the surfaces of the test specimens; damage became severe at 1560 K. Although melting was never observed in any of these tests even up to. 1620 K, it was concluded from these data that the Inconel 718 clad should not be expected to protect the underlying tungsten at temperatures above 1540 K.« less

Electrical Conductivity of Partially Molten Peridotite Analogue Under Shear: Supporting Evidence to the Partial Melting Hypothesis for the Oceanic Plate Motion

NASA Astrophysics Data System (ADS)

Manthilake, G.; Matsuzaki, T.; Yoshino, T.; Yamazaki, D.; Yoneda, A.; Ito, E.; Katsura, T.

2008-12-01

So far, two hypotheses have been proposed to explain softening of the oceanic asthenosphere allowing smooth motion of the oceanic lithosphere. One is partial melting, and the other is hydraulitic weakening. Although the hydraulitic weakening hypothesis is popular recently, Yoshino et al. [2006] suggested that this hypothesis cannot explain the high and anisotropic conductivity at the top of the asthenosphere near East Pacific Rise observed by Evans et al. [2005]. In order to explain the conductivity anisotropy over one order of magnitude by the partial melting hypothesis, we measured conductivity of partially molten peridotite analogue under shear conditions. The measured samples were mixtures of forsterite and chemically simplified basalt. The samples were pre- synthesized using a piston-cylinder apparatus at 1600 K and 2 GPa to obtain textural equilibrium. The pre- synthesized samples were formed to a disk with 3 mm in diameter and 1 mm in thickness. Conductivity measurement was carried out also at 1600 K and 2 GPa in a cubic-anvil apparatus with an additional uniaxial piston. The sample was sandwiched by two alumina pistons whose top was cut to 45 degree slope to generate shear. The shear strain rates of the sample were calibrated using a Mo strain marker in separate runs. The lower alumina piston was pushed by a tungsten carbide piston embedded in a bottom anvil with a constant speed. Conductivity was measured in the directions normal and parallel to the shear direction simultaneously. We mainly studied the sample with 1.6 volume percent of basaltic component. The shear strain rates were 0, 1.2x10(-6) and 5.2x10(-6) /s. The sample without shear did not show conductivity anisotropy. In contrast, the samples with shear showed one order of magnitude higher conductivity in the direction parallel to the shear than that normal to the shear. After the total strains reached 0.3, the magnitude of anisotropy became almost constant for both of the strain rates. The magnitude is thus independent of the strain rate. This study demonstrates that the anisotropy at the top of the asthenosphere can be explained based on the partially molten asthenosphere sheared by the plate motion.

Water quality parameters controlling the photodegradation of two herbicides in surface waters of the Columbia Basin, Washington.

PubMed

Furman, Olha S; Yu, Miao; Teel, Amy L; Watts, Richard J

2013-11-01

The water quality parameters nitrate-nitrogen, dissolved organic carbon, and suspended solids were correlated with photodegradation rates of the herbicides atrazine and 2,4-D in samples collected from four sites in the Columbia River Basin, Washington, USA. Surface water samples were collected in May, July, and October 2010 and analyzed for the water quality parameters. Photolysis rates for the two herbicides in the surface water samples were then evaluated under a xenon arc lamp. Photolysis rates of atrazine and 2,4-D were similar with rate constants averaging 0.025 h(-1) for atrazine and 0.039 h(-1) for 2,4-D. Based on multiple regression analysis, nitrate-nitrogen was the primary predictor of photolysis for both atrazine and 2,4-D, with dissolved organic carbon also a predictor for some sites. However, at sites where suspended solids concentrations were elevated, photolysis rates of the two herbicides were controlled by the suspended solids concentration. The results of this research provide a basis for evaluating and predicting herbicide photolysis rates in shallow surface waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

Faulting of rocks in three-dimensional strain fields I. Failure of rocks in polyaxial, servo-control experiments

USGS Publications Warehouse

Reches, Z.; Dieterich, J.H.

1983-01-01

The dependence of the number of sets of faults and their orientation on the intermediate strain axis is investigated through polyaxial tests, reported here, and theoretical analysis, reported in an accompanying paper. In the experiments, cubic samples of Berea sandstone, Sierra-White and Westerly granites, and Candoro and Solnhofen limestones were loaded on their three pairs of faces by three independent, mutually perpendicular presses at room temperature. Two of the presses were servo-controlled and applied constant displacement rates throughout the experiment. Most samples display three or four sets of faults in orthorhombic symmetry. These faults form in several yielding events that follow a stage of elastic deformation. In many experiments, the maximum and the intermediate compressive stresses interchange orientations during the yielding events, where the corresponding strains are constant. The final stage of most experiments is characterized by slip along the faults. ?? 1983.

Faulting of rocks in three-dimensional strain fields I. Failure of rocks in polyaxial, servo-control experiments

NASA Astrophysics Data System (ADS)

Reches, Ze'ev; Dieterich, James H.

1983-05-01

The dependence of the number of sets of faults and their orientation on the intermediate strain axis is investigated through polyaxial tests, reported here, and theoretical analysis, reported in an accompanying paper. In the experiments, cubic samples of Berea sandstone, Sierra-White and Westerly granites, and Candoro and Solnhofen limestones were loaded on their three pairs of faces by three independent, mutually perpendicular presses at room temperature. Two of the presses were servo-controlled and applied constant displacement rates throughout the experiment. Most samples display three or four sets of faults in orthorhombic symmetry. These faults form in several yielding events that follow a stage of elastic deformation. In many experiments, the maximum and the intermediate compressive stresses interchange orientations during the yielding events, where the corresponding strains are constant. The final stage of most experiments is characterized by slip along the faults.

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

NASA Technical Reports Server (NTRS)

DeMore, W.; Wilson, E., Jr.

1998-01-01

Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

Probing the Jet Turnover Frequency Dependence on Mass and Mass Accretion Rate

NASA Astrophysics Data System (ADS)

Hammerstein, Erica; Gültekin, Kayhan; King, Ashley

2018-01-01

We have examined a sample of 15 sub-Eddington supermassive black holes (SMBHs) in a variety of galaxy classifications to further understand the proposed fundamental plane of black hole activity and scaling relations between black hole masses and their radio and X-ray luminosities. This plane describes black holes from stellar-mass to supermassive. The physics probed by these sub-Eddington systems is thought to be a radiatively inefficient, jet-dominated accretion flow. By studying black holes in this regime, we can learn important information on the disk-jet connection for accreting black holes.A key factor in studying the fundamental plane is the turnover frequency — the frequency at which emission transitions from optically thick at lower frequencies to optically thin at higher frequencies. This turnover point can be measured by observing the source in both radio and X-ray. Our project aims to test the dependence of the turnover frequency on mass and mass accretion rate.Radio observations of the sample were obtained using the Karl G. Jansky Very Large Array (VLA) in the range of 5-40 GHz across four different frequency bands in A configuration to give the highest spatial resolution to focus on the core emission. Our carefully chosen sample of SMBHs with dynamically measured masses consists of two sub-samples: those with approximately constant mass accretion rate (LX/LEdd ~ 10‑7) and those with approximately constant mass (MBH ~ 108 Msun). X-ray data were obtained from archival Chandra observations. To find the turnover frequency, we used Markov Chain Monte Carlo methods to fit two power laws to the radio data and the archival X-ray data. The intersection of the radio and X-ray fits is the turnover frequency.We present the results for both subsamples of SMBHs and their relationship between the turnover frequency and X-ray luminosity, which we take to scale with mass accretion rate, and jet power derived from both radio and X-ray properties.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

Mechanochemical destruction of DDTs with Fe-Zn bimetal in a high-energy planetary ball mill.

PubMed

Sui, Hong; Rong, Yuzhou; Song, Jing; Zhang, Dongge; Li, Haibo; Wu, Peng; Shen, Yangyang; Huang, Yujuan

2018-01-15

Mechanochemical destruction has been proposed as a promising, non-combustion technology for the disposal of toxic, halogenated, organic pollutants. In the study presented, additives including Fe, Zn, Fe-Zn bimetal, CaO and Fe 2 O 3 were tested for their effectiveness to remove DDTs by MC. The results showed that Fe-Zn bimetal was the most efficient additive, with 98% of DDTs removed after 4h. The Fe-Zn mass ratio was optimized to avoid possible spontaneous combustion of the ground sample during subsample collection. Inorganic water-soluble chloride in the ground sample increased by 91% after 4h of grinding, which indicated dechlorination during destruction of DDTs. In addition, relationships were established between the rate constant and the rotation speed or the charge ratio. Discrete Element Method (DEM) modeling was used to simulate the motion of the grinding ball and calculate both total impact energy and normal impact energy. The latter expressed a stronger, linear correlation with the rate constant. Therefore, normal impact energy is proposed to be the main driving force in the MC destruction of DDTs. Copyright © 2017 Elsevier B.V. All rights reserved.

Prediction of Chain Propagation Rate Constants of Polymerization Reactions in Aqueous NIPAM/BIS and VCL/BIS Systems.

PubMed

Kröger, Leif C; Kopp, Wassja A; Leonhard, Kai

2017-04-06

Microgels have a wide range of possible applications and are therefore studied with increasing interest. Nonetheless, the microgel synthesis process and some of the resulting properties of the microgels, such as the cross-linker distribution within the microgels, are not yet fully understood. An in-depth understanding of the synthesis process is crucial for designing tailored microgels with desired properties. In this work, rate constants and reaction enthalpies of chain propagation reactions in aqueous N-isopropylacrylamide/N,N'-methylenebisacrylamide and aqueous N-vinylcaprolactam/N,N'-methylenebisacrylamide systems are calculated to identify the possible sources of an inhomogeneous cross-linker distribution in the resulting microgels. Gas-phase reaction rate constants are calculated from B2PLYPD3/aug-cc-pVTZ energies and B3LYPD3/tzvp geometries and frequencies. Then, solvation effects based on COSMO-RS are incorporated into the rate constants to obtain the desired liquid-phase reaction rate constants. The rate constants agree with experiments within a factor of 2-10, and the reaction enthalpies deviate less than 5 kJ/mol. Further, the effect of rate constants on the microgel growth process is analyzed, and it is shown that differences in the magnitude of the reaction rate constants are a source of an inhomogeneous cross-linker distribution within the resulting microgel.

Microcomputer-Based Programs for Pharmacokinetic Simulations.

ERIC Educational Resources Information Center

Li, Ronald C.; And Others

1995-01-01

Microcomputer software that simulates drug-concentration time profiles based on user-assigned pharmacokinetic parameters such as central volume of distribution, elimination rate constant, absorption rate constant, dosing regimens, and compartmental transfer rate constants is described. The software is recommended for use in undergraduate…

Uranium mobility during interaction of rhyolitic obsidian, perlite and felsite with alkaline carbonate solution: T = 120° C, P = 210 kg/cm2

USGS Publications Warehouse

Zielinski, Robert A.

1979-01-01

Well-characterized samples of rhyolitic obsidian, perlite and felsite from a single lava flow are leached of U by alkaline oxidizing solutions under open-system conditions. Pressure, temperature, flow rate and solution composition are held constant in order to evaluate the relative importance of differences in surface area and crystallinity. Under the experimental conditions U removal from crushed glassy samples proceeds by a mechanism of glass dissolution in which U and silica are dissolved in approximately equal weight fractions. The rate of U removal from crushed glassy samples increases with decreasing average grain size (surface area). Initial rapid loss of a small component (≈ 2.5%) of the total U from crushed felsite. followed by much slower U loss, reflects variable rates of attack of numerous uranium sites. The fractions of U removed during the experiment ranged from 3.2% (felsite) to 27% (perlite). An empirical method for evaluating the relative rate of U loss from contemporaneous volcanic rocks is presented which incorporates leaching results and rock permeability data.

Shear Model Development of Limestone Joints with Incorporating Variations of Basic Friction Coefficient and Roughness Components During Shearing

NASA Astrophysics Data System (ADS)

Mehrishal, Seyedahmad; Sharifzadeh, Mostafa; Shahriar, Korosh; Song, Jae-Jon

2017-04-01

In relation to the shearing of rock joints, the precise and continuous evaluation of asperity interlocking, dilation, and basic friction properties has been the most important task in the modeling of shear strength. In this paper, in order to investigate these controlling factors, two types of limestone joint samples were prepared and CNL direct shear tests were performed on these joints under various shear conditions. One set of samples were travertine and another were onyx marble with slickensided surfaces, surfaces ground to #80, and rough surfaces were tested. Direct shear experiments conducted on slickensided and ground surfaces of limestone indicated that by increasing the applied normal stress, under different shearing rates, the basic friction coefficient decreased. Moreover, in the shear tests under constant normal stress and shearing rate, the basic friction coefficient remained constant for the different contact sizes. The second series of direct shear experiments in this research was conducted on tension joint samples to evaluate the effect of surface roughness on the shear behavior of the rough joints. This paper deals with the dilation and roughness interlocking using a method that characterizes the surface roughness of the joint based on a fundamental combined surface roughness concept. The application of stress-dependent basic friction and quantitative roughness parameters in the continuous modeling of the shear behavior of rock joints is an important aspect of this research.

Assessing Chemical Retention Process Controls in Ponds

NASA Astrophysics Data System (ADS)

Torgersen, T.; Branco, B.; John, B.

2002-05-01

Small ponds are a ubiquitous component of the landscape and have earned a reputation as effective chemical retention devices. The most common characterization of pond chemical retention is the retention coefficient, Ri= ([Ci]inflow-[Ci] outflow)/[Ci]inflow. However, this parameter varies widely in one pond with time and among ponds. We have re-evaluated literature reported (Borden et al., 1998) monthly average retention coefficients for two ponds in North Carolina. Employing a simple first order model that includes water residence time, the first order process responsible for species removal have been separated from the water residence time over which it acts. Assuming the rate constant for species removal is constant within the pond (arguable at least), the annual average rate constant for species removal is generated. Using the annual mean rate constant for species removal and monthly water residence times results in a significantly enhanced predictive capability for Davis Pond during most months of the year. Predictive ability remains poor in Davis Pond during winter/unstratified periods when internal loading of P and N results in low to negative chemical retention. Predictive ability for Piedmont Pond (which has numerous negative chemical retention periods) is improved but not to the same extent as Davis Pond. In Davis Pond, the rate constant for sediment removal (each month) is faster than the rate constant for water and explains the good predictability for sediment retention. However, the removal rate constant for P and N is slower than the removal rate constant for sediment (longer water column residence time for P,N than for sediment). Thus sedimentation is not an overall control on nutrient retention. Additionally, the removal rate constant for P is slower than for TOC (TOC is not the dominate removal process for P) and N is removed slower than P (different in pond controls). For Piedmont Pond, sediment removal rate constants are slower than the removal rate constant for water indicating significant sediment resuspension episodes. It appears that these sediment resuspension events are aperiodic and control the loading and the chemical retention capability of Piedmont Pond for N,P,TOC. These calculated rate constants reflect the differing internal loading processes for each component and suggest means and mechanisms for the use of ponds in water quality management.

Dynamic Characteristics of The DSI-Type Constant-Flow Valves

NASA Astrophysics Data System (ADS)

Kang, Yuan; Hu, Sheng-Yan; Chou, Hsien-Chin; Lee, Hsing-Han

Constant flow valves have been presented in industrial applications or academic studies, which compensate recess pressures of a hydrostatic bearing to resist load fluctuating. The flow rate of constant-flow valves can be constant in spite of the pressure changes in recesses, however the design parameters must be specified. This paper analyzes the dynamic responses of DSI-type constant-flow valves that is designed as double pistons on both ends of a spool with single feedback of working pressure and regulating restriction at inlet. In this study the static analysis presents the specific relationships among design parameters for constant flow rate and the dynamic analyses give the variations around the constant flow rate as the working pressure fluctuates.

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

NASA Technical Reports Server (NTRS)

DeMore, W.B.

1996-01-01

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

Design and characterization of thick InxGa1-xAs metamorphic buffer layers grown by hydride vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Schulte, K. L.; Zutter, B. T.; Wood, A. W.; Babcock, S. E.; Kuech, T. F.

2014-03-01

Thick InxGa1-xAs metamorphic buffer layers (MBLs) grown by hydride vapor phase epitaxy (HVPE) were studied. Relationships between MBL properties and growth parameters such as grading rate, cap layer thickness, final xInAs, and deposition temperature (TD) were explored. The MBLs were characterized by measurement of in-plane residual strain (ɛ¦¦), surface etch pit density (EPD), and surface roughness. Capping layer thickness had a strong effect on strain relaxation, with thickly capped samples exhibiting the lowest ɛ¦¦. EPD was higher in samples with thicker caps, reflecting their increased relaxation through dislocation generation. ɛ¦¦ and EPD were weakly affected by the grading rate, making capping layer thickness the primary structural parameter which controls these properties. MBLs graded in discrete steps had similar properties to MBLs with continuous grading. In samples with identical thickness and 10-step grading style, ɛ¦¦ increased almost linearly with final xInAs, while total relaxation stayed relatively constant. Relaxation as a function of xInAs could be described by an equilibrium model in which dislocation nucleation is impeded by the energy of the existing dislocation array. EPD was constant from xInAs = 0 to 0.24 then increased exponentially, which is related to the increased dislocation interaction and blocking seen at higher dislocation densities. RMS roughness increased with xInAs above a certain strain rate (0.15%/µm) samples grown below this level possessed large surface hillocks and high roughness values. The elimination of hillocks at higher values of xInAs is attributed to increased density of surface steps and is related to the out-of-plane component of the burgers vector of the dominant type of 60° dislocation. TD did not affect ɛ¦¦ for samples with a given xInAs. EPD tended to increase with TD, indicating dislocation glide likely is impeded at higher temperatures.

Oxidation of U-20 at% Zr alloy in air at 423 1063 K

NASA Astrophysics Data System (ADS)

Matsui, Tsuneo; Yamada, Takanobu; Ikai, Yasushi; Naito, Keiji

1993-01-01

The oxidation behavior of U 0.80Zr 0.20 alloy (two-phase mixture of U and UZr 2 below 878 K and single solid solution above 1008 K) was studied by thermogravimetry in the temperature range from 423 to 1063 K in air. During oxidation in the low temperature region (423-503 K), the sample kept its initial shape (a rectangular rod) and the surface of the sample was covered by a black thin adherent UO2 + x oxide layer. On the other hand, by oxidation in the middle temperature region, the sample broke to several pieces of thin plates and blocks, and fine powder at 643-723 K and entirely to fine powder at 775-878 K, all of which were analyzed to be a mixture of U 3O 8 and ZrO 2. By oxidation in the high temperature region (1008-1063 K) the sample broke to very fine powder, which consisted of U 3O 8 and ZrO 2. Based on the sample shape, the oxide phase identified after oxidation and the slope value of the bilogarithmic plots of the weight gain against time, the oxidation kinetics was analyzed with a paralinear equation in the low temperature region below 503 K and a linear equation in the middle and high temperature regions above 643 K. Oxidation rates of U 0.80Zr 0.20 (two-phase mixture) in the low and middle temperature regions were smaller than those of uranium metal. A discontinuity in the plot of the linear oxidation rate constant versus reciprocal temperature was found to be present between 723 and 838 K, similarly to the case of uranium metal previously reported. The linear rate constants of single-phase solid solution in the high temperature region above 1008 K seemed to be a little smaller than those estimated by the extrapolation of the values in the middle temperature region.

Investigation of dielectric constant variations for Malaysians soil species towards its natural background dose

NASA Astrophysics Data System (ADS)

Jafery, Khawarizmi Mohd; Embong, Zaidi; Khee, Yee See; Haimi Dahlan, Samsul; Tajudin, Saiful Azhar Ahmad; Ahmad, Salawati; Kudnie Sahari, Siti; Maxwell, Omeje

2018-01-01

The correlation of natural background gamma radiation and real part of the complex relative permittivity (dielectric constant) for various species Malaysian soils was investigated in this research. The sampling sites were chosen randomly according to soils groups that consist of sedentary, alluvial and miscellaneous soil which covered the area of Batu Pahat, Kluang and Johor Bahru, Johor state of Malaysia. There are 11 types of Malaysian soil species that have been studied; namely Peat, Linau-Sedu, Selangor-Kangkong, Kranji, Telemong-Akob-Local Alluvium, Holyrood-Lunas, Batu Anam-Melaka-Tavy, Harimau Tampoi, Kulai-Yong Peng, Rengam-Jerangau, and Steepland soils. In-situ exposure rates of each soil species were measured by using portable gamma survey meter and ex-situ analysis of real part of relative permittivity was performed by using DAK (Dielectric Assessment Kit assist by network analyser). Results revealed that the highest and the lowest background dose rate were 94 ± 26.28 μR hr-1 and 7 ± 0.67 μR hr-1 contributed by Rengam Jerangau and Peat soil species respectively. Meanwhile, dielectric constant measurement, it was performed in the range of frequency between 100 MHz to 3 GHz. The measurements of each soils species dielectric constant are in the range of 1 to 3. At the lower frequencies in the range of 100 MHz to 600 MHz, it was observed that the dielectric constant for each soil species fluctuated and inconsistent. But it remained consistent in plateau form of signal at higher frequency at range above 600 MHz. From the comparison of dielectric properties of each soil at above 600 MHz of frequency, it was found that Rengam-Jerangau soil species give the highest reading and followed by Selangor-Kangkong species. The average dielectric measurement for both Selangor-Kangkong and Rengam-Jerangau soil species are 2.34 and 2.35 respectively. Meanwhile, peat soil species exhibits the lowest dielectric measurement of 1.83. It can be clearly seen that the pattern of dielectric measurement for every soil at the frequency above 600 MHz demonstrated a specific distribution which can be classified into two main regions which are higher and lower between the ranges of 1.83 to 2.35. Pearson correlation analysis between the frequency of 100 MHz and 2.6 GHz with respect to exposure rate for every soil species was r = 0.38 and r = 0.51, respectively. This indicates that there was no strong correlation between both parameter, natural background dose and soils dielectric for each soils sample. This factor could be contributed by major and minor elements contained in each soils sample species, especially Ferum, Fe and Silica, Si.

Free radical kinetics on irradiated fennel

NASA Astrophysics Data System (ADS)

Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

2008-09-01

Herein, an electron spin resonance study on the behavior of organic radicals in fennel before and after irradiation is reported. The spectrum of irradiated fennel composed of the spectrum component derived from the un-irradiated sample (near g=2.005) and the spectra components derived from carbohydrates. The time decay of intensity spectral components was well explained by first-order kinetics with a variety of rate constants. Especially, the signal at near g=2.02 ascribed to stable cellulose-derivative components is expected to be a good indicator in the identification of irradiated plant samples.

BTEX and MTBE adsorption onto raw and thermally modified diatomite.

PubMed

Aivalioti, Maria; Vamvasakis, Ioannis; Gidarakos, Evangelos

2010-06-15

The removal of BTEX (benzene, toluene, ethyl-benzene and xylenes) and MTBE (methyl tertiary butyl ether) from aqueous solution by raw (D(R)) and thermally modified diatomite at 550, 750 and 950 degrees C (D(550), D(750) and D(950) respectively) was studied. Physical characteristics of both raw and modified diatomite such as specific surface, pore volume distribution, porosity and pH(solution) were determined, indicating important structural changes in the modified diatomite, due to exposure to high temperatures. Both adsorption kinetic and isotherm experiments were carried out. The kinetics data proved a closer fit to the pseudo-second order model. Maximum values for the rate constant, k(2), were obtained for MTBE and benzene (48.9326 and 18.0996 g mg(-1)h(-1), respectively) in sample D(550). The isotherm data proved to fit the Freundlich model more closely, which produced values of the isotherm constant 1/n higher than one, indicating unfavorable adsorption. The highest adsorption capacity, calculated through the values of the isotherm constant k(F), was obtained for MTBE (48.42 mg kg(-1) (mg/L)(n)) in sample D(950). Copyright 2010 Elsevier B.V. All rights reserved.

Nonlinear Stress/Strain Behavior of a Synthetic Porous Medium at Seismic Frequencies

NASA Astrophysics Data System (ADS)

Roberts, P. M.; Ibrahim, R. H.

2008-12-01

Laboratory experiments on porous core samples have shown that seismic-band (100 Hz or less) mechanical, axial stress/strain cycling of the porous matrix can influence the transport behavior of fluids and suspended particles during steady-state fluid flow through the cores. In conjunction with these stimulated transport experiments, measurements of the applied dynamic axial stress/strain were made to investigate the nonlinear mechanical response of porous media for a poorly explored range of frequencies from 1 to 40 Hz. A unique core-holder apparatus that applies low-frequency mechanical stress/strain to 2.54-cm-diameter porous samples during constant-rate fluid flow was used for these experiments. Applied stress was measured with a load cell in series with the source and porous sample, and the resulting strain was measured with an LVDT attached to the core face. A synthetic porous system consisting of packed 1-mm-diameter glass beads was used to investigate both stress/strain and stimulated mass-transport behavior under idealized conditions. The bead pack was placed in a rubber sleeve and static confining stresses of 2.4 MPa radial and 1.7 MPa axial were applied to the sample. Sinusoidal stress oscillations were applied to the sample at 1 to 40 Hz over a range of RMS stress amplitude from 37 to 275 kPa. Dynamic stress/strain was measured before and after the core was saturated with deionized water. The slope of the linear portion of each stress/strain hysteresis loop was used to estimate Young's modulus as a function of frequency and amplitude for both the dry and wet sample. The modulus was observed to increase after the dry sample was saturated. For both dry and wet cases, the modulus decreased with increasing dynamic RMS stress amplitude at a constant frequency of 23 Hz. At constant RMS stress amplitude, the modulus increased with increasing frequency for the wet sample but remained constant for the dry sample. The observed nonlinear behavior of Young's modulus and the dependence of stress/strain hysteresis on strain amplitude and frequency have implications on how seismic waves can influence the mechanical properties of granular porous materials in the Earth. This work was funded by the U.S. Department of Energy Basic Energy Sciences Program under the Los Alamos National Laboratory contract no. DE-AC52-06NA25396.

The Multiphase Rheology of Monte Nuovo's Eruption (Campi Flegrei, Italy)

NASA Astrophysics Data System (ADS)

Vona, A.; Romano, C.; Giordano, D.; Russell, K.

2011-12-01

We present a study of high-temperature, uniaxial deformation experiments of natural, partially crystallized samples from the Monte Nuovo (1538 AD) trachytic eruption. The experiments were performed at dry atmospheric conditions and controlled deformation rate using a high-temperature uniaxial Geocomp LoadTrac II press. Experiments were performed isothermally by deforming cores of the natural (i.e., crystal- and vesicle-bearing) samples at constant displacement rates (CDR) corresponding to constant strain rates between 10-7 and 10-4 s-1. The measurements were all performed in the viscous-flow regime and showed non-Newtonian shear thinning behavior. Measured viscosities vary between 1010 and 1013 Pa s. As no yield stress was detected, the flow behavior of the investigated specimens could be described with a simplified Herschel-Bulkley equation in terms of consistency K and flow index n. As the pure liquid and the liquid+crystal rheology of these samples were already measured in previous studies, we were able to estimate the net effects of crystals and vesicles on the rheology of the multiphase suspensions. The results revealed that the presence of vesicles has a major impact on the rheological response of magmas leading to a marked decrease of their viscosity, which partially balances the increase of viscosity due to the presence of crystals. At the same time, the presence of bubbles leads to a strong decrease in the shear strength of the magma inducing local and temporal variation in the deformation regimes (viscous vs. brittle). Brittle and ductile failure were in fact observed at T=600°C and strain rates of 10-5 s-1 and at T=800°C for the higher applied strain rate (10-4 s-1), respectively. During lava flow emplacement, this may explain the origin of the flow banding textures frequently observed in many silicic obsidian lava flows.

Development of a split-flow system for high precision variable sample introduction in supercritical fluid chromatography.

PubMed

Sakai, Miho; Hayakawa, Yoshihiro; Funada, Yasuhiro; Ando, Takashi; Fukusaki, Eiichiro; Bamba, Takeshi

2017-09-15

In this study, we propose a novel variable sample injection system based on full-loop injection, named the split-flow sample introduction system, for application in supercritical fluid chromatography (SFC). In this system, the mobile phase is split by the differential pressure between two back pressure regulators (BPRs) after full-loop injection suitable for SFC, and this differential pressure determines the introduction rate. Nine compounds with a wide range of characteristics were introduced with high reproducibility and universality, confirming that a robust variable sample injection system was achieved. We also investigated the control factors of our proposed system. Sample introduction was controlled by the ratio between the column-side pressure drops in splitless and split flow, ΔP columnsideinsplitless and ΔP columnsideinsplit , respectively, where ΔP columnsideinsplitless is related to the mobile phase flow rate and composition and the column resistance. When all other conditions are kept constant, increasing the make-up flow induces an additional pressure drop on the column side of the system, which leads to a reduced column-side flow rate, and hence decreased the amount of sample injected, even when the net pressure drop on the column side remains the same. Thus, sample introduction could be highly controlled at low sample introduction rate, regardless of the introduction conditions. This feature is advantageous because, as a control factor, the solvent in the make-up pump is independent of the column-side pressure drop. Copyright © 2017. Published by Elsevier B.V.

Stress corrosion crack initiation of Zircaloy-4 cladding tubes in an iodine vapor environment during creep, relaxation, and constant strain rate tests

NASA Astrophysics Data System (ADS)

Jezequel, T.; Auzoux, Q.; Le Boulch, D.; Bono, M.; Andrieu, E.; Blanc, C.; Chabretou, V.; Mozzani, N.; Rautenberg, M.

2018-02-01

During accidental power transient conditions with Pellet Cladding Interaction (PCI), the synergistic effect of the stress and strain imposed on the cladding by thermal expansion of the fuel, and corrosion by iodine released as a fission product, may lead to cladding failure by Stress Corrosion Cracking (SCC). In this study, internal pressure tests were conducted on unirradiated cold-worked stress-relieved Zircaloy-4 cladding tubes in an iodine vapor environment. The goal was to investigate the influence of loading type (constant pressure tests, constant circumferential strain rate tests, or constant circumferential strain tests) and test temperature (320, 350, or 380 °C) on iodine-induced stress corrosion cracking (I-SCC). The experimental results obtained with different loading types were consistent with each other. The apparent threshold hoop stress for I-SCC was found to be independent of the test temperature. SEM micrographs of the tested samples showed many pits distributed over the inner surface, which tended to coalesce into large pits in which a microcrack could initiate. A model for the time-to-failure of a cladding tube was developed using finite element simulations of the viscoplastic mechanical behavior of the material and a modified Kachanov's damage growth model. The times-to-failure predicted by this model are consistent with the experimental data.

Creep rupture of fiber bundles: A molecular dynamics investigation

NASA Astrophysics Data System (ADS)

Linga, G.; Ballone, P.; Hansen, Alex

2015-08-01

The creep deformation and eventual breaking of polymeric samples under a constant tensile load F is investigated by molecular dynamics based on a particle representation of the fiber bundle model. The results of the virtual testing of fibrous samples consisting of 40 000 particles arranged on Nc=400 chains reproduce characteristic stages seen in the experimental investigations of creep in polymeric materials. A logarithmic plot of the bundle lifetime τ versus load F displays a marked curvature, ruling out a simple power-law dependence of τ on F . A power law τ ˜F-4 , however, is recovered at high load. We discuss the role of reversible bond breaking and formation on the eventual fate of the sample and simulate a different type of creep testing, imposing a constant stress rate on the sample up to its breaking point. Our simulations, relying on a coarse-grained representation of the polymer structure, introduce new features into the standard fiber bundle model, such as real-time dynamics, inertia, and entropy, and open the way to more detailed models, aiming at material science aspects of polymeric fibers, investigated within a sound statistical mechanics framework.

Dataset for an analysis of tourism and economic growth: A study of Sri Lanka.

PubMed

Kumar, Ronald Ravinesh; Stauvermann, Peter Josef

2016-09-01

We use the sample from 1978 to 2014 for the paper (doi:10.1016/j.tmp.2016.05.005). The data on GDP at constant 2005 USD (US dollar), and the gross fixed capital formation at constant 2005 USD are extracted from the World Bank (2015). The labour stock which includes direct and indirect employment and the tourism receipts (in USD) are sourced from the Sri Lanka Tourism Development Authority (http://www.sltda.lk/statistics). Tourism receipts as a per cent of GDP is used to measure tourism demand. The capital stock data is computed using perpetual inventory method, where a depreciation rate of 8 per cent is assumed with the initial capital stock as 1.05 times the GDP of 1969 at constant 2005 USD. The output per worker and capital per worker is computed by dividing the GDP and capital stock by the labour stock, respectively.

CdTe quantum dot as a fluorescence probe for vitamin B12 in dosage form

NASA Astrophysics Data System (ADS)

Vaishnavi, E.; Renganathan, R.

2013-11-01

We here report the CdTe quantum dot (CdTe QDs)-based sensor for probing vitamin B12 derivatives in aqueous solution. In this paper, simple and sensitive fluorescence quenching measurements has been employed. The Stern-Volmer constant (KSV), quenching rate constant (kq) and binding constant (K) were rationalized from fluorescence quenching measurement. Furthermore, the fluorescence resonance energy transfer (FRET) mechanism was discussed. This method was applicable over the concentration ranging from 1 to 14 μg/mL (VB12) with correlation coefficient of 0.993. The limit of detection (LOD) of VB12 was found to be 0.15 μg/mL. Moreover, the present approach opens a simple pathway for developing cost-effective, sensitive and selective QD-based fluorescence sensors/probes for biologically significant VB12 in pharmaceutical sample with mean recoveries in the range of 100-102.1%.

Effect of fast neutron, gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate single crystals

NASA Technical Reports Server (NTRS)

Herley, P. J.; Wang, C. S.; Varsi, G.; Levy, P. W.

1974-01-01

The thermal decomposition kinetics have been determined for ammonium perchlorate crystals subjected to a fast neutron irradiation or to a fast neutron irradiation followed by a gamma-ray irradiation. Qualitatively, the radiation induced changes are similar to those obtained in this and in previous studies, with samples exposed only to gamma rays. The induction period is shortened and the rate constants, obtained from an Avrami-Erofeyev kinetic analysis, are modified. The acceleratory period constant increases and the decay period constant decreases. When compared on an equal deposited energy basis, the fast neutron induced changes are appreciably larger than the gamma-ray induced changes. Some, or all, of the fast neutron induced effects might be attributable to the introduction of localized regions of concentrated radiation damage ('spikes') by lattice atom recoils which become thermal decomposition sites when the crystals are heated.

Development of Pasteuria penetrans in Meloidogyne javanica females as affected by constantly high vs fluctuating temperature in an in-vivo system.

PubMed

Darban, D A; Gowen, S R; Pembroke, B; Mahar, A N

2005-03-01

Growth room and glasshouse experiment was conducted to investigate the effect of constant and fluctuating temperatures on the development of Pasteuria penetrans a hyperparasite of root-knot nematodes. Tomato plants (Lycopersicon esculentum Mill) were inoculated with Meloidogyne javanica second-stage juveniles attached with endospores of P. penetrans and were grown in growth room at 26-29 degrees C and in glasshouse at 20-32 degrees C. The tomato plants were sampled from the growth room after 600 degree-days based on 17 degrees C/d, accumulating each day above a base temperature of 10 degrees C and from the glasshouse after 36 calendar days. Temperature affected the development of P. penetrans directly. The rate of development at constant temperature in growth room was faster than that in the glasshouse at fluctuating temperatures.

Development of Pasteuria penetrans in Meloidogyne javanica females as affected by constantly high vs fluctuating temperature in an in-vivo system

PubMed Central

Darban, D.A.; Gowen, S.R.; Pembroke, B.; Mahar, A.N.

2005-01-01

Growth room and glasshouse experiment was conducted to investigate the effect of constant and fluctuating temperatures on the development of Pasteuria penetrans a hyperparasite of root-knot nematodes. Tomato plants (Lycopersicon esculentum Mill) were inoculated with Meloidogyne javanica second-stage juveniles attached with endospores of P. penetrans and were grown in growth room at 26–29 °C and in glasshouse at 20–32 °C. The tomato plants were sampled from the growth room after 600 degree-days based on 17 °C/d, accumulating each day above a base temperature of 10 °C and from the glasshouse after 36 calendar days. Temperature affected the development of P. penetrans directly. The rate of development at constant temperature in growth room was faster than that in the glasshouse at fluctuating temperatures. PMID:15682497

CdTe quantum dot as a fluorescence probe for vitamin B(12) in dosage form.

PubMed

Vaishnavi, E; Renganathan, R

2013-11-01

We here report the CdTe quantum dot (CdTe QDs)-based sensor for probing vitamin B12 derivatives in aqueous solution. In this paper, simple and sensitive fluorescence quenching measurements has been employed. The Stern-Volmer constant (KSV), quenching rate constant (kq) and binding constant (K) were rationalized from fluorescence quenching measurement. Furthermore, the fluorescence resonance energy transfer (FRET) mechanism was discussed. This method was applicable over the concentration ranging from 1 to 14μg/mL (VB12) with correlation coefficient of 0.993. The limit of detection (LOD) of VB12 was found to be 0.15μg/mL. Moreover, the present approach opens a simple pathway for developing cost-effective, sensitive and selective QD-based fluorescence sensors/probes for biologically significant VB12 in pharmaceutical sample with mean recoveries in the range of 100-102.1%. Copyright © 2013 Elsevier B.V. All rights reserved.

Simulating X-ray bursts during a transient accretion event

NASA Astrophysics Data System (ADS)

Johnston, Zac; Heger, Alexander; Galloway, Duncan K.

2018-06-01

Modelling of thermonuclear X-ray bursts on accreting neutron stars has to date focused on stable accretion rates. However, bursts are also observed during episodes of transient accretion. During such events, the accretion rate can evolve significantly between bursts, and this regime provides a unique test for burst models. The accretion-powered millisecond pulsar SAX J1808.4-3658 exhibits accretion outbursts every 2-3 yr. During the well-sampled month-long outburst of 2002 October, four helium-rich X-ray bursts were observed. Using this event as a test case, we present the first multizone simulations of X-ray bursts under a time-dependent accretion rate. We investigate the effect of using a time-dependent accretion rate in comparison to constant, averaged rates. Initial results suggest that using a constant, average accretion rate between bursts may underestimate the recurrence time when the accretion rate is decreasing, and overestimate it when the accretion rate is increasing. Our model, with an accreted hydrogen fraction of X = 0.44 and a CNO metallicity of ZCNO = 0.02, reproduces the observed burst arrival times and fluences with root mean square (rms) errors of 2.8 h, and 0.11× 10^{-6} erg cm^{-2}, respectively. Our results support previous modelling that predicted two unobserved bursts and indicate that additional bursts were also missed by observations.

Simulated remodeling of loaded collagen networks via strain-dependent enzymatic degradation and constant-rate fiber growth

PubMed Central

Hadi, M.F.; Sander, E.A.; Ruberti, J.W.; Barocas, V. H.

2011-01-01

Recent work has demonstrated that enzymatic degradation of collagen fibers exhibits strain-dependent kinetics. Conceptualizing how the strain dependence affects remodeling of collagenous tissues is vital to our understanding of collagen management in native and bioengineered tissues. As a first step towards this goal, the current study puts forward a multiscale model for enzymatic degradation and remodeling of collagen networks for two sample geometries we routinely use in experiments as model tissues. The multiscale model, driven by microstructural data from an enzymatic decay experiment, includes an exponential strain-dependent kinetic relation for degradation and constant growth. For a dogbone sample under uniaxial load, the model predicted that the distribution of fiber diameters would spread over the course of degradation because of variation in individual fiber load. In a cross-shaped sample, the central region, which experiences smaller, more isotropic loads, showed more decay and less spread in fiber diameter compared to the arms. There was also a slight shift in average orientation in different regions of the cruciform. PMID:22180691

Concurrent determination of total serum calcium and magnesium by thermometric titration with ethylenediaminetetraacetate.

PubMed

Callicott, R H; Carr, P W

1976-07-01

Total serum calcium and magnesium may be determined in one thermometric titration, with disodium ethylenediaminetetraacetate as the titrant. A 1-ml serum sample is diluted with 1 ml of tris(hydroxymethyl)aminomethane buffer (pH 8) and titrated at a constant rate with a motorized syringe buret. Results by the thermometric method compared well with those by atomic absorption spectroscopy.

A framework for establishing predictive relationships between specific bacterial 16S rRNA sequence abundances and biotransformation rates.

PubMed

Helbling, Damian E; Johnson, David R; Lee, Tae Kwon; Scheidegger, Andreas; Fenner, Kathrin

2015-03-01

The rates at which wastewater treatment plant (WWTP) microbial communities biotransform specific substrates can differ by orders of magnitude among WWTP communities. Differences in taxonomic compositions among WWTP communities may predict differences in the rates of some types of biotransformations. In this work, we present a novel framework for establishing predictive relationships between specific bacterial 16S rRNA sequence abundances and biotransformation rates. We selected ten WWTPs with substantial variation in their environmental and operational metrics and measured the in situ ammonia biotransformation rate constants in nine of them. We isolated total RNA from samples from each WWTP and analyzed 16S rRNA sequence reads. We then developed multivariate models between the measured abundances of specific bacterial 16S rRNA sequence reads and the ammonia biotransformation rate constants. We constructed model scenarios that systematically explored the effects of model regularization, model linearity and non-linearity, and aggregation of 16S rRNA sequences into operational taxonomic units (OTUs) as a function of sequence dissimilarity threshold (SDT). A large percentage (greater than 80%) of model scenarios resulted in well-performing and significant models at intermediate SDTs of 0.13-0.14 and 0.26. The 16S rRNA sequences consistently selected into the well-performing and significant models at those SDTs were classified as Nitrosomonas and Nitrospira groups. We then extend the framework by applying it to the biotransformation rate constants of ten micropollutants measured in batch reactors seeded with the ten WWTP communities. We identified phylogenetic groups that were robustly selected into all well-performing and significant models constructed with biotransformation rates of isoproturon, propachlor, ranitidine, and venlafaxine. These phylogenetic groups can be used as predictive biomarkers of WWTP microbial community activity towards these specific micropollutants. This work is an important step towards developing tools to predict biotransformation rates in WWTPs based on taxonomic composition. Copyright © 2014 Elsevier Ltd. All rights reserved.

Uptake and Disposition of Select Pharmaceuticals by Bluegill Exposed at Constant Concentrations in a Flow-Through Aquatic Exposure System.

PubMed

Zhao, Jian-Liang; Furlong, Edward T; Schoenfuss, Heiko L; Kolpin, Dana W; Bird, Kyle L; Feifarek, David J; Schwab, Eric A; Ying, Guang-Guo

2017-04-18

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish (Lepomis macrochirus) exposed to environmentally relevant concentrations (1000-4000 ng L -1 ) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g -1 , respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71-3960 and 0.13-48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log K ow (that is, log D ow ), with the strongest relations for liver and brain (r 2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants (K u ) and elimination rate constants (K e ) at 0.0066-0.0330 h -1 and 0.0075-0.0384 h -1 , respectively, and half-lives at 18.1-92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

Uptake and disposition of select pharmaceuticals by bluegill exposed at constant concentrations in a flow-through aquatic exposure system

USGS Publications Warehouse

Zhao, Jian-Liang; Furlong, Edward T.; Schoenfuss, Heiko L.; Kolpin, Dana W.; Bird, Kyle L.; Feifarek, David J.; Schwab, Eric A.; Ying, Guang-Guo

2017-01-01

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish (Lepomis macrochirus) exposed to environmentally relevant concentrations (1000–4000 ng L–1) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g–1, respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71–3960 and 0.13–48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log Kow (that is, log Dow), with the strongest relations for liver and brain (r2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants (Ku) and elimination rate constants (Ke) at 0.0066–0.0330 h–1 and 0.0075–0.0384 h–1, respectively, and half-lives at 18.1–92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

GROUND WATER ISSUE - CALCULATION AND USE OF FIRST-ORDER RATE CONSTANTS FOR MONITORED NATURAL ATTENUATION STUDIES

EPA Science Inventory

This issue paper explains when and how to apply first-order attenuation rate constant calculations in monitored natural attenuation (MNA) studies. First-order attenuation rate constant calculations can be an important tool for evaluating natural attenuation processes at ground-wa...

Trends in electron-ion dissociative recombination of benzene analogs with functional group substitutions: Negative Hammett σpara values

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick Andrew; Adams, Nigel; Dotan, Itzhak

2014-06-01

An in-depth study of the effects of functional group substitution on benzene's electron-ion dissociative recombination (e-IDR) rate constant has been conducted. The e-IDR rate constants for benzene, biphenyl, toluene, ethylbenzene, anisole, phenol, and aniline have been measured using a Flowing Afterglow equipped with an electrostatic Langmuir probe (FALP). These measurements have been made over a series of temperatures from 300 to 550 K. A relationship between the Hammett σpara values for each compound and rate constant has indicated a trend in the e-IDR rate constants and possibly in their temperature dependence data. The Hammett σpara value is a method to describe the effect a functional group substituted to a benzene ring has upon the reaction rate constant.

All human Na(+)-K(+)-ATPase alpha-subunit isoforms have a similar affinity for cardiac glycosides.

PubMed

Wang, J; Velotta, J B; McDonough, A A; Farley, R A

2001-10-01

Three alpha-subunit isoforms of the sodium pump, which is the receptor for cardiac glycosides, are expressed in human heart. The aim of this study was to determine whether these isoforms have distinct affinities for the cardiac glycoside ouabain. Equilibrium ouabain binding to membranes from a panel of different human tissues and cell lines derived from human tissues was compared by an F statistic to determine whether a single population of binding sites or two populations of sites with different affinities would better fit the data. For all tissues, the single-site model fit the data as well as the two-site model. The mean equilibrium dissociation constant (K(d)) for all samples calculated using the single-site model was 18 +/- 6 nM (mean +/- SD). No difference in K(d) was found between nonfailing and failing human heart samples, although the maximum number of binding sites in failing heart was only approximately 50% of the number of sites in nonfailing heart. Measurement of association rate constants and dissociation rate constants confirmed that the binding affinities of the different human alpha-isoforms are similar to each other, although calculated K(d) values were lower than those determined by equilibrium binding. These results indicate both that the affinity of all human alpha-subunit isoforms for ouabain is similar and that the increased sensitivity of failing human heart to cardiac glycosides is probably due to a reduction in the number of pumps in the heart rather than to a selective inhibition of a subset of pumps with different affinities for the drugs.

Equilibrium muscle cross-bridge behavior. Theoretical considerations.

PubMed Central

Schoenberg, M

1985-01-01

We have developed a model for the equilibrium attachment and detachment of myosin cross-bridges to actin that takes into account the possibility that a given cross-bridge can bind to one of a number of actin monomers, as seems likely, rather than to a site on only a single actin monomer, as is often assumed. The behavior of this multiple site model in response to constant velocity, as well as instantaneous stretches, was studied and the influence of system parameters on the force response explored. It was found that in the multiple site model the detachment rate constant has considerably greater influence on the mechanical response than the attachment rate constant. It is shown that one can obtain information about the detachment rate constants either by examining the relationship between the apparent stiffness and duration of stretch for constant velocity stretches or by examining the force-decay rate constants following an instantaneous stretch. The main effect of the attachment rate constant is to scale the mechanical response by influencing the number of attached cross-bridges. The significance of the modeling for the interpretation of experimental results is discussed. PMID:4041539

Large strain dynamic compression for soft materials using a direct impact experiment

NASA Astrophysics Data System (ADS)

Meenken, T.; Hiermaier, S.

2006-08-01

Measurement of strain rate dependent material data of low density low strength materials like polymeric foams and rubbers still poses challenges of a different kind to the experimental set up. For instance, in conventional Split Hopkinson Pressure Bar tests the impedance mismatch between the bars and the specimen makes strain measurement almost impossible. Application of viscoelastic bars poses new problems with wave dispersion. Also, maximum achievable strains and strain rates depend directly on the bar lengths, resulting in large experimental set ups in order to measure relevant data for automobile crash applications. In this paper a modified SHPB will be presented for testing low impedance materials. High strains can be achieved with nearly constant strain rate. A thin film stress measurement has been applied to the specimen/bar interfaces to investigate the initial sample ring up process. The process of stress homogeneity within the sample was investigated on EPDM and PU rubber.

Burning rate for steel-cased, pressed binderless HMX

NASA Technical Reports Server (NTRS)

Fifer, R. A.; Cole, J. E.

1980-01-01

The burning behavior of pressed binderless HMX laterally confined in 6.4 mm i.d. steel cases was measured over the pressure range 1.45 to 338 MPa in a constant pressure strand burner. The measured regression rates are compared to those reported previously for unconfined samples. It is shown that lateral confinement results in a several-fold decrease in the regression rate for the coarse particle size HMX above the transition to super fast regression. For class E samples, confinement shifts the transition to super fast regression from low pressure to high pressure. These results are interpreted in terms of the previously proposed progressive deconsolidation mechanism. Preliminary holographic photography and closed bomb tests are also described. Theoretical one dimensional modeling calculations were carried out to predict the expected flame height (particle burn out distance) as a function of particle size and pressure for binderless HMX burning by a progressive deconsolidation mechanism.

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

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

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

Acceleration and sensitivity analysis of lattice kinetic Monte Carlo simulations using parallel processing and rate constant rescaling

NASA Astrophysics Data System (ADS)

Núñez, M.; Robie, T.; Vlachos, D. G.

2017-10-01

Kinetic Monte Carlo (KMC) simulation provides insights into catalytic reactions unobtainable with either experiments or mean-field microkinetic models. Sensitivity analysis of KMC models assesses the robustness of the predictions to parametric perturbations and identifies rate determining steps in a chemical reaction network. Stiffness in the chemical reaction network, a ubiquitous feature, demands lengthy run times for KMC models and renders efficient sensitivity analysis based on the likelihood ratio method unusable. We address the challenge of efficiently conducting KMC simulations and performing accurate sensitivity analysis in systems with unknown time scales by employing two acceleration techniques: rate constant rescaling and parallel processing. We develop statistical criteria that ensure sufficient sampling of non-equilibrium steady state conditions. Our approach provides the twofold benefit of accelerating the simulation itself and enabling likelihood ratio sensitivity analysis, which provides further speedup relative to finite difference sensitivity analysis. As a result, the likelihood ratio method can be applied to real chemistry. We apply our methodology to the water-gas shift reaction on Pt(111).

Well hydraulics in pumping tests with exponentially decayed rates of abstraction in confined aquifers

NASA Astrophysics Data System (ADS)

Wen, Zhang; Zhan, Hongbin; Wang, Quanrong; Liang, Xing; Ma, Teng; Chen, Chen

2017-05-01

Actual field pumping tests often involve variable pumping rates which cannot be handled by the classical constant-rate or constant-head test models, and often require a convolution process to interpret the test data. In this study, we proposed a semi-analytical model considering an exponentially decreasing pumping rate started at a certain (higher) rate and eventually stabilized at a certain (lower) rate for cases with or without wellbore storage. A striking new feature of the pumping test with an exponentially decayed rate is that the drawdowns will decrease over a certain period of time during intermediate pumping stage, which has never been seen before in constant-rate or constant-head pumping tests. It was found that the drawdown-time curve associated with an exponentially decayed pumping rate function was bounded by two asymptotic curves of the constant-rate tests with rates equaling to the starting and stabilizing rates, respectively. The wellbore storage must be considered for a pumping test without an observation well (single-well test). Based on such characteristics of the time-drawdown curve, we developed a new method to estimate the aquifer parameters by using the genetic algorithm.

Kinetics of phase transformations in glass forming systems

NASA Technical Reports Server (NTRS)

Ray, Chandra S.

1993-01-01

In crystallization measurements of nonisothermal nucleation for Li2O.2SiO2 (LS2) glass, using DTA, the glass sample is scanned at different constant heating rates until it is crystallized. This means that the temperature range where nucleation can occur for the glass is scanned also at different rates which allows the glass to be nucleated for different time prior to crystallization. Consequently, the concentration of nuclei developed in the glass may be different for different heating rates and the DTA peak height which has shown to be sensitive to the number of nuclei present in the sample, is expected to change with heating rate. DTA peak height depends strongly on the overlap between the nucleation rate and growth rate curves, assuming the peak height is directly proportional to the total number of nuclei present in the glass sample under investigation, which, in turn, should be proportional to the volume or weight of the sample. To verify this assumption, DTA measurements were made using a LS2 glass to determine the peak height as a function of the sample weight. Using the DTA peak height technique, a nucleation rate like curve was determined for the BaO.2SiO2 (BS2) glass which showed that the temperature for nucleation ranged from 650 to 750 C for this glass and the temperature for maximum nucleation was approximately 705 C. These values are in excellent agreement with those determined by the conventional technique. There was international collaboration with Japan and Germany on this project.

Creep of Ni(3)Al in the temperature regime of anomalous flow behavior

NASA Astrophysics Data System (ADS)

Uchic, Michael David

Much attention has been paid to understanding the dynamics of dislocation motion and substructure formation in Ni3Al in the anomalous flow regime. However, most of the experimental work that has been performed in the lowest temperatures of the anomalous flow regime has been under constant-strain-rate conditions. An alternative and perhaps more fundamental way to probe the plastic behavior of materials is a monotonic creep test, in which the stress and temperature are held constant while the time-dependent strain is measured. The aim of this study is to use constant-stress experiments to further explore the plastic flow anomaly in L12 alloys at low temperatures. Tension creep experiments have been carried out on <123> oriented single crystals of Ni75Al24Ta1 at temperatures between 293 and 473 K. We have observed primary creep leading to exhaustion at all temperatures and stresses, with creep rates declining faster than predicted by the logarithmic creep law. The total strain and creep strain have an anomalous dependence on temperature, which is consistent with the flow stress anomaly. We have also observed other unusual behavior in our creep experiments; for example, the reinitiation of plastic flow at low temperatures after a modest increment in applied stress shows a sigmoidal response, i.e., there is a significant time delay before the plastic strain rate accelerates to a maximum value. We also examined the ability to reinitiate plastic flow in samples that have been crept to exhaustion by simply lowering the test temperature. In addition, we have also performed conventional constant-displacement-rate experiments in the same temperature range. From these experiments, we have discovered that unlike most metals, Ni3Al displays a negative dependence of the work hardening rate (WHR) with increasing strain rate. For tests at intermediate temperatures (373 and 423 K), the WHRs of crystals tested at moderately high strain rates (10-2 s-1) are half the WHRs of crystals tested at conventional strain rates (10 -5 s-1), and this anomalous dependence has also been shown to be reversible with changes in strain rate. The implications of all results are discussed in light of our efforts to model plastic deformation in these alloys.

Modeling and monitoring cyclic and linear volatile methylsiloxanes in a wastewater treatment plant using constant water level sequencing batch reactors.

PubMed

Wang, De-Gao; Du, Juan; Pei, Wei; Liu, Yongjun; Guo, Mingxing

2015-04-15

The fate of cyclic and linear volatile methylsiloxanes (VMSs) was evaluated in a wastewater treatment plant (WWTP) using constant water level sequencing batch reactors from Dalian, China. Influent, effluent, and sewage sludge samples were collected for seven consecutive days. The mean concentrations of cyclic VMSs (cVMSs) in influent and effluent samples are 1.05 μg L(-1) and 0.343 μg L(-1); the total removal efficiency of VMSs is >60%. Linear VMS (lVMS) concentration is under the quantification limitation in aquatic samples but is found in sludge samples with a value of 90 μg kg(-1). High solid-water partition coefficients result in high VMS concentrations in sludge with the mean value of 5030 μg kg(-1). No significant differences of the daily mass flows are found when comparing the concentration during the weekend and during working days. The estimated mass load of total cVMSs is 194 mg d(-1)1000 inhabitants(-1) derived for the population. A mass balance model of the WWTP was developed and derived to simulate the fate of cVMSs. The removal by sorption on sludge increases, and the volatilization decreases with increasing hydrophobicity and decreasing volatility for cVMSs. Sensitivity analysis shows that the total suspended solid concentration in the effluent, mixed liquor suspended solid concentration, the sewage sludge flow rate, and the influent flow rate are the most influential parameters on the mass distribution of cVMSs in this WWTP. Copyright © 2015 Elsevier B.V. All rights reserved.

Compton suppression gamma-counting: The effect of count rate

USGS Publications Warehouse

Millard, H.T.

1984-01-01

Past research has shown that anti-coincidence shielded Ge(Li) spectrometers enhanced the signal-to-background ratios for gamma-photopeaks, which are situated on high Compton backgrounds. Ordinarily, an anti- or non-coincidence spectrum (A) and a coincidence spectrum (C) are collected simultaneously with these systems. To be useful in neutron activation analysis (NAA), the fractions of the photopeak counts routed to the two spectra must be constant from sample to sample to variations must be corrected quantitatively. Most Compton suppression counting has been done at low count rate, but in NAA applications, count rates may be much higher. To operate over the wider dynamic range, the effect of count rate on the ratio of the photopeak counts in the two spectra (A/C) was studied. It was found that as the count rate increases, A/C decreases for gammas not coincident with other gammas from the same decay. For gammas coincident with other gammas, A/C increases to a maximum and then decreases. These results suggest that calibration curves are required to correct photopeak areas so quantitative data can be obtained at higher count rates. ?? 1984.

Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Newsome, Ben; Evans, Mat

2017-12-01

Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M HNO3 and O3 + NO → NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote regions such as the tropics, poles and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered alongside other processes when model results disagree with measurement. Calculations for the pre-industrial simulation allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 W m-2. This uncertainty (13 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model intercomparison studies where the rate constants used in the models are all identical or very similar. Thus, the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well-known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

Testing for variation in taxonomic extinction probabilities: a suggested methodology and some results

USGS Publications Warehouse

Conroy, M.J.; Nichols, J.D.

1984-01-01

Several important questions in evolutionary biology and paleobiology involve sources of variation in extinction rates. In all cases of which we are aware, extinction rates have been estimated from data in which the probability that an observation (e.g., a fossil taxon) will occur is related both to extinction rates and to what we term encounter probabilities. Any statistical method for analyzing fossil data should at a minimum permit separate inferences on these two components. We develop a method for estimating taxonomic extinction rates from stratigraphic range data and for testing hypotheses about variability in these rates. We use this method to estimate extinction rates and to test the hypothesis of constant extinction rates for several sets of stratigraphic range data. The results of our tests support the hypothesis that extinction rates varied over the geologic time periods examined. We also present a test that can be used to identify periods of high or low extinction probabilities and provide an example using Phanerozoic invertebrate data. Extinction rates should be analyzed using stochastic models, in which it is recognized that stratigraphic samples are random varlates and that sampling is imperfect

Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

PubMed

Allison, Thomas C

2016-03-03

Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

A Computational Framework for Analyzing Stochasticity in Gene Expression

PubMed Central

Sherman, Marc S.; Cohen, Barak A.

2014-01-01

Stochastic fluctuations in gene expression give rise to distributions of protein levels across cell populations. Despite a mounting number of theoretical models explaining stochasticity in protein expression, we lack a robust, efficient, assumption-free approach for inferring the molecular mechanisms that underlie the shape of protein distributions. Here we propose a method for inferring sets of biochemical rate constants that govern chromatin modification, transcription, translation, and RNA and protein degradation from stochasticity in protein expression. We asked whether the rates of these underlying processes can be estimated accurately from protein expression distributions, in the absence of any limiting assumptions. To do this, we (1) derived analytical solutions for the first four moments of the protein distribution, (2) found that these four moments completely capture the shape of protein distributions, and (3) developed an efficient algorithm for inferring gene expression rate constants from the moments of protein distributions. Using this algorithm we find that most protein distributions are consistent with a large number of different biochemical rate constant sets. Despite this degeneracy, the solution space of rate constants almost always informs on underlying mechanism. For example, we distinguish between regimes where transcriptional bursting occurs from regimes reflecting constitutive transcript production. Our method agrees with the current standard approach, and in the restrictive regime where the standard method operates, also identifies rate constants not previously obtainable. Even without making any assumptions we obtain estimates of individual biochemical rate constants, or meaningful ratios of rate constants, in 91% of tested cases. In some cases our method identified all of the underlying rate constants. The framework developed here will be a powerful tool for deducing the contributions of particular molecular mechanisms to specific patterns of gene expression. PMID:24811315

Class Projects in Physical Organic Chemistry: The Hydrolysis of Aspirin

ERIC Educational Resources Information Center

Marrs, Peter S.

2004-01-01

An exercise that provides a hands-on demonstration of the hydrolysis of aspirin is presented. The key to understanding the hydrolysis is recognizing that all six process may occur simultaneously and that the observed rate constant is the sum of the rate constants that one rate constant dominates the overall process.

Quantum calculations of the rate constant for the O(3P)+HCl reaction on new ab initio 3A″ and 3A' surfaces

NASA Astrophysics Data System (ADS)

Xie, Tiao; Bowman, Joel M.; Peterson, K. A.; Ramachandran, B.

2003-11-01

We report the thermal rate constant of the O(3P)+HCl→OH+Cl reaction calculated from 200 to 3200 K, using new fits to extensive ab initio calculations [B. Ramachandran and K. A. Peterson, J. Chem. Phys. 119, 9590 (2003), preceding paper]. The rate constants are obtained for both the 3A″ and 3A' surfaces using exact quantum reactive scattering calculations for selected values of the total angular momentum and the J-shifting approximation for both the 3A″ and 3A' surfaces. The results are compared with the ICVT/μOMT rate constants calculated by the POLYRATE program and all available experimental data. Other related high-energy reaction channels are also studied qualitatively for their contribution to the total thermal rate constant at high temperature.

Species abundance distributions in neutral models with immigration or mutation and general lifetimes.

PubMed

Lambert, Amaury

2011-07-01

We consider a general, neutral, dynamical model of biodiversity. Individuals have i.i.d. lifetime durations, which are not necessarily exponentially distributed, and each individual gives birth independently at constant rate λ. Thus, the population size is a homogeneous, binary Crump-Mode-Jagers process (which is not necessarily a Markov process). We assume that types are clonally inherited. We consider two classes of speciation models in this setting. In the immigration model, new individuals of an entirely new species singly enter the population at constant rate μ (e.g., from the mainland into the island). In the mutation model, each individual independently experiences point mutations in its germ line, at constant rate θ. We are interested in the species abundance distribution, i.e., in the numbers, denoted I(n)(k) in the immigration model and A(n)(k) in the mutation model, of species represented by k individuals, k = 1, 2, . . . , n, when there are n individuals in the total population. In the immigration model, we prove that the numbers (I(t)(k); k ≥ 1) of species represented by k individuals at time t, are independent Poisson variables with parameters as in Fisher's log-series. When conditioning on the total size of the population to equal n, this results in species abundance distributions given by Ewens' sampling formula. In particular, I(n)(k) converges as n → ∞ to a Poisson r.v. with mean γ/k, where γ : = μ/λ. In the mutation model, as n → ∞, we obtain the almost sure convergence of n (-1) A(n)(k) to a nonrandom explicit constant. In the case of a critical, linear birth-death process, this constant is given by Fisher's log-series, namely n(-1) A(n)(k) converges to α(k)/k, where α : = λ/(λ + θ). In both models, the abundances of the most abundant species are briefly discussed.

Inflation with a constant rate of roll

NASA Astrophysics Data System (ADS)

Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi

2015-09-01

We consider an inflationary scenario where the rate of inflaton roll defined by ̈phi/H dot phi remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.

On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

PubMed

Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

2016-07-13

If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; DeMore, W. B.

1995-01-01

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Biogeochemical factors influencing net mercury methylation in contaminated freshwater sediments from the St. Lawrence River in Cornwall, Ontario, Canada.

PubMed

Avramescu, Mary-Luyza; Yumvihoze, Emmanuel; Hintelmann, Holger; Ridal, Jeff; Fortin, Danielle; Lean, David R S

2011-02-01

The activity of various anaerobic microbes, including sulfate reducers (SRB), iron reducers (FeRP) and methanogens (MPA) has been linked to mercury methylation in aquatic systems, although the relative importance of each microbial group in the overall process is poorly understood in natural sediments. The present study focused on the biogeochemical factors (i.e. the relative importance of various groups of anaerobic microbes (FeRP, SRB, and MPA) that affect net monomethylmercury (MMHg) formation in contaminated sediments of the St. Lawrence River (SRL) near Cornwall (Zone 1), Ontario, Canada. Methylation and demethylation potentials were measured separately by using isotope-enriched mercury species ((200)Hg(2+) and MM(199)Hg(+)) in sediment microcosms treated with specific microbial inhibitors. Sediments were sampled and incubated in the dark at room temperature in an anaerobic chamber for 96h. The potential methylation rate constants (K(m)) and demethylation rates (K(d)) were found to differ significantly between microcosms. The MPA-inhibited microcosm had the highest potential methylation rate constant (0.016d(-1)), whereas the two SRB-inhibited microcosms had comparable potential methylation rate constants (0.003d(-1) and 0.002d(-1), respectively). The inhibition of methanogens stimulated net methylation by inhibiting demethylationand by stimulating methylation along with SRB activity. The inhibition of both methanogens and SRB was found to enhance the iron reduction rates but did not completely stop MMHg production. The strong positive correlation between K(m) and Sulfate Reduction Rates (SRR) and between K(d) and Methane Production Rates (MPR) supports the involvement of SRB in Hg methylation and MPA in MMHg demethylation in the sediments. In contrast, the strong negative correlation between K(d) and Iron Reduction Rates (FeRR) shows that the increase in FeRR corresponds to a decrease in demethylation, indicating that iron reduction may influence net methylation in the SLR sediments by decreasing demethylation rather than favouring methylation. Copyright © 2010 Elsevier B.V. All rights reserved.

Reaction of SO2 with OH in the atmosphere.

PubMed

Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

2017-03-15

The OH + SO 2 reaction plays a critical role in understanding the oxidation of SO 2 in the atmosphere, and its rate constant is critical for clarifying the fate of SO 2 in the atmosphere. The rate constant of the OH + SO 2 reaction is calculated here by using beyond-CCSDT correlation energy calculations for a benchmark, validated density functional methods for direct dynamics, canonical variational transition state theory with anharmonicity and multidimensional tunneling for the high-pressure rate constant, and system-specific quantum RRK theory for pressure effects; the combination of these methods can compete in accuracy with experiments. There has been a long-term debate in the literature about whether the OH + SO 2 reaction is barrierless, but our calculations indicate a positive barrier with an transition structure that has an enthalpy of activation of 0.27 kcal mol -1 at 0 K. Our results show that the high-pressure limiting rate constant of the OH + SO 2 reaction has a positive temperature dependence, but the rate constant at low pressures has a negative temperature dependence. The computed high-pressure limiting rate constant at 298 K is 1.25 × 10 -12 cm 3 molecule -1 s -1 , which agrees excellently with the value (1.3 × 10 -12 cm 3 molecule -1 s -1 ) recommended in the most recent comprehensive evaluation for atmospheric chemistry. We show that the atmospheric lifetime of SO 2 with respect to oxidation by OH depends strongly on altitude (in the range 0-50 km) due to the falloff effect. We introduce a new interpolation procedure for fitting the combined temperature and pressure dependence of the rate constant, and it fits the calculated rate constants over the whole range with a mean unsigned error of only 7%. The present results provide reliable kinetics data for this specific reaction, and also they demonstrate convenient theoretical methods that can be reliable for predicting rate constants of other gas-phase reactions.

Electrohydrodynamic distortion of sample streams in continuous flow electrophoresis

NASA Technical Reports Server (NTRS)

Rhodes, Percy H.; Snyder, Robert S.; Roberts, Glyn O.

1989-01-01

Continuous flow electrophoresis experiments were carried out, using an electrolyte and a sample both made of aqueous solutions of phosphate buffer (with polystyrene latex added for visibility), to investigate causes of the sample spreading in this procedure. It is shown theoretically that an electric field perpendicular to a circular filament of conducting fluid surrounded by a fluid of different conductivity produces an electrohydrodynamic flow, which distorts the filament into an ellipse. Experimental results were found to be fully consistent with theretical predictions. It was found that the rate of distortion of the sample stream into a ribbon was proportional to the square of the applied voltage gradient. Furthermore, the orientation of the ribbon depends on the ratios of dielectric constant and electrical conductivity between the buffer and the sample.

Rate constant for the fraction of atomic chlorine with formaldehyde from 200 to 500K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.

1978-01-01

A flash photolysis - resonance fluorescence technique was used to measure rate constant. The results were independent of substantial variations in H2CO, total pressure (Ar), and flash intensity (i.e., initial Cl). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being K = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

Kinetic analysis of volatile formation in milk subjected to pressure-assisted thermal treatments.

PubMed

Vazquez-Landaverde, P A; Qian, M C; Torres, J A

2007-09-01

Volatile formation in milk subjected to pressure-assisted thermal processing (PATP) was investigated from a reaction kinetic analysis point of view to illustrate the advantages of this technology. The concentration of 27 volatiles of different chemical class in milk subjected to pressure, temperature, and time treatments was fitted to zero-, 1st-, and 2nd-order chemical reaction models. Temperature and pressure effects on rate constants were analyzed to obtain activation energy (E(a)) and activation volume (deltaV*) values. Hexanal, heptanal, octanal, nonanal, and decanal followed 1st-order kinetics with rate constants characterized by E(a) values decreasing with pressure reflecting negative deltaV* values. Formation of 2-methylpropanal, 2,3-butanedione, and hydrogen sulfide followed zero-order kinetics with rate constants increasing with temperature but with unclear pressure effects. E(a) values for 2-methylpropanal and 2,3-butanedione increased with pressure, that is, deltaV* > 0, whereas values for hydrogen sulfide remained constant, that is, deltaV* = 0. The concentration of all other volatiles, including methanethiol, remained unchanged in pressure-treated samples, suggesting large negative deltaV* values. The concentration of methyl ketones, including 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, 2-decanone, and 2-undecanone, was independent of pressure and pressure-holding time. PATP promoted the formation of few compounds, had no effect on some, and inhibited the formation of volatiles reported to be factors of the consumer rejection of "cooked" milk flavor. The kinetic behavior observed suggested that new reaction formation mechanisms were not likely involved in volatile formation in PATP milk. The application of the Le Chatelier principle frequently used to explain the high quality of pressure-treated foods, often with no supporting experimental evidence, was not necessary.

Digital timing: sampling frequency, anti-aliasing filter and signal interpolation filter dependence on timing resolution.

PubMed

Cho, Sanghee; Grazioso, Ron; Zhang, Nan; Aykac, Mehmet; Schmand, Matthias

2011-12-07

The main focus of our study is to investigate how the performance of digital timing methods is affected by sampling rate, anti-aliasing and signal interpolation filters. We used the Nyquist sampling theorem to address some basic questions such as what will be the minimum sampling frequencies? How accurate will the signal interpolation be? How do we validate the timing measurements? The preferred sampling rate would be as low as possible, considering the high cost and power consumption of high-speed analog-to-digital converters. However, when the sampling rate is too low, due to the aliasing effect, some artifacts are produced in the timing resolution estimations; the shape of the timing profile is distorted and the FWHM values of the profile fluctuate as the source location changes. Anti-aliasing filters are required in this case to avoid the artifacts, but the timing is degraded as a result. When the sampling rate is marginally over the Nyquist rate, a proper signal interpolation is important. A sharp roll-off (higher order) filter is required to separate the baseband signal from its replicates to avoid the aliasing, but in return the computation will be higher. We demonstrated the analysis through a digital timing study using fast LSO scintillation crystals as used in time-of-flight PET scanners. From the study, we observed that there is no significant timing resolution degradation down to 1.3 Ghz sampling frequency, and the computation requirement for the signal interpolation is reasonably low. A so-called sliding test is proposed as a validation tool checking constant timing resolution behavior of a given timing pick-off method regardless of the source location change. Lastly, the performance comparison for several digital timing methods is also shown.

Reaction kinetics of resveratrol with tert-butoxyl radicals

NASA Astrophysics Data System (ADS)

Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

2012-09-01

The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

Kinetic Analysis for the Multistep Profiles of Organic Reactions: Significance of the Conformational Entropy on the Rate Constants of the Claisen Rearrangement.

PubMed

Sumiya, Yosuke; Nagahata, Yutaka; Komatsuzaki, Tamiki; Taketsugu, Tetsuya; Maeda, Satoshi

2015-12-03

The significance of kinetic analysis as a tool for understanding the reactivity and selectivity of organic reactions has recently been recognized. However, conventional simulation approaches that solve rate equations numerically are not amenable to multistep reaction profiles consisting of fast and slow elementary steps. Herein, we present an efficient and robust approach for evaluating the overall rate constants of multistep reactions via the recursive contraction of the rate equations to give the overall rate constants for the products and byproducts. This new method was applied to the Claisen rearrangement of allyl vinyl ether, as well as a substituted allyl vinyl ether. Notably, the profiles of these reactions contained 23 and 84 local minima, and 66 and 278 transition states, respectively. The overall rate constant for the Claisen rearrangement of allyl vinyl ether was consistent with the experimental value. The selectivity of the Claisen rearrangement reaction has also been assessed using a substituted allyl vinyl ether. The results of this study showed that the conformational entropy in these flexible chain molecules had a substantial impact on the overall rate constants. This new method could therefore be used to estimate the overall rate constants of various other organic reactions involving flexible molecules.

Determination of human albumin in serum and urine samples by constant-energy synchronous fluorescence method.

PubMed

Madrakian, Tayyebeh; Bagheri, Habibollah; Afkhami, Abbas

2015-08-01

A sensitive spectrofluorimetric method using constant-energy synchronous fluorescence technique is proposed for the determination of human albumin without separation. In this method, no reagent was used for enhancement of the fluorescence signal of albumin in the solution. Effects of some parameters, such as energy difference between excitation and emission monochromators (ΔE), emission and excitation slit widths and scan rate of wavelength were studied and the optimum conditions were established. For this purpose factorial design and response surface method were employed for optimization of the effective parameters on the fluorescence signal. The results showed that the scan rate of the wavelength has no significant effect on the analytical signal. The calibration curve was linear in the range 0.1-220.0 µg mL(-1) of albumin with a detection limit of 7.0 × 10(-3)  µg mL(-1). The relative standard deviations (RSD) for six replicate measurements of albumin were calculated as 2.2%, 1.7% and 1.3% for 0.5, 10.0 and 100.0 µg mL(-1) albumin, respectively. Furthermore the proposed method has been employed for the determination of albumin in human serum and urine samples. Copyright © 2014 John Wiley & Sons, Ltd.

Temporal Gillespie Algorithm: Fast Simulation of Contagion Processes on Time-Varying Networks

PubMed Central

Vestergaard, Christian L.; Génois, Mathieu

2015-01-01

Stochastic simulations are one of the cornerstones of the analysis of dynamical processes on complex networks, and are often the only accessible way to explore their behavior. The development of fast algorithms is paramount to allow large-scale simulations. The Gillespie algorithm can be used for fast simulation of stochastic processes, and variants of it have been applied to simulate dynamical processes on static networks. However, its adaptation to temporal networks remains non-trivial. We here present a temporal Gillespie algorithm that solves this problem. Our method is applicable to general Poisson (constant-rate) processes on temporal networks, stochastically exact, and up to multiple orders of magnitude faster than traditional simulation schemes based on rejection sampling. We also show how it can be extended to simulate non-Markovian processes. The algorithm is easily applicable in practice, and as an illustration we detail how to simulate both Poissonian and non-Markovian models of epidemic spreading. Namely, we provide pseudocode and its implementation in C++ for simulating the paradigmatic Susceptible-Infected-Susceptible and Susceptible-Infected-Recovered models and a Susceptible-Infected-Recovered model with non-constant recovery rates. For empirical networks, the temporal Gillespie algorithm is here typically from 10 to 100 times faster than rejection sampling. PMID:26517860

Temporal Gillespie Algorithm: Fast Simulation of Contagion Processes on Time-Varying Networks.

PubMed

Vestergaard, Christian L; Génois, Mathieu

2015-10-01

Stochastic simulations are one of the cornerstones of the analysis of dynamical processes on complex networks, and are often the only accessible way to explore their behavior. The development of fast algorithms is paramount to allow large-scale simulations. The Gillespie algorithm can be used for fast simulation of stochastic processes, and variants of it have been applied to simulate dynamical processes on static networks. However, its adaptation to temporal networks remains non-trivial. We here present a temporal Gillespie algorithm that solves this problem. Our method is applicable to general Poisson (constant-rate) processes on temporal networks, stochastically exact, and up to multiple orders of magnitude faster than traditional simulation schemes based on rejection sampling. We also show how it can be extended to simulate non-Markovian processes. The algorithm is easily applicable in practice, and as an illustration we detail how to simulate both Poissonian and non-Markovian models of epidemic spreading. Namely, we provide pseudocode and its implementation in C++ for simulating the paradigmatic Susceptible-Infected-Susceptible and Susceptible-Infected-Recovered models and a Susceptible-Infected-Recovered model with non-constant recovery rates. For empirical networks, the temporal Gillespie algorithm is here typically from 10 to 100 times faster than rejection sampling.

A first-passage scheme for determination of overall rate constants for non-diffusion-limited suspensions

NASA Astrophysics Data System (ADS)

Lu, Shih-Yuan; Yen, Yi-Ming

2002-02-01

A first-passage scheme is devised to determine the overall rate constant of suspensions under the non-diffusion-limited condition. The original first-passage scheme developed for diffusion-limited processes is modified to account for the finite incorporation rate at the inclusion surface by using a concept of the nonzero survival probability of the diffusing entity at entity-inclusion encounters. This nonzero survival probability is obtained from solving a relevant boundary value problem. The new first-passage scheme is validated by an excellent agreement between overall rate constant results from the present development and from an accurate boundary collocation calculation for the three common spherical arrays [J. Chem. Phys. 109, 4985 (1998)], namely simple cubic, body-centered cubic, and face-centered cubic arrays, for a wide range of P and f. Here, P is a dimensionless quantity characterizing the relative rate of diffusion versus surface incorporation, and f is the volume fraction of the inclusion. The scheme is further applied to random spherical suspensions and to investigate the effect of inclusion coagulation on overall rate constants. It is found that randomness in inclusion arrangement tends to lower the overall rate constant for f up to the near close-packing value of the regular arrays because of the inclusion screening effect. This screening effect turns stronger for regular arrays when f is near and above the close-packing value of the regular arrays, and consequently the overall rate constant of the random array exceeds that of the regular array. Inclusion coagulation too induces the inclusion screening effect, and leads to lower overall rate constants.

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

NASA Astrophysics Data System (ADS)

McKelvie, Jennifer R.; Mackay, Douglas M.; de Sieyes, Nicholas R.; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2007-12-01

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The δ 13C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of - 31.3 ± 0.5‰ ( n = 40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in 13C of MTBE by 40.6‰, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 μg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of δ 13C for TBA in groundwater samples in the "With ethanol lane" was - 26.0 ± 1.0‰ ( n = 32). Uniform δ 13C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of - 9.2‰ to - 15.6‰, and values of δ 13C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year - 1 ( n = 18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year - 1 calculated using contaminant mass-discharge for the "With ethanol lane".

Dissolution kinetics of volatile organic compound vapors in water: An integrated experimental and computational study

NASA Astrophysics Data System (ADS)

Mahmoodlu, Mojtaba G.; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Majid Hassanizadeh, S.; van Genuchten, Martinus Th.

2017-01-01

In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass cylinder filled with pure volatile organic compound (VOC). Results showed that air phase concentrations of both TCE and toluene increased relatively quickly to their maximum values and then became constant. We considered subsequent dissolution into both stirred and unstirred water reservoirs. Results of the stirred experiments showed a quick increase in the VOC concentrations with time up to their solubility limit in water. VOC vapor dissolution was found to be independent of pH. In contrast, salinity had a significant effect on the solubility of TCE and toluene vapors. VOC evaporation and vapor dissolution in the stirred water reservoirs followed first-order rate processes. Observed data could be described well using both simplified analytical solutions, which decoupled the VOC dynamics in the air and water phases, as well as using more complete coupled solutions. However, the estimated evaporation (ke) and dissolution (kd) rate constants differed by up to 70% between the coupled and uncoupled formulations. We also numerically investigated the effects of fluid withdrawal from the small water reservoir due to sampling. While decoupling the VOC air and water phase mass transfer processes produced unreliable estimates of kd, the effects of fluid withdrawal on the estimated rate constants were found to be less important. The unstirred experiments showed a much slower increase in the dissolved VOC concentrations versus time. Molecular diffusion of the VOCs within the aqueous phase became then the limiting factor for mass transfer from air to water. Fluid withdrawal during sampling likely caused some minor convection within the reservoir, which was simulated by increasing the apparent liquid diffusion coefficient.

Population pharmacokinetics of olmesartan following oral administration of its prodrug, olmesartan medoxomil: in healthy volunteers and hypertensive patients.

PubMed

Yoshihara, Kazutaka; Gao, Yuying; Shiga, Hiroshi; Wada, D Russell; Hisaoka, Masafumi

2005-01-01

Olmesartan medoxomil (CS-866) is a new orally active angiotensin II receptor antagonist that is highly selective for the AT1 receptor subtype. To develop a population pharmacokinetic model for olmesartan (RNH-6270), the active metabolite of olmesartan medoxomil, in healthy volunteers and hypertensive patients, and to evaluate effects of covariates on the apparent oral clearance (CL/F), with particular emphasis on the effect of race. Retrospective analysis of data from 12 phase I-III trials in the US, Europe and Japan. Eighty-nine healthy volunteers and 383 hypertensive patients. Nonlinear mixed-effects modelling was used to evaluate 7911 olmesartan plasma sample concentrations. The covariates included age, bodyweight, sex, race (Westerners [including Caucasians and Hispanics] versus Japanese), patient status (hypertensive patients versus healthy volunteers), serum creatinine level as an index of renal function and serum chemistry data as indices of hepatic function. The pharmacokinetic data of olmesartan were well described by a two-compartment linear model with first-order absorption and an absorption lag-time, parameterised in terms of CL/F (6.66 L/h for a typical male Western hypertensive patient), absorption rate constant (1.46h-1), elimination rate constant (0.193h-1), rate constant from the central to peripheral compartment (0.061h-1), rate constant from the peripheral to central compartment (0.079h-1) and absorption lag-time (0.427h). Analysis of covariates showed that age, bodyweight, sex, patient status and renal function were factors influencing the clearance of olmesartan. The population pharmacokinetic analysis of olmesartan showed that: (i) severe renal impairment (serum creatinine >265 micromol/L [approximately 3 mg/dL]) could cause a clearance decrease of > or =30%; (ii) older age, lower bodyweight and being female were determinants of lower clearance but their effects on olmesartan clearance were within 20%; (iii) no statistically significant difference in clearance was found between Westerners and Japanese.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

PubMed

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

A new analytical method for estimating lumped parameter constants of linear viscoelastic models from strain rate tests

NASA Astrophysics Data System (ADS)

Mattei, G.; Ahluwalia, A.

2018-04-01

We introduce a new function, the apparent elastic modulus strain-rate spectrum, E_{app} ( \\dot{ɛ} ), for the derivation of lumped parameter constants for Generalized Maxwell (GM) linear viscoelastic models from stress-strain data obtained at various compressive strain rates ( \\dot{ɛ}). The E_{app} ( \\dot{ɛ} ) function was derived using the tangent modulus function obtained from the GM model stress-strain response to a constant \\dot{ɛ} input. Material viscoelastic parameters can be rapidly derived by fitting experimental E_{app} data obtained at different strain rates to the E_{app} ( \\dot{ɛ} ) function. This single-curve fitting returns similar viscoelastic constants as the original epsilon dot method based on a multi-curve global fitting procedure with shared parameters. Its low computational cost permits quick and robust identification of viscoelastic constants even when a large number of strain rates or replicates per strain rate are considered. This method is particularly suited for the analysis of bulk compression and nano-indentation data of soft (bio)materials.

Equilibration kinetics in isolated and membrane-bound photosynthetic reaction centers upon illumination: a method to determine the photoexcitation rate.

PubMed

Manzo, Anthony J; Goushcha, Alexander O; Barabash, Yuri M; Kharkyanen, Valery N; Scott, Gary W

2009-07-01

Kinetics of electron transfer, following variation of actinic light intensity, for photosynthetic reaction centers (RCs) of purple bacteria (isolated and membrane-bound) were analyzed by measuring absorbance changes in the primary photoelectron donor absorption band at 865 nm. The bleaching of the primary photoelectron donor absorption band in RCs, following a sudden increase of illumination from the dark to an actinic light intensity of I(exp), obeys a simple exponential law with the rate constant alphaI(exp) + k(rec), in which alpha is a parameter relating the light intensity, measured in mW/cm(2), to a corresponding theoretical rate in units of reciprocal seconds, and k(rec) is the effective rate constant of the charge recombination in the photosynthetic RCs. In this work, a method for determining the alpha parameter value is developed and experimentally verified for isolated and membrane-bound RCs, allowing for rigorous modeling of RC macromolecule dynamics under varied photoexcitation conditions. Such modeling is necessary for RCs due to alterations of the forward photoexcitation rates and relaxation rates caused by illumination history and intramolecular structural dynamics effects. It is demonstrated that the classical Bouguer-Lambert-Beer formalism can be applied for the samples with relatively low scattering, which is not necessarily the case with strongly scattering media or high light intensity excitation.

Fractionating power and outlet stream polydispersity in asymmetrical flow field-flow fractionation. Part II: programmed operation.

PubMed

Williams, P Stephen

2017-01-01

Asymmetrical flow field-flow fractionation (As-FlFFF) is a widely used technique for analyzing polydisperse nanoparticle and macromolecular samples. The programmed decay of cross flow rate is often employed. The interdependence of the cross flow rate through the membrane and the fluid flow along the channel length complicates the prediction of elution time and fractionating power. The theory for their calculation is presented. It is also confirmed for examples of exponential decay of cross flow rate with constant channel outlet flow rate that the residual sample polydispersity at the channel outlet is quite well approximated by the reciprocal of four times the fractionating power. Residual polydispersity is of importance when online MALS or DLS detection are used to extract quantitative information on particle size or molecular weight. The theory presented here provides a firm basis for the optimization of programmed flow conditions in As-FlFFF. Graphical abstract Channel outlet polydispersity remains significant following fractionation by As-FlFFF under conditions of programmed decay of cross flow rate.

Kinetics of phloretin binding to phosphatidylcholine vesicle membranes

PubMed Central

1980-01-01

The submillisecond kinetics for phloretin binding to unilamellar phosphatidylcholine (PC) vesicles was investigated using the temperature-jump technique. Spectrophotometric studies of the equilibrium binding performed at 328 nm demonstrated that phloretin binds to a single set of independent, equivalent sites on the vesicle with a dissociation constant of 8.0 microM and a lipid/site ratio of 4.0. The temperature of the phloretin-vesicle solution was jumped by 4 degrees C within 4 microseconds producing a monoexponential, concentration-dependent relaxation process with time constants in the 30--200-microseconds time range. An analysis of the concentration dependence of relaxation time constants at pH 7.30 and 24 degrees C yielded a binding rate constant of 2.7 X 10(8) M-1 s-1 and an unbinding constant of 2,900 s-1; approximately 66 percent of total binding sites are exposed at the outer vesicle surface. The value of the binding rate constant and three additional observations suggest that the binding kinetics are diffusion limited. The phloretin analogue, naringenin, which has a diffusion coefficient similar to phloretin yet a dissociation constant equal to 24 microM, bound to PC vesicle with the same rate constant as phloretin did. In addition, the phloretin-PC system was studied in buffers made one to six times more viscous than water by addition of sucrose or glycerol to the differ. The equilibrium affinity for phloretin binding to PC vesicles is independent of viscosity, yet the binding rate constant decreases with the expected dependence (kappa binding alpha 1/viscosity) for diffusion-limited processes. Thus, the binding rate constant is not altered by differences in binding affinity, yet depends upon the diffusion coefficient in buffer. Finally, studies of the pH dependence of the binding rate constant showed a dependence (kappa binding alpha [1 + 10pH-pK]) consistent with the diffusion-limited binding of a weak acid. PMID:7391812

Application of a whole-body pharmacokinetic model for targeted radionuclide therapy to NM404 and FLT

NASA Astrophysics Data System (ADS)

Grudzinski, Joseph J.; Floberg, John M.; Mudd, Sarah R.; Jeffery, Justin J.; Peterson, Eric T.; Nomura, Alice; Burnette, Ronald R.; Tomé, Wolfgang A.; Weichert, Jamey P.; Jeraj, Robert

2012-03-01

We have previously developed a model that provides relative dosimetry estimates for targeted radionuclide therapy (TRT) agents. The whole-body and tumor pharmacokinetic (PK) parameters of this model can be noninvasively measured with molecular imaging, providing a means of comparing potential TRT agents. Parameter sensitivities and noise will affect the accuracy and precision of the estimated PK values and hence dosimetry estimates. The aim of this work is to apply a PK model for TRT to two agents with different magnitudes of clearance rates, NM404 and FLT, explore parameter sensitivity with respect to time and investigate the effect of noise on parameter precision and accuracy. Twenty-three tumor bearing mice were injected with a ‘slow-clearing’ agent, 124I-NM404 (n = 10), or a ‘fast-clearing’ agent, 18F-FLT (3‧-deoxy-3‧-fluorothymidine) (n = 13) and imaged via micro-PET/CT pseudo-dynamically or dynamically, respectively. Regions of interest were drawn within the heart and tumor to create time-concentration curves for blood pool and tumor. PK analysis was performed to estimate the mean and standard error of the central compartment efflux-to-influx ratio (k12/k21), central elimination rate constant (kel), and tumor influx-to-efflux ratio (k34/k43), as well as the mean and standard deviation of the dosimetry estimates. NM404 and FLT parameter estimation results were used to analyze model accuracy and parameter sensitivity. The accuracy of the experimental sampling schedule was compared to that of an optimal sampling schedule found using Cramer-Rao lower bounds theory. Accuracy was assessed using correlation coefficient, bias and standard error of the estimate normalized to the mean (SEE/mean). The PK parameter estimation of NM404 yielded a central clearance, kel (0.009 ± 0.003 h-1), normal body retention, k12/k21 (0.69 ± 0.16), tumor retention, k34/k43 (1.44 ± 0.46) and predicted dosimetry, Dtumor (3.47 ± 1.24 Gy). The PK parameter estimation of FLT yielded a central elimination rate constant, kel (0.050 ± 0.025 min-1), normal body retention, k12/k21 (2.21 ± 0.62) and tumor retention, k34/k43 (0.65 ± 0.17), and predicted dosimetry, Dtumor (0.61 ± 0.20 Gy). Compared to experimental sampling, optimal sampling decreases the dosimetry bias and SEE/mean for NM404; however, it increases bias and decreases SEE/mean for FLT. For both NM404 and FLT, central compartment efflux rate constant, k12, and central compartment influx rate constant, k21, possess mirroring sensitivities at relatively early time points. The instantaneous concentration in the blood, C0, was most sensitive at early time points; central elimination, kel, and tumor efflux, k43, are most sensitive at later time points. A PK model for TRT was applied to both a slow-clearing, NM404, and a fast-clearing, FLT, agents in a xenograft murine model. NM404 possesses more favorable PK values according to the PK TRT model. The precise and accurate measurement of k12, k21, kel, k34 and k43 will translate into improved and precise dosimetry estimations. This work will guide the future use of this PK model for assessing the relative effectiveness of potential TRT agents.

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

NASA Technical Reports Server (NTRS)

Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

1984-01-01

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Determination of Bimolecular Rate Constants for Reactions of Hydroxyl Radical with Pharmaceutical and Cosmetics Chemicals - Implications to the Fate in the Aquatic Environment

NASA Astrophysics Data System (ADS)

Nakajima, H.; Arakaki, T.; Anastasio, C.

2008-12-01

Large organic compounds such as hyaluronic acid and chondroitin sulfate are often used in pharmaceutical and cosmetics products, but their chemical degradation pathways are not well understood. To better elucidate their fate in the aquatic environment, we initiated a study to determine bimolecular rate constants between these organic compounds and hydroxyl radical (OH), which is a potent oxidant in the environment. The lifetimes of many organic compounds are determined by reactions with OH radicals, and the lifetime of OH is often controlled by reactions with organic compounds. To determine these bimolecular rate constants we used a competition kinetics technique with either hydrogen peroxide or nitrate as a source of OH and benzoate as the competing sink. Since the molecular weights of some of the large organic compounds we studied were not known, we used dissolved organic carbon (DOC) concentrations to determine mole-carbon based bimolecular rate constants, instead of the commonly used molar-based bimolecular rate constants. We will report the mole-carbon based bimolecular rate constants of OH, determined at room temperature, with hyaluronic acid, chondroitin sulfate and some other large organic compounds.

Effective optical constants of anisotropic materials

NASA Technical Reports Server (NTRS)

Aronson, J. R.; Emslie, A. G.

1980-01-01

The applicability of a technique for determining the optical constants of soil or aerosol components on the basis of measurements of the reflectance or transmittance of inhomogeneous samples of component material is investigated. Optical constants for a sample of very pure quartzite were obtained by a specular reflection technique and line parameters were calculated by classical dispersion theory. Predictions of the reflectance of powdered quartz were then derived from optical constants measured for the anisotropic quartz and for pure quartz crystals, and compared with experimental measurements. The calculated spectra are found to resemble each other moderately well in shape, however the reflectance level calculated from the psuedo-optical constants (quartzite) is consistently below that calculated from quartz values. The spectrum calculated from the quartz optical constants is also shown to represent the experimental nonrestrahlen features more accurately. It is thus concluded that although optical constants derived from inhomogeneous materials may represent the spectral features of a powdered sample qualitatively a quantitative fit to observed data is not likely.

The uncertainty of biodegradation rate constants of emerging organic compounds in soil and groundwater - A compilation of literature values for 82 substances.

PubMed

Greskowiak, Janek; Hamann, Enrico; Burke, Victoria; Massmann, Gudrun

2017-12-01

The present study reports on biodegradation rate constants of emerging organic compounds (EOCs) in soil and groundwater available in the literature. The major aim of this compilation was to provide an assessment of the uncertainty of hydrological models with respect to the fate of EOCs. The literature search identified a total number of 82 EOCs for which 1st-order rate constants could be derived. It was found that for the majority of compounds degradation rate constants vary over more than three orders of magnitude. Correlation to factors that are well known to affect the degradation rate, such as temperature or redox condition was weak. No correlation at all was found with results from available quantitative structure-activity relationship models. This suggests that many unknown site specific or experimentally specific factors influence the degradation behavior of EOCs in the environment. Thus, local and catchment scale predictive models to estimate EOC concentration at receptors, e.g., receiving waters or drinking water wells, need to consider the large uncertainty in 1st-order rate constants. As a consequence, applying rate constants that were derived from one experiment or field site investigation to other experiments or field sites should be done with extreme caution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of rate of drug release from oil vehicle using a rotating dialysis cell.

PubMed

Larsen, D H; Fredholt, K; Larsen, C

2000-09-01

The rate constants for transfer of model compounds (naproxen and lidocaine) from oily vehicle (Viscoleo) to aqueous buffer phases were determined by use of the rotating dialysis cell. Release studies were done for the partly ionized compounds at several pH values. A correlation between the overall first-order rate constant related to attainment of equilibrium, k(obs), and the pH-dependent distribution coefficient, D, determined between oil vehicle and aqueous buffer was established according to the equation: logk(obs)=-0.71 logD-0.22 (k(obs) in h(-1)). Based on this correlation it was suggested that the rate constant of a weak electrolyte at a specified D value could be considered equal to the k(obs) value for a non-electrolyte possessing a partition coefficient, P(app), the magnitude of which was equal to D. Specific rate constants k(ow) and k(wo) were calculated from the overall rate constant and the pH-dependent distribution coefficient. The rate constant representing the transport from oily vehicle to aqueous phase, k(ow), was found to be significantly influenced by the magnitude of the partition coefficient P(app) according to: logk(ow)=-0.71 logP(app)-log(P(app)+1)-0.22 (k(ow) in h(-1)).

Development of the permeability/performance reference compound approach for in situ calibration of semipermeable membrane devices

USGS Publications Warehouse

Huckins, J.N.; Petty, J.D.; Lebo, J.A.; Almeida, F.V.; Booij, K.; Alvarez, D.A.; Cranor, W.L.; Clark, R.C.; Mogensen, B.B.

2002-01-01

Permeability/performance reference compounds (PRCs) are analytically noninterfering organic compounds with moderate to high fugacity from semipermeable membrane devices (SPMDs) that are added to the lipid prior to membrane enclosure. Assuming that isotropic exchange kinetics (IEK) apply and that SPMD-water partition coefficients are known, measurement of PRC dissipation rate constants during SPMD field exposures and laboratory calibration studies permits the calculation of an exposure adjustment factor (EAF). In theory, PRC-derived EAF ratios reflect changes in SPMD sampling rates (relative to laboratory data) due to differences in exposure temperature, membrane biofouling, and flow velocity-turbulence at the membrane surface. Thus, the PRC approach should allow for more accurate estimates of target solute/vapor concentrations in an exposure medium. Under some exposure conditions, the impact of environmental variables on SPMD sampling rates may approach an order of magnitude. The results of this study suggest that most of the effects of temperature, facial velocity-turbulence, and biofouling on the uptake rates of analytes with a wide range of hydrophobicities can be deduced from PRCs with a much narrower range of hydrophobicities. Finally, our findings indicate that the use of PRCs permits prediction of in situ SPMD sampling rates within 2-fold of directly measured values.

Application of the compensated arrhenius formalism to dielectric relaxation.

PubMed

Petrowsky, Matt; Frech, Roger

2009-12-17

The temperature dependence of the dielectric rate constant, defined as the reciprocal of the dielectric relaxation time, is examined for several groups of organic solvents. Early studies of linear alcohols using a simple Arrhenius equation found that the activation energy was dependent on the chain length of the alcohol. This paper re-examines the earlier data using a compensated Arrhenius formalism that assumes the presence of a temperature-dependent static dielectric constant in the exponential prefactor. Scaling temperature-dependent rate constants to isothermal rate constants so that the dielectric constant dependence is removed results in calculated energies of activation E(a) in which there is a small increase with chain length. These energies of activation are very similar to those calculated from ionic conductivity data using compensated Arrhenius formalism. This treatment is then extended to dielectic relaxation data for n-alkyl bromides, n-nitriles, and n-acetates. The exponential prefactor is determined by dividing the temperature-dependent rate constants by the Boltzmann term exp(-E(a)/RT). Plotting the prefactors versus the static dielectric constant places the data on a single master curve for each group of solvents.

Inflation with a constant rate of roll

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

Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi, E-mail: motohashi@kicp.uchicago.edu, E-mail: alstar@landau.ac.ru, E-mail: yokoyama@resceu.s.u-tokyo.ac.jp

2015-09-01

We consider an inflationary scenario where the rate of inflaton roll defined by {sup ··}φ/H φ-dot remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs formore » unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.« less

Multi-target QSPR modeling for simultaneous prediction of multiple gas-phase kinetic rate constants of diverse chemicals

NASA Astrophysics Data System (ADS)

Basant, Nikita; Gupta, Shikha

2018-03-01

The reactions of molecular ozone (O3), hydroxyl (•OH) and nitrate (NO3) radicals are among the major pathways of removal of volatile organic compounds (VOCs) in the atmospheric environment. The gas-phase kinetic rate constants (kO3, kOH, kNO3) are thus, important in assessing the ultimate fate and exposure risk of atmospheric VOCs. Experimental data for rate constants are not available for many emerging VOCs and the computational methods reported so far address a single target modeling only. In this study, we have developed a multi-target (mt) QSPR model for simultaneous prediction of multiple kinetic rate constants (kO3, kOH, kNO3) of diverse organic chemicals considering an experimental data set of VOCs for which values of all the three rate constants are available. The mt-QSPR model identified and used five descriptors related to the molecular size, degree of saturation and electron density in a molecule, which were mechanistically interpretable. These descriptors successfully predicted three rate constants simultaneously. The model yielded high correlations (R2 = 0.874-0.924) between the experimental and simultaneously predicted endpoint rate constant (kO3, kOH, kNO3) values in test arrays for all the three systems. The model also passed all the stringent statistical validation tests for external predictivity. The proposed multi-target QSPR model can be successfully used for predicting reactivity of new VOCs simultaneously for their exposure risk assessment.

Rationalizing 5000-Fold Differences in Receptor-Binding Rate Constants of Four Cytokines

PubMed Central

Pang, Xiaodong; Qin, Sanbo; Zhou, Huan-Xiang

2011-01-01

The four cytokines erythropoietin (EPO), interleukin-4 (IL4), human growth hormone (hGH), and prolactin (PRL) all form four-helix bundles and bind to type I cytokine receptors. However, their receptor-binding rate constants span a 5000-fold range. Here, we quantitatively rationalize these vast differences in rate constants by our transient-complex theory for protein-protein association. In the transient complex, the two proteins have near-native separation and relative orientation, but have yet to form the short-range specific interactions of the native complex. The theory predicts the association rate constant as ka=ka0exp(−ΔGel∗/kBT) where ka0 is the basal rate constant for reaching the transient complex by random diffusion, and the Boltzmann factor captures the rate enhancement due to electrostatic attraction. We found that the vast differences in receptor-binding rate constants of the four cytokines arise mostly from the differences in charge complementarity among the four cytokine-receptor complexes. The basal rate constants (ka0) of EPO, IL4, hGH, and PRL were similar (5.2 × 105 M−1s−1, 2.4 × 105 M−1s−1, 1.7 × 105 M−1s−1, and 1.7 × 105 M−1s−1, respectively). However, the average electrostatic free energies (ΔGe1∗) were very different (−4.2 kcal/mol, −2.4 kcal/mol, −0.1 kcal/mol, and −0.5 kcal/mol, respectively, at ionic strength = 160 mM). The receptor-binding rate constants predicted without adjusting any parameters, 6.2 × 108 M−1s−1, 1.3 × 107 M−1s−1, 2.0 × 105 M−1s−1, and 7.6 × 104 M−1s−1, respectively, for EPO, IL4, hGH, and PRL agree well with experimental results. We uncover that these diverse rate constants are anticorrelated with the circulation concentrations of the cytokines, with the resulting cytokine-receptor binding rates very close to the limits set by the half-lives of the receptors, suggesting that these binding rates are functionally relevant and perhaps evolutionarily tuned. Our calculations also reproduced well-observed effects of mutations and ionic strength on the rate constants and produced a set of mutations on the complex of hGH with its receptor that putatively enhances the rate constant by nearly 100-fold through increasing charge complementarity. To quantify charge complementarity, we propose a simple index based on the charge distribution within the binding interface, which shows good correlation with ΔGe1∗. Together these results suggest that protein charges can be manipulated to tune ka and control biological function. PMID:21889455

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.

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.

Theoretical rate constants of super-exchange hole transfer and thermally induced hopping in DNA.

PubMed

Shimazaki, Tomomi; Asai, Yoshihiro; Yamashita, Koichi

2005-01-27

Recently, the electronic properties of DNA have been extensively studied, because its conductivity is important not only to the study of fundamental biological problems, but also in the development of molecular-sized electronics and biosensors. We have studied theoretically the reorganization energies, the activation energies, the electronic coupling matrix elements, and the rate constants of hole transfer in B-form double-helix DNA in water. To accommodate the effects of DNA nuclear motions, a subset of reaction coordinates for hole transfer was extracted from classical molecular dynamics (MD) trajectories of DNA in water and then used for ab initio quantum chemical calculations of electron coupling constants based on the generalized Mulliken-Hush model. A molecular mechanics (MM) method was used to determine the nuclear Franck-Condon factor. The rate constants for two types of mechanisms of hole transfer-the thermally induced hopping (TIH) and the super-exchange mechanisms-were determined based on Marcus theory. We found that the calculated matrix elements are strongly dependent on the conformations of the nucleobase pairs of hole-transferable DNA and extend over a wide range of values for the "rise" base-step parameter but cluster around a particular value for the "twist" parameter. The calculated activation energies are in good agreement with experimental results. Whereas the rate constant for the TIH mechanism is not dependent on the number of A-T nucleobase pairs that act as a bridge, the rate constant for the super-exchange process rapidly decreases when the length of the bridge increases. These characteristic trends in the calculated rate constants effectively reproduce those in the experimental data of Giese et al. [Nature 2001, 412, 318]. The calculated rate constants were also compared with the experimental results of Lewis et al. [Nature 2000, 406, 51].

F-centers mechanism of long-term relaxation in lead zirconate-titanate based piezoelectric ceramics. 2. After-field relaxation

NASA Astrophysics Data System (ADS)

Ishchuk, V. M.; Kuzenko, D. V.

2016-08-01

The paper presents results of experimental study of the dielectric constant relaxation during aging process in Pb(Zr,Ti)O3 based solid solutions (PZT) after action of external DC electric field. The said process is a long-term one and is described by the logarithmic function of time. Reversible and nonreversible relaxation process takes place depending on the field intensity. The relaxation rate depends on the field strength also, and the said dependence has nonlinear and nonmonotonic form, if external field leads to domain disordering. The oxygen vacancies-based model for description of the long-term relaxation processes is suggested. The model takes into account the oxygen vacancies on the sample's surface ends, their conversion into F+- and F0-centers under external effects and subsequent relaxation of these centers into the simple oxygen vacancies after the action termination. F-centers formation leads to the violation of the original sample's electroneutrality, and generate intrinsic DC electric field into the sample. Relaxation of F-centers is accompanied by the reduction of the electric field, induced by them, and relaxation of the dielectric constant, as consequent effect.

Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

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

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

2014-01-01

A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertaintiesmore » with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.« less

[Key physical parameters of hawthorn leaf granules by stepwise regression analysis method].

PubMed

Jiang, Qie-Ying; Zeng, Rong-Gui; Li, Zhe; Luo, Juan; Zhao, Guo-Wei; Lv, Dan; Liao, Zheng-Gen

2017-05-01

The purpose of this study was to investigate the effect of key physical properties of hawthorn leaf granule on its dissolution behavior. Hawthorn leaves extract was utilized as a model drug. The extract was mixed with microcrystalline cellulose or starch with the same ratio by using different methods. Appropriate amount of lubricant and disintegrating agent was added into part of the mixed powder, and then the granules were prepared by using extrusion granulation and high shear granulation. The granules dissolution behavior was evaluated by using equilibrium dissolution quantity and dissolution rate constant of the hypericin as the indicators. Then the effect of physical properties on dissolution behavior was analyzed through the stepwise regression analysis method. The equilibrium dissolution quantity of hypericin and adsorption heat constant in hawthorn leaves were positively correlated with the monolayer adsorption capacity and negatively correlated with the moisture absorption rate constant. The dissolution rate constants were decreased with the increase of Hausner rate, monolayer adsorption capacity and adsorption heat constant, and were increased with the increase of Carr index and specific surface area. Adsorption heat constant, monolayer adsorption capacity, moisture absorption rate constant, Carr index and specific surface area were the key physical properties of hawthorn leaf granule to affect its dissolution behavior. Copyright© by the Chinese Pharmaceutical Association.

Estimation of a Constant False Alarm Rate Processing Loss for a High-Resolution Maritime Radar System

DTIC Science & Technology

2008-08-01

a sample with clutter of mean level y0 and noise of variance σ 2, with a threshold CACA zt β= . Using the results presented in [15, 16, 23], it can...level y0 and noise of variance σ 2, with a threshold CACA zt β= . Using (3.107) and (3.98), the expression for the expected Pd of a Swerling 2 target can

Studies of CO oxidation on Pt/SnO2 catalyst in a surrogate CO2 laser facility

NASA Technical Reports Server (NTRS)

Batten, Carmen E.; Miller, Irvin M.; Paulin, Patricia A.; Schryer, Jacqueline

1987-01-01

Samples of 1% Pt/SnO2 catalyst were exposed to a stoichiometric gas mixture of 1% CO and 1.2% O2 in helium over a range of flowrates from 5 to 15 sccm and temperatures from 338 to 394 Kelvin. Reaction rate constants for the catalytic oxidation of carbon monoxide and their temperature dependence were determined and compared with previous literature values.

Effect of dairy farming system, herd, season, parity, and days in milk on modeling of the coagulation, curd firming, and syneresis of bovine milk.

PubMed

Bittante, G; Cipolat-Gotet, C; Malchiodi, F; Sturaro, E; Tagliapietra, F; Schiavon, S; Cecchinato, A

2015-04-01

The objectives of this study were to characterize the variation in curd firmness model parameters obtained from coagulating bovine milk samples, and to investigate the effects of the dairy system, season, individual farm, and factors related to individual cows (days in milk and parity). Individual milk samples (n = 1,264) were collected during the evening milking of 85 farms representing different environments and farming systems in the northeastern Italian Alps. The dairy herds were classified into 4 farming system categories: traditional system with tied animals (29 herds), modern dairy systems with traditional feeding based on hay and compound feed (30 herds), modern dairy system with total mixed ration (TMR) that included silage as a large proportion of the diet (9 herds), and modern dairy system with silage-free TMR (17 herds). Milk samples were analyzed for milk composition and coagulation properties, and parameters were modeled using curd firmness measures (CFt) collected every 15 s from a lacto-dynamographic analysis of 90 min. When compared with traditional milk coagulation properties (MCP), the curd firming measures showed greater variability and yielded a more accurate description of the milk coagulation process: the model converged for 93.1% of the milk samples, allowing estimation of 4 CFt parameters and 2 derived traits [maximum CF (CF(max)) and time from rennet addition to CF(max) (t(max))] for each sample. The milk samples whose CFt equations did not converge showed longer rennet coagulation times obtained from the model (RCT(eq)) and higher somatic cell score, and came from less-productive cows. Among the sources of variation tested for the CFt parameters, dairy herd system yielded the greatest differences for the contrast between the traditional farm and the 3 modern farms, with the latter showing earlier coagulation and greater instant syneresis rate constant (k(SR)). The use of TMR yielded a greater tmax because of a higher instant curd-firming rate constant (k(CF)). Season of sampling was found to be very important, yielding higher values during winter for all traits except k(CF) and k(SR). All CFt traits were affected by individual cow factors. For parity, milk produced by first-lactation cows showed higher k(CF) and k(SR), but delays in achieving CF(max). With respect to stage of lactation, RCT(eq) and potential asymptotic CF increased during the middle of lactation and stabilized thereafter, whereas the 2 instant rate constants presented the opposite pattern, with the lowest (k(CF)) and highest (k(SR)) values occurring in mid lactation. The new challenge offered by prolonging the test interval and individual modeling of milk technological properties allowed us to study the effects of parameters related to the environment and to individual cows. This novel strategy may be useful for investigating the genetic variability of these new coagulation traits. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Determination of equilibrium and rate constants for complex formation by fluorescence correlation spectroscopy supplemented by dynamic light scattering and Taylor dispersion analysis.

PubMed

Zhang, Xuzhu; Poniewierski, Andrzej; Jelińska, Aldona; Zagożdżon, Anna; Wisniewska, Agnieszka; Hou, Sen; Hołyst, Robert

2016-10-04

The equilibrium and rate constants of molecular complex formation are of great interest both in the field of chemistry and biology. Here, we use fluorescence correlation spectroscopy (FCS), supplemented by dynamic light scattering (DLS) and Taylor dispersion analysis (TDA), to study the complex formation in model systems of dye-micelle interactions. In our case, dyes rhodamine 110 and ATTO-488 interact with three differently charged surfactant micelles: octaethylene glycol monododecyl ether C 12 E 8 (neutral), cetyltrimethylammonium chloride CTAC (positive) and sodium dodecyl sulfate SDS (negative). To determine the rate constants for the dye-micelle complex formation we fit the experimental data obtained by FCS with a new form of the autocorrelation function, derived in the accompanying paper. Our results show that the association rate constants for the model systems are roughly two orders of magnitude smaller than those in the case of the diffusion-controlled limit. Because the complex stability is determined by the dissociation rate constant, a two-step reaction mechanism, including the diffusion-controlled and reaction-controlled rates, is used to explain the dye-micelle interaction. In the limit of fast reaction, we apply FCS to determine the equilibrium constant from the effective diffusion coefficient of the fluorescent components. Depending on the value of the equilibrium constant, we distinguish three types of interaction in the studied systems: weak, intermediate and strong. The values of the equilibrium constant obtained from the FCS and TDA experiments are very close to each other, which supports the theoretical model used to interpret the FCS data.

Rate constant for reaction of atomic hydrogen with germane

NASA Technical Reports Server (NTRS)

Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

1990-01-01

Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

A simple approach to power and sample size calculations in logistic regression and Cox regression models.

PubMed

Vaeth, Michael; Skovlund, Eva

2004-06-15

For a given regression problem it is possible to identify a suitably defined equivalent two-sample problem such that the power or sample size obtained for the two-sample problem also applies to the regression problem. For a standard linear regression model the equivalent two-sample problem is easily identified, but for generalized linear models and for Cox regression models the situation is more complicated. An approximately equivalent two-sample problem may, however, also be identified here. In particular, we show that for logistic regression and Cox regression models the equivalent two-sample problem is obtained by selecting two equally sized samples for which the parameters differ by a value equal to the slope times twice the standard deviation of the independent variable and further requiring that the overall expected number of events is unchanged. In a simulation study we examine the validity of this approach to power calculations in logistic regression and Cox regression models. Several different covariate distributions are considered for selected values of the overall response probability and a range of alternatives. For the Cox regression model we consider both constant and non-constant hazard rates. The results show that in general the approach is remarkably accurate even in relatively small samples. Some discrepancies are, however, found in small samples with few events and a highly skewed covariate distribution. Comparison with results based on alternative methods for logistic regression models with a single continuous covariate indicates that the proposed method is at least as good as its competitors. The method is easy to implement and therefore provides a simple way to extend the range of problems that can be covered by the usual formulas for power and sample size determination. Copyright 2004 John Wiley & Sons, Ltd.

Pumping tests of well Campbell et al. No. 2, Gila Hot Springs, Grant County, New Mexico

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

Schwab, G.E.; Summers, W.K.; Colpitts, R.M. Jr.

1982-03-01

Well Campbell et al. No. 2 near Gila Hot Springs in southwestern New Mexico (Section 5, Township 13 South, Range 13 West) was pumped for a five-step test and a 48-hour constant-rate test during October 1981. Measurements included depth to water in the pumping well and two observation wells, and discharge rates at the pumping well and two springs. The water level in the pumping well responded during both tests. However, water-level changes in the observation wells were too small for analytical use and discharge rates from the springs showed no change. Chemical analyses of water samples collected from twomore » springs and the pumping well show very similar water chemistries. Estimates of hydraulic properties show transmissivity from 12,000 to 14,000 gpd/ft and a storativity of 0.05. Combining these parameters with well data gives the first-year optimum discharge rate as 50 gpm with 20 feet of drawdown. Pumping this well at 50 gpm for forty years should produce only small water-level changes in wells a few hundred feet away. It would diminish the flow of the springs, and for planning purposes the combined discharge of the springs and well should be considered constant.« less

Protein A chromatography increases monoclonal antibody aggregation rate during subsequent low pH virus inactivation hold

PubMed Central

Mazzer, Alice R.; Perraud, Xavier; Halley, Jennifer; O’Hara, John; Bracewell, Daniel G.

2015-01-01

Protein A chromatography is a near-ubiquitous method of mAb capture in bioprocesses. The use of low pH buffer for elution from protein A is known to contribute to product aggregation. Yet, a more limited set of evidence suggests that low pH may not be the sole cause of aggregation in protein A chromatography, rather, other facets of the process may contribute significantly. This paper presents a well-defined method for investigating this problem. An IgG4 was incubated in elution buffer after protein A chromatography (typical of the viral inactivation hold) and the quantity of monomer in neutralised samples was determined by size exclusion chromatography; elution buffers of different pH values predetermined to induce aggregation of the IgG4 were used. Rate constants for monomer decay over time were determined by fitting exponential decay functions to the data. Similar experiments were implemented in the absence of a chromatography step, i.e. IgG4 aggregation at low pH. Rate constants for aggregation after protein A chromatography were considerably higher than those from low pH exposure alone; a distinct shift in aggregation rates was apparent across the pH range tested. PMID:26346187

Biokinetics of 13C in the human body after oral administration of 13C-labeled glucose as an index for the biokinetics of 14C.

PubMed

Masuda, Tsuyoshi; Tako, Yasuhiro; Matsushita, Kensaku; Takeda, Hiroshi; Endo, Masahiro; Nakamura, Yuji; Hisamatsu, Shun'ichi

2016-09-01

The retention of 13 C in the human body after oral administration of 13 C-labeled glucose was studied in three healthy volunteer subjects to estimate the 50 year cumulative body burden for 13 C as an index of the committed dose of the radioisotope 14 C. After administration of 13 C-labeled glucose, the volunteers ingested controlled diets with a fixed number of calories for 112 d. Samples of breath and urine were collected up to 112 d after administration. Samples of feces were collected up to 14 d after administration. Hair samples were obtained at 119 d after administration and analyzed as a representative index of the rate of excretion of organic 13 C via pathways such as skin cell exfoliation and mucus secretion. All samples were analyzed for 13 C/ 12 C atomic ratio to determine the rate of excretion via each pathway. We then constructed a metabolic model with a total of four pathways (breath, urine, feces, and other) comprising seven compartments. We determined the values of the biokinetic parameters in the model by using the obtained excretion data. From 74% to 94% of the 13 C administered was excreted in breath, whereas  <2% was excreted in urine and feces. In the other pathway, the excretion rate constant in the compartment with the longest residence time stretched to hundreds of days but the rate constant for each subject was not statistically significant (P value  >  0.1). In addition, the dataset for one of the three subjects was markedly different from those of the other two. When we estimated the 50 year cumulative body burden for 13 C by using our model and we included non-statistically significant parameters, a considerable cumulative body burden was found in the compartments excreting to the other pathway. Although our results on the cumulative body burden of 13 C from orally administered carbon as glucose were inconclusive, we found that the compartments excreting to the other pathway had a markedly long residence time and therefore should be studied further to clarify the fate of carbon in the human body. In addition to excreta, data for serum and blood cell samples were also collected from the subjects to examine the metabolism of 13 C in human body.

Comparison of steam gasification reactivity of algal and lignocellulosic biomass: influence of inorganic elements.

PubMed

Hognon, Céline; Dupont, Capucine; Grateau, Maguelone; Delrue, Florian

2014-07-01

This study aims at comparing the steam gasification behaviour of two species of algal biomass (Chlamydomonas reinhardtii and Arthrospira platensis) and three species of lignocellulosic biomass (miscanthus, beech and wheat straw). Isothermal experiments were carried out in a thermobalance under chemical regime. Samples had very different contents in inorganic elements, which resulted in different reactivities, with about a factor of 5 between samples. For biomasses with ratio between potassium content and phosphorus and silicon content K/(Si+P) higher than one, the reaction rate was constant during most of the reaction and then slightly increased at high conversion. On the contrary, for biomasses with ratio K/(Si+P) lower than one, the reaction rate decreased along conversion. A simple kinetic model was proposed to predict these behaviours. Copyright © 2014 Elsevier Ltd. All rights reserved.

Probable age of Autolycus and calibration of lunar stratigraphy

NASA Technical Reports Server (NTRS)

Ryder, G.; Bogard, D.; Garrison, D.

1991-01-01

Ar-39 - Ar-40 analyses of three petrographically distinct, shocked Apollo 15 KREEP (i.e., high K, rare earth element, P, and other trace element contents) basalt samples demonstrate that a major impact event affected all three samples at about 2.1 Ga. The Copernican System craters Aristillus and Autolycus are to the north. Autolycus, the older of the two, is in a particularly appropriate terrain and is the most likely source of the 2.1 Ga heating and delivery event. With this calibration point, and if Autolycus really is a Copernican crater, the Copernican System lasted twice as long as has previously been suggested. Furthermore, the moon was not subjected to a constant cratering rate over the past 3 billion years; the average rate in the preceding Eratosthenian must have been twice that in the Copernican.

XRD monitoring of α self-irradiation in uranium-americium mixed oxides.

PubMed

Horlait, Denis; Lebreton, Florent; Roussel, Pascal; Delahaye, Thibaud

2013-12-16

The structural evolution under (241)Am self-irradiation of U(1-x)Am(x)O(2±δ) transmutation fuels (with x ≤ 0.5) was studied by X-ray diffraction (XRD). Samples first underwent a preliminary heat treatment performed under a reducing atmosphere (Ar/H2(4%)) aiming to recover the previously accumulated structural defects. Over all measurements (carried out over up to a full year and for integrated doses up to 1.5 × 10(18) α-decay events·g(-1)), only fluorite U(1-x)Am(x)O(2±δ) solid solutions were observed. Within a few days after the end of the heat treatment, each of the five studied samples was slowly oxidized as a consequence of their move to air atmosphere, which is evidenced by XRD by an initial sharp decrease of the unit cell parameter. For the compounds with x ≤ 0.15, this oxidation occurred without any phase transitions, but for U0.6Am0.4O(2±δ) and U0.5Am0.5O(2±δ), this process is accompanied by a transition from a first fluorite solid solution to a second oxidized one, as the latter is thermodynamically stable in ambient conditions. In the meantime and after the oxidation process, (241)Am α self-irradiation caused a structural swelling up to ∼0.8 vol %, independently of the sample composition. The kinetic constants of swelling were also determined by regression of experimental data and are, as expected, dependent on x and thus on the dose rate. The normalization of these kinetic constants by sample α-activity, however, leads to very close swelling rates among the samples. Finally, evolutions of microstrain and crystallite size were also monitored, but for the considered dose rates and cumulated doses, α self-irradiation was found, within the limits of the diffractometer used, to have almost no impact on these characteristics. Microstrain was found to be influenced instead by the americium content in the materials (i.e., by the impurities associated with americium starting material and the increase of cationic charge heterogeneity with increasing americium content).

Adaptive control of theophylline therapy: importance of blood sampling times.

PubMed

D'Argenio, D Z; Khakmahd, K

1983-10-01

A two-observation protocol for estimating theophylline clearance during a constant-rate intravenous infusion is used to examine the importance of blood sampling schedules with regard to the information content of resulting concentration data. Guided by a theory for calculating maximally informative sample times, population simulations are used to assess the effect of specific sampling times on the precision of resulting clearance estimates and subsequent predictions of theophylline plasma concentrations. The simulations incorporated noise terms for intersubject variability, dosing errors, sample collection errors, and assay error. Clearance was estimated using Chiou's method, least squares, and a Bayesian estimation procedure. The results of these simulations suggest that clinically significant estimation and prediction errors may result when using the above two-point protocol for estimating theophylline clearance if the time separating the two blood samples is less than one population mean elimination half-life.

Is it really theoretical? A review of sampling in grounded theory studies in nursing journals.

PubMed

McCrae, Niall; Purssell, Edward

2016-10-01

Grounded theory is a distinct method of qualitative research, where core features are theoretical sampling and constant comparative analysis. However, inconsistent application of these activities has been observed in published studies. This review assessed the use of theoretical sampling in grounded theory studies in nursing journals. An adapted systematic review was conducted. Three leading nursing journals (2010-2014) were searched for studies stating grounded theory as the method. Sampling was assessed using a concise rating tool. A high proportion (86%) of the 134 articles described an iterative process of data collection and analysis. However, half of the studies did not demonstrate theoretical sampling, with many studies declaring or indicating a purposive sampling approach throughout. Specific reporting guidelines for grounded theory studies should be developed to ensure that study reports describe an iterative process of fieldwork and theoretical development. © 2016 John Wiley & Sons Ltd.

A Bayesian framework to estimate diversification rates and their variation through time and space

PubMed Central

2011-01-01

Background Patterns of species diversity are the result of speciation and extinction processes, and molecular phylogenetic data can provide valuable information to derive their variability through time and across clades. Bayesian Markov chain Monte Carlo methods offer a promising framework to incorporate phylogenetic uncertainty when estimating rates of diversification. Results We introduce a new approach to estimate diversification rates in a Bayesian framework over a distribution of trees under various constant and variable rate birth-death and pure-birth models, and test it on simulated phylogenies. Furthermore, speciation and extinction rates and their posterior credibility intervals can be estimated while accounting for non-random taxon sampling. The framework is particularly suitable for hypothesis testing using Bayes factors, as we demonstrate analyzing dated phylogenies of Chondrostoma (Cyprinidae) and Lupinus (Fabaceae). In addition, we develop a model that extends the rate estimation to a meta-analysis framework in which different data sets are combined in a single analysis to detect general temporal and spatial trends in diversification. Conclusions Our approach provides a flexible framework for the estimation of diversification parameters and hypothesis testing while simultaneously accounting for uncertainties in the divergence times and incomplete taxon sampling. PMID:22013891

Role of dielectric constant in electrohydrodynamics of conducting fluids

NASA Technical Reports Server (NTRS)

Rhodes, Percy H.; Snyder, Robert S.; Roberts, Glyn O.

1994-01-01

Electrohydrodynamic sample distortion during continuous flow electrophoresis is an experiment to be conducted during the second International Microgravity Laboratory (IML-2) in July 1994. The specific objective of this experiment is the distortion caused by the difference in dielectric constant between the sample and surrounding buffer. Although the role of sample conductivity in electrohydrodynamic has been the subject of both flight and ground experiments, the separate role of dielectric constant, independent of sample conductivity, has not been measured. This paper describes some of the laboratory research and model development that will support the flight experiment on IML-2.

Determination of temperature dependence of full matrix material constants of PZT-8 piezoceramics using only one sample.

PubMed

Zhang, Yang; Tang, Liguo; Tian, Hua; Wang, Jiyang; Cao, Wenwu; Zhang, Zhongwu

2017-08-15

Resonant ultrasound spectroscopy (RUS) was used to determine the temperature dependence of full matrix material constants of PZT-8 piezoceramics from room temperature to 100 °C. Property variations from sample to samples can be eliminated by using only one sample, so that data self-consistency can be guaranteed. The RUS measurement system error was estimated to be lower than 2.35%. The obtained full matrix material constants at different temperatures all have excellent self-consistency, which can help accurately predict device performance at high temperatures using finite element simulations.

Toward an understanding of the turbidity measurement of heterocoagulation rate constants of dispersions containing particles of different sizes.

PubMed

Liu, Jie; Xu, Shenghua; Sun, Zhiwei

2007-11-06

Our previous studies have shown that the determination of coagulation rate constants by turbidity measurement becomes impossible for a certain operating wavelength (that is, its blind point) because at this wavelength the change in the turbidity of a dispersion completely loses its response to the coagulation process. Therefore, performing the turbidity measurement in the wavelength range near the blind point should be avoided. In this article, we demonstrate that the turbidity measurement of the rate constant for coagulation of a binary dispersion containing particles of two different sizes (heterocoagulation) presents special difficulties because the blind point shifts with not only particle size but also with the component fraction. Some important aspects of the turbidity measurement for the heterocoagulation rate constant are discussed and experimentally tested. It is emphasized that the T-matrix method can be used to correctly evaluate extinction cross sections of doublets formed during the heterocoagulation process, which is the key data determining the rate constant from the turbidity measurement, and choosing the appropriate operating wavelength and component fraction are important to achieving a more accurate rate constant. Finally, a simple scheme in experimentally determining the sensitivity of the turbidity changes with coagulation over a wavelength range is proposed.

Digital Synchronizer without Metastability

NASA Technical Reports Server (NTRS)

Simle, Robert M.; Cavazos, Jose A.

2009-01-01

A proposed design for a digital synchronizing circuit would eliminate metastability that plagues flip-flop circuits in digital input/output interfaces. This metastability is associated with sampling, by use of flip-flops, of an external signal that is asynchronous with a clock signal that drives the flip-flops: it is a temporary flip-flop failure that can occur when a rising or falling edge of an asynchronous signal occurs during the setup and/or hold time of a flip-flop. The proposed design calls for (1) use of a clock frequency greater than the frequency of the asynchronous signal, (2) use of flip-flop asynchronous preset or clear signals for the asynchronous input, (3) use of a clock asynchronous recovery delay with pulse width discriminator, and (4) tying the data inputs to constant logic levels to obtain (5) two half-rate synchronous partial signals - one for the falling and one for the rising edge. Inasmuch as the flip-flop data inputs would be permanently tied to constant logic levels, setup and hold times would not be violated. The half-rate partial signals would be recombined to construct a signal that would replicate the original asynchronous signal at its original rate but would be synchronous with the clock signal.

Fabrication of microfluidic architectures for optimal flow rate and concentration measurement for lab on chip application

NASA Astrophysics Data System (ADS)

Adam, Tijjani; Hashim, U.

2017-03-01

Optimum flow in micro channel for sensing purpose is challenging. In this study, The optimizations of the fluid sample flows are made through the design and characterization of the novel microfluidics' architectures to achieve the optimal flow rate in the micro channels. The biocompatibility of the Polydimetylsiloxane (Sylgard 184 silicon elastomer) polymer used to fabricate the device offers avenue for the device to be implemented as the universal fluidic delivery system for bio-molecules sensing in various bio-medical applications. The study uses the following methodological approaches, designing a novel microfluidics' architectures by integrating the devices on a single 4 inches silicon substrate, fabricating the designed microfluidic devices using low-cost solution soft lithography technique, characterizing and validating the flow throughput of urine samples in the micro channels by generating pressure gradients through the devices' inlets. The characterization on the urine samples flow in the micro channels have witnessed the constant flow throughout the devices.

Time since death and decay rate constants of Norway spruce and European larch deadwood in subalpine forests determined using dendrochronology and radiocarbon dating

NASA Astrophysics Data System (ADS)

Petrillo, Marta; Cherubini, Paolo; Fravolini, Giulia; Marchetti, Marco; Ascher-Jenull, Judith; Schärer, Michael; Synal, Hans-Arno; Bertoldi, Daniela; Camin, Federica; Larcher, Roberto; Egli, Markus

2016-03-01

Due to the large size (e.g. sections of tree trunks) and highly heterogeneous spatial distribution of deadwood, the timescales involved in the coarse woody debris (CWD) decay of Picea abies (L.) Karst. and Larix decidua Mill. in Alpine forests are largely unknown. We investigated the CWD decay dynamics in an Alpine valley in Italy using the chronosequence approach and the five-decay class system that is based on a macromorphological assessment. For the decay classes 1-3, most of the dendrochronological samples were cross-dated to assess the time that had elapsed since tree death, but for decay classes 4 and 5 (poorly preserved tree rings) radiocarbon dating was used. In addition, density, cellulose, and lignin data were measured for the dated CWD. The decay rate constants for spruce and larch were estimated on the basis of the density loss using a single negative exponential model, a regression approach, and the stage-based matrix model. In the decay classes 1-3, the ages of the CWD were similar and varied between 1 and 54 years for spruce and 3 and 40 years for larch, with no significant differences between the classes; classes 1-3 are therefore not indicative of deadwood age. This seems to be due to a time lag between the death of a standing tree and its contact with the soil. We found distinct tree-species-specific differences in decay classes 4 and 5, with larch CWD reaching an average age of 210 years in class 5 and spruce only 77 years. The mean CWD rate constants were estimated to be in the range 0.018 to 0.022 y-1 for spruce and to about 0.012 y-1 for larch. Snapshot sampling (chronosequences) may overestimate the age and mean residence time of CWD. No sampling bias was, however, detectable using the stage-based matrix model. Cellulose and lignin time trends could be derived on the basis of the ages of the CWD. The half-lives for cellulose were 21 years for spruce and 50 years for larch. The half-life of lignin is considerably higher and may be more than 100 years in larch CWD. Consequently, the decay of Picea abies and Larix decidua is very low. Several uncertainties, however, remain: 14C dating of CWD from decay classes 4 and 5 and having a pre-bomb age is often difficult (large age range due to methodological constraints) and fall rates of both European larch and Norway spruce are missing.

(In)validity of the constant field and constant currents assumptions in theories of ion transport.

PubMed Central

Syganow, A; von Kitzing, E

1999-01-01

Constant electric fields and constant ion currents are often considered in theories of ion transport. Therefore, it is important to understand the validity of these helpful concepts. The constant field assumption requires that the charge density of permeant ions and flexible polar groups is virtually voltage independent. We present analytic relations that indicate the conditions under which the constant field approximation applies. Barrier models are frequently fitted to experimental current-voltage curves to describe ion transport. These models are based on three fundamental characteristics: a constant electric field, negligible concerted motions of ions inside the channel (an ion can enter only an empty site), and concentration-independent energy profiles. An analysis of those fundamental assumptions of barrier models shows that those approximations require large barriers because the electrostatic interaction is strong and has a long range. In the constant currents assumption, the current of each permeating ion species is considered to be constant throughout the channel; thus ion pairing is explicitly ignored. In inhomogeneous steady-state systems, the association rate constant determines the strength of ion pairing. Among permeable ions, however, the ion association rate constants are not small, according to modern diffusion-limited reaction rate theories. A mathematical formulation of a constant currents condition indicates that ion pairing very likely has an effect but does not dominate ion transport. PMID:9929480

Development of a new aerosol monitoring system and its application in Fukushima nuclear accident related aerosol radioactivity measurement at the CTBT radionuclide station in Sidney of Canada.

PubMed

Zhang, Weihua; Bean, Marc; Benotto, Mike; Cheung, Jeff; Ungar, Kurt; Ahier, Brian

2011-12-01

A high volume aerosol sampler ("Grey Owl") has been designed and developed at the Radiation Protection Bureau, Health Canada. Its design guidance is based on the need for a low operational cost and reliable sampler to provide daily aerosol monitoring samples that can be used as reference samples for radiological studies. It has been developed to provide a constant air flow rate at low pressure drops (∼3 kPa for a day sampling) with variations of less than ±1% of the full scale flow rate. Its energy consumption is only about 1.5 kW for a filter sampling over 22,000 standard cubic meter of air. It has been demonstrated in this Fukushima nuclear accident related aerosol radioactivity monitoring study at Sidney station, B.C. that the sampler is robust and reliable. The results provided by the new monitoring system have been used to support decision-making in Canada during an emergency response. Copyright © 2011 Elsevier Ltd. All rights reserved.

Coffee Consumption Habits and the Risk of Mild Cognitive Impairment: The Italian Longitudinal Study on Aging.

PubMed

Solfrizzi, Vincenzo; Panza, Francesco; Imbimbo, Bruno P; D'Introno, Alessia; Galluzzo, Lucia; Gandin, Claudia; Misciagna, Giovanni; Guerra, Vito; Osella, Alberto; Baldereschi, Marzia; Di Carlo, Antonio; Inzitari, Domenico; Seripa, Davide; Pilotto, Alberto; Sabbá, Carlo; Logroscino, Giancarlo; Scafato, Emanuele

2015-01-01

Coffee, tea, or caffeine consumption may be protective against cognitive impairment and dementia. We estimated the association between change or constant habits in coffee consumption and the incidence of mild cognitive impairment (MCI). We evaluated 1,445 individuals recruited from 5,632 subjects, aged 65-84 year old, from the Italian Longitudinal Study on Aging, a population-based sample from eight Italian municipalities with a 3.5-year median follow-up. Cognitively normal older individuals who habitually consumed moderate amount of coffee (from 1 to 2 cups of coffee/day) had a lower rate of the incidence of MCI than those who never or rarely consumed coffee [1 cup/day: hazard ratio (HR): 0.47, 95% confidence interval (CI): 0.211 to 1.02 or 1-2 cups/day: HR: 0.31 95% CI: 0.13 to 0.75]. For cognitively normal older subjects who changed their coffee consumption habits, those increasing coffee consumption (>1 cup of coffee/day) had higher rate of the incidence of MCI compared to those with constant habits (up to ±1 cup of coffee/day) (HR: 1.80, 95% CI: 1.11 to 2.92) or those with reduced consumption (<1 cup of coffee/day) (HR: 2.17, 95% CI: 1.16 to 4.08). Finally, there was no significant association between subjects with higher levels of coffee consumption (>2 cups of coffee/day) and the incidence of MCI in comparison with those who never or rarely consumed coffee (HR: 0.26, 95% CI: 0.03 to 2.11). In conclusion, cognitively normal older individuals who increased their coffee consumption had a higher rate of developing MCI, while a constant in time moderate coffee consumption was associated to a reduced rate of the incidence of MCI.

Measurement of biochemical oxygen demand of the leachates.

PubMed

Fulazzaky, Mohamad Ali

2013-06-01

Biochemical oxygen demand (BOD) of the leachates originally from the different types of landfill sites was studied based on the data measured using the two manometric methods. The measurements of BOD using the dilution method were carried out to assess the typical physicochemical and biological characteristics of the leachates together with some other parameters. The linear regression analysis was used to predict rate constants for biochemical reactions and ultimate BOD values of the different leachates. The rate of a biochemical reaction implicated in microbial biodegradation of pollutants depends on the leachate characteristics, mass of contaminant in the leachate, and nature of the leachate. Character of leachate samples for BOD analysis of using the different methods may differ significantly during the experimental period, resulting in different BOD values. This work intends to verify effect of the different dilutions for the manometric method tests on the BOD concentrations of the leachate samples to contribute to the assessment of reaction rate and microbial consumption of oxygen.

Predicting fractional bed load transport rates: Application of the Wilcock‐Crowe equations to a regulated gravel bed river

USGS Publications Warehouse

Gaeuman, David; Andrews, E.D.; Krause, Andreas; Smith, Wes

2009-01-01

Bed load samples from four locations in the Trinity River of northern California are analyzed to evaluate the performance of the Wilcock‐Crowe bed load transport equations for predicting fractional bed load transport rates. Bed surface particles become smaller and the fraction of sand on the bed increases with distance downstream from Lewiston Dam. The dimensionless reference shear stress for the mean bed particle size (τ*rm) is largest near the dam, but varies relatively little between the more downstream locations. The relation between τ*rm and the reference shear stresses for other size fractions is constant across all locations. Total bed load transport rates predicted with the Wilcock‐Crowe equations are within a factor of 2 of sampled transport rates for 68% of all samples. The Wilcock‐Crowe equations nonetheless consistently under‐predict the transport of particles larger than 128 mm, frequently by more than an order of magnitude. Accurate prediction of the transport rates of the largest particles is important for models in which the evolution of the surface grain size distribution determines subsequent bed load transport rates. Values of τ*rm estimated from bed load samples are up to 50% larger than those predicted with the Wilcock‐Crowe equations, and sampled bed load transport approximates equal mobility across a wider range of grain sizes than is implied by the equations. Modifications to the Wilcock‐Crowe equation for determining τ*rm and the hiding function used to scale τ*rm to other grain size fractions are proposed to achieve the best fit to observed bed load transport in the Trinity River.

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

NASA Technical Reports Server (NTRS)

Kawamura, K.; Ferris, J. P.

1999-01-01

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

Fiber release from impacted graphite reinforced epoxy composites

NASA Technical Reports Server (NTRS)

Babinsky, T. C.

1980-01-01

Carbon fibers released from composites by aircraft fires and crashes can cause electrical shorts and consequent equipment damage. This report investigates less vigorous release mechanisms than that previously simulated by explosive burn/blast tests. When AS/3501-6 composites are impacted by various head and weight configurations of a pendulum impactor, less than 0.2 percent by weight of the original sample is released as single fibers. Other fiber release mechanisms studied were air blasts, constant airflow, torsion, flexural, and vibration of composite samples. The full significance of the low single fiber release rates found here is to be evaluated by NASA in their aircraft vulnerability studies.

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, Jr., A. Burtron; Levy, Ira S.; Trimble, Dennis J.; Lanning, Donald D.; Gerber, Franna S.

1990-01-01

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-bsed materials is disclosed. Samples of zirconium-based materials having different composition and/or fabrication are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280.degree. to 316.degree. C.). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hyriding for the same materials when subject to in-reactor (irradiated) corrision.

Size-Based Separation of Particles and Cells Utilizing Viscoelastic Effects in Straight Microchannels.

PubMed

Liu, Chao; Xue, Chundong; Chen, Xiaodong; Shan, Lei; Tian, Yu; Hu, Guoqing

2015-06-16

Viscoelasticity-induced particle migration has recently received increasing attention due to its ability to obtain high-quality focusing over a wide range of flow rates. However, its application is limited to low throughput regime since the particles can defocus as flow rate increases. Using an engineered carrier medium with constant and low viscosity and strong elasticity, the sample flow rates are improved to be 1 order of magnitude higher than those in existing studies. Utilizing differential focusing of particles of different sizes, here, we present sheathless particle/cell separation in simple straight microchannels that possess excellent parallelizability for further throughput enhancement. The present method can be implemented over a wide range of particle/cell sizes and flow rates. We successfully separate small particles from larger particles, MCF-7 cells from red blood cells (RBCs), and Escherichia coli (E. coli) bacteria from RBCs in different straight microchannels. The proposed method could broaden the applications of viscoelastic microfluidic devices to particle/cell separation due to the enhanced sample throughput and simple channel design.

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

NASA Technical Reports Server (NTRS)

DeMore, W.; Bayes, K.

1998-01-01

Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

An Observation of Repeating Events at local asperities during a Laboratory Stick-slip Experiment of a Saw-cut Cylindrical Lucite Sample

NASA Astrophysics Data System (ADS)

Gu, C.; Mighani, S.; Prieto, G. A.; Mok, U.; Evans, J. B.; Hager, B. H.; Toksoz, M. N.

2017-12-01

Repeating earthquakes have been found in subduction zones and interpreted as repeated ruptures of small local asperities. Repeating earthquakes have also been found in oil/gas fields, interpreted as the reactivation of pre-existing faults due to fluid injection/extraction. To mimic the fault rupture of a fault with local asperities, we designed a "stick-slip" experiment using a saw-cut cylindrical Lucite sample, which had sharp localized ridges parallel to the strike of the fault plane. The sample was subjected to conventional triaxial loading with a constant confining pressure of 10 MPa. The axial load was then increased to 6 MPa at a constant rate of 0.12 MPa/sec until the sliding occurred along the fault plane. Ultrasonic acoustic emissions (AEs) were monitored with eight PZT sensors. Two cycles of AEs were detected with the occurrence rate that decreased from the beginning to the end of each cycle, while the relative magnitudes increased. Correlation analysis indicated that these AEs were clustered into two groups - those with frequency content between 200-300kHz and a second group with frequency content between 10-50kHz. The locations of the high-frequency events, with almost identical waveforms, show that these events are from the sharp localized ridges on the saw-cut plane. The locations of the low-frequency events show an approaching process to the high-frequency events for each cycle. In this single experiment, there was a correlation of the proximity of the low-frequency events with the subsequent triggering of large high-frequency repeating events.

A case study of real-time monitoring of solid-state phase transformations in acoustically levitated particles using near infrared and Raman spectroscopy.

PubMed

Rehder, Sönke; Wu, Jian X; Laackmann, Julian; Moritz, Hans-Ulrich; Rantanen, Jukka; Rades, Thomas; Leopold, Claudia S

2013-01-23

The objective of this study was to monitor the amorphous-to-crystalline solid-state phase transformation kinetics of the model drug ibuprofen with spectroscopic methods during acoustic levitation. Chemical and physical information was obtained by real-time near infrared (NIRS) and Raman spectroscopy measurements. The recrystallisation kinetic parameters (overall recrystallisation rate constant β and the time needed to reach 50% of the equilibrated level t(50)), were determined using a multivariate curve resolution approach. The acoustic levitation device coupled with non-invasive spectroscopy enabled monitoring of the recrystallisation process of the difficult-to-handle (adhesive) amorphous sample. The application of multivariate curve resolution enabled isolation of the underlying pure spectra, which corresponded well with the reference spectra of amorphous and crystalline ibuprofen. The recrystallisation kinetic parameters were estimated from the recrystallisation profiles. While the empirical recrystallisation rate constant determined by NIR and Raman spectroscopy were comparable, the lag time for recrystallisation was significantly lower with Raman spectroscopy as compared to NIRS. This observation was explained by the high energy density of the Raman laser beam, which might have led to local heating effects of the sample and thus reduced the recrystallisation onset time. It was concluded that acoustic levitation with NIR and Raman spectroscopy combined with multivariate curve resolution allowed direct determination of the recrystallisation kinetics of amorphous drugs and thus is a promising technique for monitoring solid-state phase transformations of adhesive small-sized samples during the early phase of drug development. Copyright © 2012 Elsevier B.V. All rights reserved.

Hydro-geophysical responses to the injection of CO2 in core plugs of Berea sandstone

NASA Astrophysics Data System (ADS)

Song, I.; Park, K. G.

2017-12-01

We have built a laboratory-scale core flooding system to measure the relative permeability of a core sample and the acoustic response to the CO2 saturation degree at in situ condition of pressure and temperature down to a few kilometer depths. The system consisted of an acoustic velocity core holder (AVC model from the Core Laboratories) between upstream where CO2 and H2O were injected separately and downstream where the mixed fluids came out of a core sample. Core samples with 4 cm in diameter and 5 cm in length of Berea sandstone were in turn placed in the core holder for confining and axial pressures. The flooding operations of the multiphase fluids were conducted through the sample at 40ºC in temperature and 8 MPa in backpressure. CO2 and H2O in the physical condition were injected separately into a sample at constant rate with various ratios. The two phases were mixed during flowing through the sample. The mixed fluids out of the sample were separated again by their different densities in a chamber equipped with a level gauge of the interface. From the level change of the water in the separator, we measured the volume of water coming out of the sample for each test with a constant ratio of the injection rates. Then it was possible to calculate the saturation degree of CO2 from the difference between input volume and output volume of water. The differential pressure between upstream and downstream was directly measured to calculate the relative permeability as a function of the CO2 saturation degree. We also conducted ultrasonic measurements using piezoelectric sensors on the end plugs. An electric pulse was given to a sensor on one end of sample, and then ultrasonic waves were recorded from the other end. The various ratios of injection rate of CO2 and H2O into Berea sandstone yielded a range of 0.1-0.7 in CO2 saturation degree. The relative permeability was obtained at the condition of steady-state flow for given stages from the velocity of each phase and the pressure gradient. The arrival time of P-wave became retarded and its amplitude became smaller as the degree of CO2 saturation increases. However no change was observed in S-wave in both characters. According to our results, time-lapse measurements of P-wave signals can be a monitoring tool of the subsurface migration of CO2, thus of detecting even its leakage.

High-Temperature Slow Crack Growth of Silicon Carbide Determined by Constant-Stress-Rate and Constant-Stress Testing

NASA Technical Reports Server (NTRS)

Choi, Sung H.; Salem, J. A.; Nemeth, N. N.

1998-01-01

High-temperature slow-crack-growth behaviour of hot-pressed silicon carbide was determined using both constant-stress-rate ("dynamic fatigue") and constant-stress ("static fatigue") testing in flexure at 1300 C in air. Slow crack growth was found to be a governing mechanism associated with failure of the material. Four estimation methods such as the individual data, the Weibull median, the arithmetic mean and the median deviation methods were used to determine the slow crack growth parameters. The four estimation methods were in good agreement for the constant-stress-rate testing with a small variation in the slow-crack-growth parameter, n, ranging from 28 to 36. By contrast, the variation in n between the four estimation methods was significant in the constant-stress testing with a somewhat wide range of n= 16 to 32.

The Influence of Uncompensated Solution Resistance on the Determination and Standard Electrochemical Rate Constants Using Cyclic Voltammetry, and Some Comparisons with AC Voltammetry.

DTIC Science & Technology

1987-09-25

rate constants, k2r using cyclic voltametry . The res tss are expressed in terms of systematic deviations oP sapparent measured" rate constants, k~b(app...concentration was taken to be lum unless otherwise noted. The voltammetric sweep rate was set at 20 V sŕ unless specified otherwise. The general procedure...peaks for the negative- and positive-going potential sweeps have opposite signs, the measured cathodic-anodic peak separation, AEp, will clearly be

Assessing the effect of different treatments on decomposition rate of dairy manure.

PubMed

Khalil, Tariq M; Higgins, Stewart S; Ndegwa, Pius M; Frear, Craig S; Stöckle, Claudio O

2016-11-01

Confined animal feeding operations (CAFOs) contribute to greenhouse gas emission, but the magnitude of these emissions as a function of operation size, infrastructure, and manure management are difficult to assess. Modeling is a viable option to estimate gaseous emission and nutrient flows from CAFOs. These models use a decomposition rate constant for carbon mineralization. However, this constant is usually determined assuming a homogenous mix of manure, ignoring the effects of emerging manure treatments. The aim of this study was to measure and compare the decomposition rate constants of dairy manure in single and three-pool decomposition models, and to develop an empirical model based on chemical composition of manure for prediction of a decomposition rate constant. Decomposition rate constants of manure before and after an anaerobic digester (AD), following coarse fiber separation, and fine solids removal were determined under anaerobic conditions for single and three-pool decomposition models. The decomposition rates of treated manure effluents differed significantly from untreated manure for both single and three-pool decomposition models. In the single-pool decomposition model, AD effluent containing only suspended solids had a relatively high decomposition rate of 0.060 d(-1), while liquid with coarse fiber and fine solids removed had the lowest rate of 0.013 d(-1). In the three-pool decomposition model, fast and slow decomposition rate constants (0.25 d(-1) and 0.016 d(-1) respectively) of untreated AD influent were also significantly different from treated manure fractions. A regression model to predict the decomposition rate of treated dairy manure fitted well (R(2) = 0.83) to observed data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pulsed Tm:YAG laser ablation of knee joint tissues

NASA Astrophysics Data System (ADS)

Shi, Wei-Qiang; Vari, Sandor G.; Duffy, J. T.; Miller, J. M.; Weiss, Andrew B.; Fishbein, Michael C.; Grundfest, Warren S.

1992-06-01

We investigated the effect of a free-running 2.01 micron pulsed Tm:YAG laser on bovine knee joint tissues. Ablation rates of fresh fibrocartilage, hyaline cartilage, and bone were measured in saline as a function of laser fluence (160 - 640 J/cm2) and fiber core size (400 and 600 microns). All tissues could be effectively ablated and the ablation rate increased linearly with the increasing fluence. Use of fibers of different core sizes, while maintaining constant energy fluence, did not result in significant difference in ablation rate. Histology analyses of the ablated tissue samples reveal average Tm:YAG radiation induced thermal damage (denatunalization) zones ranging between 130 and 540 microns, depending on the laser parameters and the tissue type.

The accretion rate of extraterrestrial 3He based on oceanic 230Th flux and the relation to Os isotope variation over the past 200,000 years in an Indian Ocean core

NASA Astrophysics Data System (ADS)

Marcantonio, Franco; Turekian, Karl K.; Higgins, Sean; Anderson, Robert F.; Stute, Martin; Schlosser, Peter

1999-07-01

In the eastern equatorial Indian Ocean, the flux of extraterrestrial 3He, a proxy of interplanetary dust particles (IDPs), has been relatively constant over the past 200 ka. The flux is equal to (1.1±0.4)×10 -12 cm 3 STP cm -2 ka -1, a value obtained using the xs 230Th profiling method. Variations in mass accumulation rates (MARs) derived assuming a constant extraterrestrial 3He flux have a 40-ka periodicity similar to that observed in the δ 18O-derived MARs. This frequency is similar to that of the Earth's obliquity. Measured 187Os/ 188Os ratios are less radiogenic than present-day seawater (0.49-0.98), reflecting the mixing of Os derived from extraterrestrial, terrigenous and hydrogenous sources. When coupled with He data measured on the same samples, Os isotope data yield important information about the terrigenous component supplied to the eastern equatorial Indian Ocean. The amount of Os in the sample derived from the extraterrestrial component can be deduced with the help of the helium systematics. Once corrected for the extraterrestrial component of Os, Os isotope signatures, in conjunction with the 4He concentrations, suggest a supply of terrigenous material from Indonesian ultramafic and Himalayan crustal sources that clearly varies through time.

Nitrogen-doped diamond thin films: potential application in Fabry-Pérot interferometer

NASA Astrophysics Data System (ADS)

Kosowska, M.; Majchrowicz, D.; Sankaran, K. J.; Ficek, M.; Jedrzejewska-Szczerska, M.; Haenen, M. K.

2018-04-01

In this paper we present results of preliminary research of using nitrogen-doped diamond (NDD) films as reflective layer in Fabry-Pérot interferometer. NDD films were deposited on Si substrates by Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) with the use of CH4, H2 and N2 gas mixtures. During deposition process methane flow rate varied while nitrogen flow was constant. We performed series of measurements which showed that NDD can be used as a mirror in Fabry-Pérot interferometer. The best signal visibility and repeatability of measurements were obtained for sample made with 3 sccm methane flow rate.

On the early stages of wind wave under non-stationary wind conditions.

NASA Astrophysics Data System (ADS)

Robles-Diaz, Lucia; Ocampo-Torres, Francisco J.; Branger, Hubert

2017-04-01

Most efforts in the study of the generation and evolution of wind waves have been conducted under constant wind. The balance of the transfer of different properties has been studied mainly for situations where the wave has already reached the equilibrium with the constant wind conditions. The purpose of these experiments is to study the early stages of the generation of waves under non-stationary wind conditions and to determine a balance in the exchange at the air-water interface for non-equilibrium wind conditions. A total of 16 experiments with a characteristic acceleration and deceleration rate of wind speed were conducted in a large wind-wave facility of Institut Pythéas (Marseille-France). The wave tank is 40 m long, 2.7 m wide and 1 m deep. The air section is 50 m long, 3 m wide and 1.8 m height. The momentum fluxes were estimated from hot wire anemometry at station 7. Also, the free surface displacement was measured along the channel tank at 11 stations where resistance wires were installed, except at stations 1, 2, and 7 where capacitance wires were installed. The sampling frequency for wind velocity and surface displacement measurements was 256 Hz. During experiments the wind intensity was abruptly increased with a constant acceleration rate over time, reaching a constant maximum intensity of 13 m/s. This constant velocity remains some time until the intensity is again reduced suddenly. We observed that wind drag coefficient values are higher for the experiments that present the lower acceleration rate; some field data from previous studies is presented for reference (Large and Pond 1981; Ocampo-Torres et al. 2011; Smith 1980; Yelland and Taylor 1996). The empirical grow curves show that in the experiments with lower acceleration, the wave field is more developed, showing higher dimensional energy and lower dimensional peak frequency. In the evolution of the spectral wave energy, there is first high frequency energy saturation, followed by a downshift of the wave-spectral peak frequency. Under the same wind speed, these two processes are more developed when the acceleration is low. Therefore, the acceleration rate has a direct impact in controlling how the energy and momentum transfer take place from the wind to the wave field. This work represents a contribution of RugDiSMar Project (CONACYT 155793), and of project CONACYT CB-2015-01 255377.

Application of dielectric constant measurement in microwave sludge disintegration and wastewater purification processes.

PubMed

Kovács, Petra Veszelovszki; Lemmer, Balázs; Keszthelyi-Szabó, Gábor; Hodúr, Cecilia; Beszédes, Sándor

2018-05-01

It has been numerously verified that microwave radiation could be advantageous as a pre-treatment for enhanced disintegration of sludge. Very few data related to the dielectric parameters of wastewater of different origins are available; therefore, the objective of our work was to measure the dielectric constant of municipal and meat industrial wastewater during a continuous flow operating microwave process. Determination of the dielectric constant and its change during wastewater and sludge processing make it possible to decide on the applicability of dielectric measurements for detecting the organic matter removal efficiency of wastewater purification process or disintegration degree of sludge. With the measurement of dielectric constant as a function of temperature, total solids (TS) content and microwave specific process parameters regression models were developed. Our results verified that in the case of municipal wastewater sludge, the TS content has a significant effect on the dielectric constant and disintegration degree (DD), as does the temperature. The dielectric constant has a decreasing tendency with increasing temperature for wastewater sludge of low TS content, but an adverse effect was found for samples with high TS and organic matter contents. DD of meat processing wastewater sludge was influenced significantly by the volumetric flow rate and power level, as process parameters of continuously flow microwave pre-treatments. It can be concluded that the disintegration process of food industry sludge can be detected by dielectric constant measurements. From technical purposes the applicability of dielectric measurements was tested in the purification process of municipal wastewater, as well. Determination of dielectric behaviour was a sensitive method to detect the purification degree of municipal wastewater.

Constant-Distance Mode Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging of Biological Samples with Complex Topography

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

Nguyen, Son N.; Liyu, Andrey V.; Chu, Rosalie K.

A new approach for constant distance mode mass spectrometry imaging of biological samples using nanospray desorption electrospray ionization (nano-DESI MSI) was developed by integrating a shear-force probe with nano-DESI probe. The technical concept and basic instrumental setup as well as general operation of the system are described. Mechanical dampening of resonant oscillations due to the presence of shear forces between the probe and the sample surface enables constant-distance imaging mode via a computer controlled closed feedback loop. The capability of simultaneous chemical and topographic imaging of complex biological samples is demonstrated using living Bacillus Subtilis ATCC 49760 colonies on agarmore » plates. The constant-distance mode nano-DESI MSI enabled imaging of many metabolites including non-ribosomal peptides (surfactin, plipastatin and iturin) and iron-bound heme on the surface of living bacterial colonies ranging in diameter from 10 mm to 13 mm with height variations of up to 0.8 mm above the agar plate. Co-registration of ion images to topographic images provided higher-contrast images. Constant-mode nano-DESI MSI is ideally suited for imaging biological samples of complex topography in their native state.« less

ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS - ALKALINE HYDROLYSIS

EPA Science Inventory

SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to allow the calculation of alkaline hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition state...

Magnetic-time model at off-season germination

NASA Astrophysics Data System (ADS)

Mahajan, Tarlochan Singh; Pandey, Om Prakash

2014-03-01

Effect of static magnetic field on germination of mung beans is described. Seeds of mung beans, were exposed in batches to static magnetic fields of 87 to 226 mT intensity for 100 min. Magnetic time constant - 60.743 Th (Tesla hour) was determined experimentally. High value of magnetic time constant signifies lower effect of magnetic field on germination rate as this germination was carried out at off-season (13°C). Using decay function, germination magnetic constant was calculated. There was a linear increase in germination magnetic constant with increasing intensity of magnetic field. Calculated values of mean germination time, mean germination rate, germination rate coefficient, germination magnetic constant, transition time, water uptake, indicate that the impact of applied static magnetic field improves the germination of mung beans seeds even in off-season

Kinetic analysis of cooperative interactions induced by Mn2+ binding to the chloroplast H(+)-ATPase.

PubMed

Hiller, R; Carmeli, C

1990-07-03

The kinetics of Mn2+ binding to three cooperatively interacting sites in chloroplast H(+)-ATPase (CF1) were measured by EPR following rapid mixing of the enzyme with MnCl2 with a time resolution of 8 ms. Mixing of the enzyme-bound Mn2+ with MgCl2 gave a measure of the rate of exchange. The data could be best fitted to a kinetic model assuming three sequential, positively cooperative binding sites. (1) In the latent CF1, the binding to all three sites had a similar on-rate constants of (1.1 +/- 0.04) X 10(4) M-1s-1. (2) Site segregation was found in the release of ions with off-rate constants of 0.69 +/- 0.04 s-1 for the first two and 0.055 +/- 0.003 s-1 for the third. (3) Addition of one ADP per CF1 caused a decrease in the off-rate constants to 0.31 +/- 0.02 and 0.033 +/- 0.008 s-1 for the first two and the third sites, respectively. (4) Heat activation of CF1 increased the on-rate constant to (4.2 +/- 0.92) X 10(4) M-1s-1 and the off-rate constants of the first two and the third site to 1.34 +/- 0.08 and 0.16 +/- 0.07 s-1, respectively. (5) The calculated thermodynamic dissociation constants were similar to those previously obtained from equilibrium binding studies. These findings were correlated to the rate constants obtained from studies of the catalysis and regulation of the H(+)-ATPase. The data support the suggestion that regulation induces sequential progress of catalysis through the three active sites of the enzyme.

Accelerated Testing Methodology for the Determination of Slow Crack Growth of Advanced Ceramics

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Salem, Jonathan A.; Gyekenyesi, John P.

1997-01-01

Constant stress-rate (dynamic fatigue) testing has been used for several decades to characterize slow crack growth behavior of glass and ceramics at both ambient and elevated temperatures. The advantage of constant stress-rate testing over other methods lies in its simplicity: Strengths are measured in a routine manner at four or more stress rates by applying a constant crosshead speed or constant loading rate. The slow crack growth parameters (n and A) required for design can be estimated from a relationship between strength and stress rate. With the proper use of preloading in constant stress-rate testing, an appreciable saving of test time can be achieved. If a preload corresponding to 50 % of the strength is applied to the specimen prior to testing, 50 % of the test time can be saved as long as the strength remains unchanged regardless of the applied preload. In fact, it has been a common, empirical practice in strength testing of ceramics or optical fibers to apply some preloading (less then 40%). The purpose of this work is to study the effect of preloading on the strength to lay a theoretical foundation on such an empirical practice. For this purpose, analytical and numerical solutions of strength as a function of preloading were developed. To verify the solution, constant stress-rate testing using glass and alumina at room temperature and alumina silicon nitride, and silicon carbide at elevated temperatures was conducted in a range of preloadings from O to 90 %.

HO + CO reaction rates and H/D kinetic isotope effects: master equation models with ab initio SCTST rate constants.

PubMed

Weston, Ralph E; Nguyen, Thanh Lam; Stanton, John F; Barker, John R

2013-02-07

Ab initio microcanonical rate constants were computed using Semi-Classical Transition State Theory (SCTST) and used in two master equation formulations (1D, depending on active energy with centrifugal corrections, and 2D, depending on total energy and angular momentum) to compute temperature-dependent rate constants for the title reactions using a potential energy surface obtained by sophisticated ab initio calculations. The 2D master equation was used at the P = 0 and P = ∞ limits, while the 1D master equation with centrifugal corrections and an empirical energy transfer parameter could be used over the entire pressure range. Rate constants were computed for 75 K ≤ T ≤ 2500 K and 0 ≤ [He] ≤ 10(23) cm(-3). For all temperatures and pressures important for combustion and for the terrestrial atmosphere, the agreement with the experimental rate constants is very good, but at very high pressures and T ≤ 200 K, the theoretical rate constants are significantly smaller than the experimental values. This effect is possibly due to the presence in the experiments of dimers and prereactive complexes, which were not included in the model calculations. The computed H/D kinetic isotope effects are in acceptable agreement with experimental data, which show considerable scatter. Overall, the agreement between experimental and theoretical H/D kinetic isotope effects is much better than in previous work, and an assumption of non-RRKM behavior does not appear to be needed to reproduce experimental observations.

Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

PubMed

Minakata, Daisuke; Crittenden, John

2011-04-15

The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

Absolute protein-protein association rate constants from flexible, coarse-grained Brownian dynamics simulations: the role of intermolecular hydrodynamic interactions in barnase-barstar association.

PubMed

Frembgen-Kesner, Tamara; Elcock, Adrian H

2010-11-03

Theory and computation have long been used to rationalize the experimental association rate constants of protein-protein complexes, and Brownian dynamics (BD) simulations, in particular, have been successful in reproducing the relative rate constants of wild-type and mutant protein pairs. Missing from previous BD studies of association kinetics, however, has been the description of hydrodynamic interactions (HIs) between, and within, the diffusing proteins. Here we address this issue by rigorously including HIs in BD simulations of the barnase-barstar association reaction. We first show that even very simplified representations of the proteins--involving approximately one pseudoatom for every three residues in the protein--can provide excellent reproduction of the absolute association rate constants of wild-type and mutant protein pairs. We then show that simulations that include intermolecular HIs also produce excellent estimates of association rate constants, but, for a given reaction criterion, yield values that are decreased by ∼35-80% relative to those obtained in the absence of intermolecular HIs. The neglect of intermolecular HIs in previous BD simulation studies, therefore, is likely to have contributed to the somewhat overestimated absolute rate constants previously obtained. Consequently, intermolecular HIs could be an important component to include in accurate modeling of the kinetics of macromolecular association events. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

A theoretical and shock tube kinetic study on hydrogen abstraction from phenyl formate.

PubMed

Ning, Hongbo; Liu, Dapeng; Wu, Junjun; Ma, Liuhao; Ren, Wei; Farooq, Aamir

2018-06-12

The hydrogen abstraction reactions of phenyl formate (PF) by different radicals (H/O(3P)/OH/HO2) were theoretically investigated. We calculated the reaction energetics for PF + H/O/OH using the composite method ROCBS-QB3//M06-2X/cc-pVTZ and that for PF + HO2 at the M06-2X/cc-pVTZ level of theory. The high-pressure limit rate constants were calculated using the transition state theory in conjunction with the 1-D hindered rotor approximation and tunneling correction. Three-parameter Arrhenius expressions of rate constants were provided over the temperature range of 500-2000 K. To validate the theoretical calculations, the overall rate constants of PF + OH → Products were measured in shock tube experiments at 968-1128 K and 1.16-1.25 atm using OH laser absorption. The predicted overall rate constants agree well with the shock tube data (within 15%) over the entire experimental conditions. Rate constant analysis indicates that the H-abstraction at the formic acid site dominates the PF consumption, whereas the contribution of H-abstractions at the aromatic ring increases with temperature. Additionally, comparisons of site-specific H-abstractions from PF with methyl formate, ethyl formate, benzene, and toluene were performed to understand the effects of the aromatic ring and side-chain substituent on H-abstraction rate constants.

Model calibration and validation for OFMSW and sewage sludge co-digestion reactors

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

Esposito, G., E-mail: giovanni.esposito@unicas.it; Frunzo, L., E-mail: luigi.frunzo@unina.it; Panico, A., E-mail: anpanico@unina.it

2011-12-15

Highlights: > Disintegration is the limiting step of the anaerobic co-digestion process. > Disintegration kinetic constant does not depend on the waste particle size. > Disintegration kinetic constant depends only on the waste nature and composition. > The model calibration can be performed on organic waste of any particle size. - Abstract: A mathematical model has recently been proposed by the authors to simulate the biochemical processes that prevail in a co-digestion reactor fed with sewage sludge and the organic fraction of municipal solid waste. This model is based on the Anaerobic Digestion Model no. 1 of the International Watermore » Association, which has been extended to include the co-digestion processes, using surface-based kinetics to model the organic waste disintegration and conversion to carbohydrates, proteins and lipids. When organic waste solids are present in the reactor influent, the disintegration process is the rate-limiting step of the overall co-digestion process. The main advantage of the proposed modeling approach is that the kinetic constant of such a process does not depend on the waste particle size distribution (PSD) and rather depends only on the nature and composition of the waste particles. The model calibration aimed to assess the kinetic constant of the disintegration process can therefore be conducted using organic waste samples of any PSD, and the resulting value will be suitable for all the organic wastes of the same nature as the investigated samples, independently of their PSD. This assumption was proven in this study by biomethane potential experiments that were conducted on organic waste samples with different particle sizes. The results of these experiments were used to calibrate and validate the mathematical model, resulting in a good agreement between the simulated and observed data for any investigated particle size of the solid waste. This study confirms the strength of the proposed model and calibration procedure, which can thus be used to assess the treatment efficiency and predict the methane production of full-scale digesters.« less

Evaluation of the MICAST #2-12 AI-7wt%Si Sample Directionally Solidified Aboard the International Space Station

NASA Technical Reports Server (NTRS)

Tewari, Surendra N.; Ghods, Masoud; Angart, Samuel G.; Lauer, Mark; Grugel, Richard N.; Poirier, David R.

2016-01-01

The US team of the European led "MIcrostructure Formation in CASTing of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions" (MICAST) program recently received a third Aluminum - 7wt% silicon alloy that was processed in the microgravity environment aboard the International Space Station. The sample, designated MICAST#2-12, was directionally solidified in the Solidification with Quench Furnace (SQF) at a constant rate of 40micometers/s through an imposed temperature gradient of 31K/cm. Procedures taken to evaluate the state of the sample prior to sectioning for metallographic analysis are reviewed and rational for measuring the microstructural constituents, in particular the primary dendrite arm spacing (Lambda (sub1)), is given. The data are presented, put in context with the earlier samples, and evaluated in view of a relevant theoretical model.

Effects of growth rate, size, and light availability on tree survival across life stages: a demographic analysis accounting for missing values and small sample sizes.

PubMed

Moustakas, Aristides; Evans, Matthew R

2015-02-28

Plant survival is a key factor in forest dynamics and survival probabilities often vary across life stages. Studies specifically aimed at assessing tree survival are unusual and so data initially designed for other purposes often need to be used; such data are more likely to contain errors than data collected for this specific purpose. We investigate the survival rates of ten tree species in a dataset designed to monitor growth rates. As some individuals were not included in the census at some time points we use capture-mark-recapture methods both to allow us to account for missing individuals, and to estimate relocation probabilities. Growth rates, size, and light availability were included as covariates in the model predicting survival rates. The study demonstrates that tree mortality is best described as constant between years and size-dependent at early life stages and size independent at later life stages for most species of UK hardwood. We have demonstrated that even with a twenty-year dataset it is possible to discern variability both between individuals and between species. Our work illustrates the potential utility of the method applied here for calculating plant population dynamics parameters in time replicated datasets with small sample sizes and missing individuals without any loss of sample size, and including explanatory covariates.

Monitoring survival rates of Swainson's Thrush Catharus ustulatus at multiple spatial scales

USGS Publications Warehouse

Rosenberg, D.K.; DeSante, D.F.; McKelvey, K.S.; Hines, J.E.

1999-01-01

We estimated survival rates of Swainson's Thrush, a common, neotropical, migratory landbird, at multiple spatial scales, using data collected in the western USA from the Monitoring Avian Productivity and Survivorship Programme. We evaluated statistical power to detect spatially heterogeneous survival rates and exponentially declining survival rates among spatial scales with simulated populations parameterized from results of the Swainson's Thrush analyses. Models describing survival rates as constant across large spatial scales did not fit the data. The model we chose as most appropriate to describe survival rates of Swainson's Thrush allowed survival rates to vary among Physiographic Provinces, included a separate parameter for the probability that a newly captured bird is a resident individual in the study population, and constrained capture probability to be constant across all stations. Estimated annual survival rates under this model varied from 0.42 to 0.75 among Provinces. The coefficient of variation of survival estimates ranged from 5.8 to 20% among Physiographic Provinces. Statistical power to detect exponentially declining trends was fairly low for small spatial scales, although large annual declines (3% of previous year's rate) were likely to be detected when monitoring was conducted for long periods of time (e.g. 20 years). Although our simulations and field results are based on only four years of data from a limited number and distribution of stations, it is likely that they illustrate genuine difficulties inherent to broadscale efforts to monitor survival rates of territorial landbirds. In particular, our results suggest that more attention needs to be paid to sampling schemes of monitoring programmes, particularly regarding the trade-off between precision and potential bias of parameter estimates at varying spatial scales.

Monitoring survival rates of Swainson's Thrush Catharus ustulatus at multiple spatial scales

USGS Publications Warehouse

Rosenberg, D.K.; DeSante, D.F.; McKelvey, K.S.; Hines, J.E.

1999-01-01

We estimated survival rates of Swainson's Thrush, a common, neotropical, migratory landbird, at multiple spatial scales, using data collected in the western USA from the Monitoring Avian Productivity and Survivorship Programme. We evaluated statistical power to detect spatially heterogeneous survival rates and exponentially declining survival rates among spatial scales with simulated populations parameterized from results of the Swainson's Thrush analyses. Models describing survival rates as constant across large spatial scales did not fit the data. The model we chose as most appropriate to describe survival rates of Swainson's Thrush allowed survival rates to vary among Physiographic Provinces, included a separate parameter for the probability that a newly captured bird is a resident individual in the study population, and constrained capture probability to be constant across all stations. Estimated annual survival rates under this model varied from 0.42 to 0.75 among Provinces. The coefficient of variation of survival estimates ranged from 5.8 to 20% among Physiographic Provinces. Statistical power to detect exponentially declining trends was fairly low for small spatial scales, although large annual declines (3% of previous year's rate) were likely to be detected when monitoring was conducted for long periods of time (e.g. 20 years). Although our simulations and field results are based on only four years of date from a limited number and distribution of stations, it is likely that they illustrate genuine difficulties inherent to broadscale efforts to monitor survival rates of territorial landbirds. In particular, our results suggest that more attention needs to be paid to sampling schemes of monitoring programmes particularly regarding the trade-off between precison and potential bias o parameter estimates at varying spatial scales.

ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. I. ALKALINE HYDROLYSIS

EPA Science Inventory

SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to allow the calculation of alkaline hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition state...

MICROBIAL TRANSFORMATION RATE CONSTANTS OF STRUCTURALLY DIVERSE MAN-MADE CHEMICALS

EPA Science Inventory

To assist in estimating microbially mediated transformation rates of man-made chemicals from their chemical structures, all second order rate constants that have been measured under conditions that make the values comparable have been extracted from the literature and combined wi...

Kinetic modeling of benzodiazepine receptor binding with PET and high specific activity [(11)C]Iomazenil in healthy human subjects.

PubMed

Bremner, J D; Horti, A; Staib, L H; Zea-Ponce, Y; Soufer, R; Charney, D S; Baldwin, R

2000-01-01

Quantitation of the PET benzodiazepine receptor antagonist, [(11)C]Iomazenil, using low specific activity radioligand was recently described. The purpose of this study was to quantitate benzodiazepine receptor binding in human subjects using PET and high specific activity [(11)C]Iomazenil. Six healthy human subjects underwent PET imaging following a bolus injection of high specific activity (>100 Ci/mmol) [(11)C]iomazenil. Arterial samples were collected at multiple time points after injection for measurement of unmetabolized total and nonprotein-bound parent compound in plasma. Time activity curves of radioligand concentration in brain and plasma were analyzed using two and three compartment model. Kinetic rate constants of transfer of radioligand between plasma, nonspecifically bound brain tissue, and specifically bound brain tissue compartments were fitted to the model. Values for fitted kinetic rate constants were used in the calculation of measures of benzodiazepine receptor binding, including binding potential (the ratio of receptor density to affinity), and product of BP and the fraction of free nonprotein-bound parent compound (V(3)'). Use of the three compartment model improved the goodness of fit in comparison to the two compartment model. Values for kinetic rate constants and measures of benzodiazepine receptor binding, including BP and V(3)', were similar to results obtained with the SPECT radioligand [(123)I]iomazenil, and a prior report with low specific activity [(11)C]Iomazenil. Kinetic modeling using the three compartment model with PET and high specific activity [(11)C]Iomazenil provides a reliable measure of benzodiazepine receptor binding. Synapse 35:68-77, 2000. Published 2000 Wiley-Liss, Inc.

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

Transverse spin relaxation and diffusion-constant measurements of spin-polarized 129Xe nuclei in the presence of a magnetic field gradient

PubMed Central

Liu, Xiaohu; Chen, Chang; Qu, Tianliang; Yang, Kaiyong; Luo, Hui

2016-01-01

The presence of a magnetic field gradient in a sample cell containing spin-polarized 129Xe atoms will cause an increased relaxation rate. We measured the transverse spin relaxation time of 129Xe verse the applied magnetic field gradient and the cell temperature. We then compared the different transverse spin relaxation behavior of dual isotopes of xenon (129Xe and 131Xe) due to magnetic field gradient in the same cell. The experiment results show the residual magnetic field gradient can be measured and compensated by applying a negative magnetic gradient in the sample cell. The transverse spin relaxation time of 129Xe could be increased 2–7 times longer when applying an appropriate magnetic field gradient. The experiment results can also be used to determine the diffusion constant of 129Xe in H2 and N2 to be 0.4 ± 0.26 cm2/sec and 0.12 ± 0.02 cm2/sec. The results are close with theoretical calculation. PMID:27049237

Estimation of absorption rate constant (ka) following oral administration by Wagner-Nelson, Loo-Riegelman, and statistical moments in the presence of a secondary peak.

PubMed

Mahmood, Iftekhar

2004-01-01

The objective of this study was to evaluate the performance of Wagner-Nelson, Loo-Reigelman, and statistical moments methods in determining the absorption rate constant(s) in the presence of a secondary peak. These methods were also evaluated when there were two absorption rates without a secondary peak. Different sets of plasma concentration versus time data for a hypothetical drug following one or two compartment models were generated by simulation. The true ka was compared with the ka estimated by Wagner-Nelson, Loo-Riegelman and statistical moments methods. The results of this study indicate that Wagner-Nelson, Loo-Riegelman and statistical moments methods may not be used for the estimation of absorption rate constants in the presence of a secondary peak or when absorption takes place with two absorption rates.

The rate constant of a quantum-diffusion-controlled bimolecular reaction

NASA Astrophysics Data System (ADS)

Bondarev, B. V.

1986-04-01

A quantum-mechanical equation is derived in the tight-bond approximation which describes the motion and chemical interaction of a pair of species A and B when their displacement in the matrix is caused by tunnelling. Within the framework of the discrete model of random walks, definitions are given of the probability and rate constant of a reaction A + B → P (products) proceeding in a condensed medium. A method is suggested for calculating the rate constant of a quantum-diffusion-controlled bimolecular reaction. By this method, an expression is obtained for the rate constant in the stationary spherically symmetrical case. An equation for the density matrix is also proposed which describes the motion and chemical interaction of a pair of species when the quantum and classical diffusion are competitive.

Molecular-dynamic study of the influence of temperature on the process of metallic nanocrystals fracture

NASA Astrophysics Data System (ADS)

Demianenko, A. M.; Golovnev, I. F.; Golovneva, E. I.

2017-10-01

The behavior of the fracture processes of a metal nanostructure under deformation in the temperature range 0-550 K was investigated by the molecular dynamics method. An ideal copper crystal was used as a sample in the form of a rectangular parallelepiped with the number of crystalline cells nx = 50, ny = nz = 5 along the corresponding axes. The deformation was carried out by uniaxial stretching of the sample between two clamps (movable and fixed) with a constant speed. The stretching rate varied from 50 to 500 m/s. To describe the interatomic interaction, the Voter many-body EAM potential was used. The effect of temperature on macro characteristics of fracture (the fracture place, the number of fragments formed, the stress on the clamps), and also on the kinetic characteristics (fracture rate, time of formation of maximum stress values on the clamps, mass transfer phenomena and formation of the fracture neck) were revealed.

Characterization of the strain-life fatigue properties of thin sheet metal using an optical extensometer

NASA Astrophysics Data System (ADS)

Zhang, Shuiqiang; Mao, Shuangshuang; Arola, Dwayne; Zhang, Dongsheng

2014-09-01

Characterizing the strain-life fatigue behavior of thin sheet metals is often challenging since the required specimens have short gauge lengths to avoid buckling, thereby preventing the use of conventional mechanical extensometers. To overcome this obstacle a microscopic optical imaging system has been developed to measure the strain amplitude during fatigue testing using Digital Image Correlation (DIC). A strategy for rapidly recording images is utilized to enable sequential image sampling rates of at least 10 frames per second (fps) using a general digital camera. An example of a complete strain-life fatigue test for thin sheet steel under constant displacement control is presented in which the corresponding strain within the gage section of the specimen is measured using the proposed imaging system. The precision in strain measurement is assessed and methods for improving the image sampling rates in dynamic testing are discussed.

Concentration dependence of biotransformation in fish liver S9: Optimizing substrate concentrations to estimate hepatic clearance for bioaccumulation assessment.

PubMed

Lo, Justin C; Allard, Gayatri N; Otton, S Victoria; Campbell, David A; Gobas, Frank A P C

2015-12-01

In vitro bioassays to estimate biotransformation rate constants of contaminants in fish are currently being investigated to improve bioaccumulation assessments of hydrophobic contaminants. The present study investigates the relationship between chemical substrate concentration and in vitro biotransformation rate of 4 environmental contaminants (9-methylanthracene, pyrene, chrysene, and benzo[a]pyrene) in rainbow trout (Oncorhynchus mykiss) liver S9 fractions and methods to determine maximum first-order biotransformation rate constants. Substrate depletion experiments using a series of initial substrate concentrations showed that in vitro biotransformation rates exhibit strong concentration dependence, consistent with a Michaelis-Menten kinetic model. The results indicate that depletion rate constants measured at initial substrate concentrations of 1 μM (a current convention) could underestimate the in vitro biotransformation potential and may cause bioconcentration factors to be overestimated if in vitro biotransformation rates are used to assess bioconcentration factors in fish. Depletion rate constants measured using thin-film sorbent dosing experiments were not statistically different from the maximum depletion rate constants derived using a series of solvent delivery-based depletion experiments for 3 of the 4 test chemicals. Multiple solvent delivery-based depletion experiments at a range of initial concentrations are recommended for determining the concentration dependence of in vitro biotransformation rates in fish liver fractions, whereas a single sorbent phase dosing experiment may be able to provide reasonable approximations of maximum depletion rates of very hydrophobic substances. © 2015 SETAC.

Real-time association rate constant measurement using combination tapered fiber-optic biosensor (CTFOB) dip-probes

NASA Astrophysics Data System (ADS)

Simmonds, Boris; Wang, Chun-Wei; Kapoor, Rakesh

2010-02-01

This document reports a novel method of measuring association rate constant (ka) for antibody-antigen interaction using evanescent wave-based combination tapered fiber-optic biosensor (CTFOB) dip-probes. The method was demonstrated by measuring association rate constant for bovine serum albumin (BSA) and anti-BSA antibody interaction. "Direct method" was used for detection; goat anti-BSA "capture" antibodies were immobilized on the probe surfaces while the antigen (BSA) was directly labeled with Alexa 488 dye. The probes were subsequently submerged in 3nM Labeled BSA in egg albumin (1 mg/ml). The fluorescence signal recorded was proportional to BSA anti-BSA conjugates and continuous signal was acquired suing a fiber optic spectrometer (Ocean Optics, Inc.). A 476 nm diode laser was use as an excitation source. Association constant was estimated from a plot of signal as a function of time. Measured association rate constant ka for the binding of BSA with anti-BSA at room temperature is (8.33 +/- 0.01) x 104 M-1s-1.

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, S. R.; Gyekenyesi, J. P.

2001-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress- rate/constant stress-rate testing (Case I loading), constant stress/constant stress-rate testing (Case II loading), and cyclic stress/constant stress-rate testing (Case III loading). Strength degradation due to slow crack growth and/or damage accumulation was determined numerically as a function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case I loading history, and alumina for the Case II loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the rest materials.

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2000-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress-rate/constant stress-rate testing (Case 1 loading), constant stress/constant stress-rate testing (Case 2 loading), and cyclic stress/constant stress-rate testing (Case 2 loading). Strength degradation due to slow crack growth and/or damage accumulation was determined numerically as a function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case 1 loading history, and alumina for the Case 3 loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the test materials.

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2000-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress-rate/constant stress-rate testing (Case I loading), constant stress/constant stress-rate testing (Case II loading), and cyclic stress/constant stress-rate testing (Case III loading). Strength degradation due to slow crack growth arid/or damage accumulation was determined numerically as a Function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case I loading history, and alumina for the Case II loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the test material&

Compressive Force Spectroscopy: From Living Cells to Single Proteins.

PubMed

Wang, Jiabin; Liu, Meijun; Shen, Yi; Sun, Jielin; Shao, Zhifeng; Czajkowsky, Daniel Mark

2018-03-23

One of the most successful applications of atomic force microscopy (AFM) in biology involves monitoring the effect of force on single biological molecules, often referred to as force spectroscopy. Such studies generally entail the application of pulling forces of different magnitudes and velocities upon individual molecules to resolve individualistic unfolding/separation pathways and the quantification of the force-dependent rate constants. However, a less recognized variation of this method, the application of compressive force, actually pre-dates many of these "tensile" force spectroscopic studies. Further, beyond being limited to the study of single molecules, these compressive force spectroscopic investigations have spanned samples as large as living cells to smaller, multi-molecular complexes such as viruses down to single protein molecules. Correspondingly, these studies have enabled the detailed characterization of individual cell states, subtle differences between seemingly identical viral structures, as well as the quantification of rate constants of functionally important, structural transitions in single proteins. Here, we briefly review some of the recent achievements that have been obtained with compressive force spectroscopy using AFM and highlight exciting areas of its future development.

A global benchmark study using affinity-based biosensors

PubMed Central

Rich, Rebecca L.; Papalia, Giuseppe A.; Flynn, Peter J.; Furneisen, Jamie; Quinn, John; Klein, Joshua S.; Katsamba, Phini S.; Waddell, M. Brent; Scott, Michael; Thompson, Joshua; Berlier, Judie; Corry, Schuyler; Baltzinger, Mireille; Zeder-Lutz, Gabrielle; Schoenemann, Andreas; Clabbers, Anca; Wieckowski, Sebastien; Murphy, Mary M.; Page, Phillip; Ryan, Thomas E.; Duffner, Jay; Ganguly, Tanmoy; Corbin, John; Gautam, Satyen; Anderluh, Gregor; Bavdek, Andrej; Reichmann, Dana; Yadav, Satya P.; Hommema, Eric; Pol, Ewa; Drake, Andrew; Klakamp, Scott; Chapman, Trevor; Kernaghan, Dawn; Miller, Ken; Schuman, Jason; Lindquist, Kevin; Herlihy, Kara; Murphy, Michael B.; Bohnsack, Richard; Andrien, Bruce; Brandani, Pietro; Terwey, Danny; Millican, Rohn; Darling, Ryan J.; Wang, Liann; Carter, Quincy; Dotzlaf, Joe; Lopez-Sagaseta, Jacinto; Campbell, Islay; Torreri, Paola; Hoos, Sylviane; England, Patrick; Liu, Yang; Abdiche, Yasmina; Malashock, Daniel; Pinkerton, Alanna; Wong, Melanie; Lafer, Eileen; Hinck, Cynthia; Thompson, Kevin; Primo, Carmelo Di; Joyce, Alison; Brooks, Jonathan; Torta, Federico; Bagge Hagel, Anne Birgitte; Krarup, Janus; Pass, Jesper; Ferreira, Monica; Shikov, Sergei; Mikolajczyk, Malgorzata; Abe, Yuki; Barbato, Gaetano; Giannetti, Anthony M.; Krishnamoorthy, Ganeshram; Beusink, Bianca; Satpaev, Daulet; Tsang, Tiffany; Fang, Eric; Partridge, James; Brohawn, Stephen; Horn, James; Pritsch, Otto; Obal, Gonzalo; Nilapwar, Sanjay; Busby, Ben; Gutierrez-Sanchez, Gerardo; Gupta, Ruchira Das; Canepa, Sylvie; Witte, Krista; Nikolovska-Coleska, Zaneta; Cho, Yun Hee; D’Agata, Roberta; Schlick, Kristian; Calvert, Rosy; Munoz, Eva M.; Hernaiz, Maria Jose; Bravman, Tsafir; Dines, Monica; Yang, Min-Hsiang; Puskas, Agnes; Boni, Erica; Li, Jiejin; Wear, Martin; Grinberg, Asya; Baardsnes, Jason; Dolezal, Olan; Gainey, Melicia; Anderson, Henrik; Peng, Jinlin; Lewis, Mark; Spies, Peter; Trinh, Quyhn; Bibikov, Sergei; Raymond, Jill; Yousef, Mohammed; Chandrasekaran, Vidya; Feng, Yuguo; Emerick, Anne; Mundodo, Suparna; Guimaraes, Rejane; McGirr, Katy; Li, Yue-Ji; Hughes, Heather; Mantz, Hubert; Skrabana, Rostislav; Witmer, Mark; Ballard, Joshua; Martin, Loic; Skladal, Petr; Korza, George; Laird-Offringa, Ite; Lee, Charlene S.; Khadir, Abdelkrim; Podlaski, Frank; Neuner, Phillippe; Rothacker, Julie; Rafique, Ashique; Dankbar, Nico; Kainz, Peter; Gedig, Erk; Vuyisich, Momchilo; Boozer, Christina; Ly, Nguyen; Toews, Mark; Uren, Aykut; Kalyuzhniy, Oleksandr; Lewis, Kenneth; Chomey, Eugene; Pak, Brian J.; Myszka, David G.

2013-01-01

To explore the variability in biosensor studies, 150 participants from 20 countries were given the same protein samples and asked to determine kinetic rate constants for the interaction. We chose a protein system that was amenable to analysis using different biosensor platforms as well as by users of different expertise levels. The two proteins (a 50-kDa Fab and a 60-kDa glutathione S-transferase [GST] antigen) form a relatively high-affinity complex, so participants needed to optimize several experimental parameters, including ligand immobilization and regeneration conditions as well as analyte concentrations and injection/dissociation times. Although most participants collected binding responses that could be fit to yield kinetic parameters, the quality of a few data sets could have been improved by optimizing the assay design. Once these outliers were removed, the average reported affinity across the remaining panel of participants was 620 pM with a standard deviation of 980 pM. These results demonstrate that when this biosensor assay was designed and executed appropriately, the reported rate constants were consistent, and independent of which protein was immobilized and which biosensor was used. PMID:19133223

The fracture strength of cryomilled 99.7 Al nanopowders consolidated by high frequency induction sintering

NASA Astrophysics Data System (ADS)

El-Danaf, Ehab A.; Baig, Muneer; Almajid, Abdulhakim A.; Soliman, Mahmoud S.

2014-08-01

Mechanical Attrition of metallic powders induces severe plastic deformation and consequently reduces the average grain size. Powders of 99.7 Al (45μm particle size), cryomilled for 7 hrs having a crystal size of ~ 20 nm, were consolidated by high frequency induction sintering under a constant pressure of 50 MPa and at two temperatures of 500 and 550 °C for two sintering dwell times of 1 and 3 minutes at a constant heating rate of 400 °C/min. The bright field TEM image and X-ray line broadening technique, for the cryomilled powders, were used to measure-the crystallite size. Simple compression at an initial strain rate of 10-4 s-1 was conducted at room temperature, 373 and 473 K, and the yield strength was documented and correlated with the sintering parameters. The as-received 99.7 Al powders-consolidated using one of the sintering parameters was used as a reference material to compare the mechanical properties. Hardness, density and crystal size of the consolidated sample, that gave the highest yield and fracture strength, were measured.

Regularized learning of linear ordered-statistic constant false alarm rate filters (Conference Presentation)

NASA Astrophysics Data System (ADS)

Havens, Timothy C.; Cummings, Ian; Botts, Jonathan; Summers, Jason E.

2017-05-01

The linear ordered statistic (LOS) is a parameterized ordered statistic (OS) that is a weighted average of a rank-ordered sample. LOS operators are useful generalizations of aggregation as they can represent any linear aggregation, from minimum to maximum, including conventional aggregations, such as mean and median. In the fuzzy logic field, these aggregations are called ordered weighted averages (OWAs). Here, we present a method for learning LOS operators from training data, viz., data for which you know the output of the desired LOS. We then extend the learning process with regularization, such that a lower complexity or sparse LOS can be learned. Hence, we discuss what 'lower complexity' means in this context and how to represent that in the optimization procedure. Finally, we apply our learning methods to the well-known constant-false-alarm-rate (CFAR) detection problem, specifically for the case of background levels modeled by long-tailed distributions, such as the K-distribution. These backgrounds arise in several pertinent imaging problems, including the modeling of clutter in synthetic aperture radar and sonar (SAR and SAS) and in wireless communications.

Constitutive Model Constants for Al7075-T651 and Al7075-T6

NASA Astrophysics Data System (ADS)

Brar, N. S.; Joshi, V. S.; Harris, B. W.

2009-12-01

Aluminum 7075-T651 and 7075-T6 are characterized at quasi-static and high strain rates to determine Johnson-Cook (J-C) strength and fracture model constants. Constitutive model constants are required as input to computer codes to simulate projectile (fragment) impact or similar impact events on structural components made of these materials. Although the two tempers show similar elongation at breakage, the ultimate tensile strength of T651 temper is generally lower than the T6 temper. Johnson-Cook strength model constants (A, B, n, C, and m) for the two alloys are determined from high strain rate tension stress-strain data at room and high temperature to 250°C. The Johnson-Cook fracture model constants are determined from quasi-static and medium strain rate as well as high temperature tests on notched and smooth tension specimens. Although the J-C strength model constants are similar, the fracture model constants show wide variations. Details of the experimental method used and the results for the two alloys are presented.

Bioconcentration kinetics of hydrophobic chemicals in different densities of Chlorella pyrenoidosa

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

Sijm, D.T.H.M.; Broersen, K.W.; Roode, D.F. de

1998-09-01

Algal density-dependent bioconcentration factors and rate constants were determined for a series of hydrophobic compounds in Chlorella pyrenoidosa. The apparent uptake rate constants of the hydrophobic compounds in algae varied between 200 and 710,000 L/kg/d, slightly increased with hydrophobicity within an experiment, were relatively constant for each algal density, and fitted fairly within existing allometric relationships. The bioavailability of the hydrophobic test compounds was significantly reduced by sorption by algal exudates. The sorption coefficients of the hydrophobic compounds to the algal exudates were between 80 and 1,200 L/kg, and were for most algal densities in the same order of magnitudemore » as the apparent bioconcentration factors to the algae, that is, between 80 and 60,200 L/kg. In typical field situations, however, no significant reduction in bioavailability due to exudates is expected. The apparent elimination rate constants of the hydrophobic compounds were high and fairly constant for each algal density and varied between 2 and 190/d. Because the apparent elimination rate constants were higher than the growth rate constant, and were independent of hydrophobicity, the authors speculated that other factors dominate excretion, such as exudate excretion-enhanced elimination. Bioconcentration factors increased less than proportional with hydrophobicity, i.e., the octanol-water partition coefficient [K{sub ow}]. The role of algal composition in bioconcentration is evaluated. Bioconcentrations (kinetics) of hydrophobic compounds that are determined at high algal densities should be applied with caution to field situations.« less

Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

NASA Astrophysics Data System (ADS)

Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

2017-12-01

In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than previously reported. This complex formation/chaperone mechanism is similar to that found for methanol, but different in that it occurs at room temperature. No precursor concentration dependence was found for the acetonylperoxy radical reactions. The equilibrium constant for the complex formation will also be presented.

Microstructure and Texture Evolution in Double-Cone Samples of Ti-6Al-4V Alloy with Colony Preform Microstructure

NASA Astrophysics Data System (ADS)

Yang, Kun Vanna; Lim, Chao Voon Samuel; Zhang, Kai; Sun, Jifeng; Yang, Xiaoguang; Huang, Aijun; Wu, Xinhua; Davies, Christopher H.

2015-12-01

Heat-treated Ti-6Al-4V forged bar with colony microstructure was machined into double-cone-shaped samples for a series of isothermal uniaxial compression test at 1223 K (950 °C) with varying constant crosshead speeds of 12.5, 1.25, and 0.125 mms-1 to a height reduction of 70 pct. Another set of samples deformed under the same conditions were heat treated at 1173 K (900 °C) for an hour followed by water quench. Finite element modeling was used to provide the strains, strain rates, and temperature profiles of the hot compression samples, and the microstructure and texture evolution was examined at four positions on each sample, representative of different strain ranges. Lamellae fragmentation and kinking are the dominant microstructural features at lower strain range up to a maximum of 2.0, whereas globularization dominates at strains above 2.0 for the as-deformed samples. The globularization fraction generally increases with strain, or by post-deformation heat treatment, but fluctuates at lower strain. The grain size of the globular α is almost constant with strain and maximizes for samples with the lowest crosshead speed due to the longer deformation time. The globular α grain also coarsens because of post-deformation heat treatment, with its size increasing with strain level. With respect to texture evolution, a basal transverse ring and another component 30 deg from ND is determined for samples deformed at 12.5 mms-1, which is consistent with the temperature increase to close to β-transus from simulation results. The texture type remains unchanged with its intensity increased and spreads with increasing strain.

Studies of the physical, yield and failure behavior of aliphatic polyketones

NASA Astrophysics Data System (ADS)

Karttunen, Nicole Renee

This thesis describes an investigation into the multiaxial yield and failure behavior of an aliphatic polyketone terpolymer. The behavior is studied as a function of: stress state, strain rate, temperature, and sample processing conditions. Results of this work include: elucidation of the behavior of a recently commercialized polymer, increased understanding of the effects listed above, insight into the effects of processing conditions on the morphology of the polyketone, and a description of yield strength of this material as a function of stress state, temperature, and strain rate. The first portion of work focuses on the behavior of a set of samples that are extruded under "common" processing conditions. Following this reference set of tests, the effect of testing this material at different temperatures is studied. A total of four different temperatures are examined. In addition, the effect of altering strain rate is examined. Testing is performed under pseudo-strain rate control at constant nominal octahedral shear strain rate for each failure envelope. A total of three different rates are studied. An extension of the first portion of work involves modeling the yield envelope. This is done by combining two approaches: continuum level and molecular level. The use of both methods allows the description of the yield envelope as a function of stress state, strain rate and temperature. The second portion of work involves the effects of processing conditions. For this work, additional samples are extruded with different shear and thermal histories than the "standard" material. One set of samples is processed with shear rates higher and lower than the standard. A second set is processed at higher and lower cooling rates than the standard. In order to understand the structural cause for changes in behavior with processing conditions, morphological characterization is performed on these samples. In particular, the effect on spherulitic structure is important. Residual stresses are also determined to be important to the behavior of the samples. Finally, an investigation into the crystalline structure of a family of aliphatic polyketones is performed. The effects of side group concentration and size are described.

Characterization of Full Set Material Constants and Their Temperature Dependence for Piezoelectric Materials Using Resonant Ultrasound Spectroscopy

PubMed Central

Tang, Liguo; Cao, Wenwu

2016-01-01

During the operation of high power electromechanical devices, a temperature rise is unavoidable due to mechanical and electrical losses, causing the degradation of device performance. In order to evaluate such degradations using computer simulations, full matrix material properties at elevated temperatures are needed as inputs. It is extremely difficult to measure such data for ferroelectric materials due to their strong anisotropic nature and property variation among samples of different geometries. Because the degree of depolarization is boundary condition dependent, data obtained by the IEEE (Institute of Electrical and Electronics Engineers) impedance resonance technique, which requires several samples with drastically different geometries, usually lack self-consistency. The resonant ultrasound spectroscopy (RUS) technique allows the full set material constants to be measured using only one sample, which can eliminate errors caused by sample to sample variation. A detailed RUS procedure is demonstrated here using a lead zirconate titanate (PZT-4) piezoceramic sample. In the example, the complete set of material constants was measured from room temperature to 120 °C. Measured free dielectric constants and  were compared with calculated ones based on the measured full set data, and piezoelectric constants d15 and d33 were also calculated using different formulas. Excellent agreement was found in the entire range of temperatures, which confirmed the self-consistency of the data set obtained by the RUS. PMID:27168336

The computational analysis and modelling of substitution effects on hydrolysis of formanilides in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Lukeš, Vladimír; Škorňa, Peter; Michalík, Martin; Klein, Erik

2017-11-01

Various para, meta and ortho substituted formanilides have been theoretically studied. For trans and cis-isomers of non-substituted formanilide, the calculated B3LYP vibration normal modes were analyzed. Substituent effect on the selected normal modes was described and the comparison with the available experimental data is presented. The calculated B3LYP proton affinities were correlated with Hammett constants, Fujita-Nishioka equation and the rate constants of the hydrolysis in 1 M HCl. Found linear dependences allow predictions of dissociation constants (pKBH+) and hydrolysis rate constants. Obtained results indicate that protonation of amide group may represent the rate determining step of acid catalyzed hydrolysis.

Computation of Kinetics for the Hydrogen/Oxygen System Using the Thermodynamic Method

NASA Technical Reports Server (NTRS)

Marek, C. John

1996-01-01

A new method for predicting chemical rate constants using thermodynamics has been applied to the hydrogen/oxygen system. This method is based on using the gradient of the Gibbs free energy and a single proportionality constant D to determine the kinetic rate constants. Using this method the rate constants for any gas phase reaction can be computed from thermodynamic properties. A modified reaction set for the H/O system is determined. A11 of the third body efficiencies M are taken to be unity. Good agreement was obtained between the thermodynamic method and the experimental shock tube data. In addition, the hydrogen bromide experimental data presented in previous work is recomputed with M's of unity.

Decomposition rates for hand-piled fuels

Treesearch

Clinton S. Wright; Alexander M. Evans; Joseph C. Restaino

2017-01-01

Hand-constructed piles in eastern Washington and north-central New Mexico were weighed periodically between October 2011 and June 2015 to develop decay-rate constants that are useful for estimating the rate of piled biomass loss over time. Decay-rate constants (k) were determined by fitting negative exponential curves to time series of pile weight for each site. Piles...

Indispensable finite time corrections for Fokker-Planck equations from time series data.

PubMed

Ragwitz, M; Kantz, H

2001-12-17

The reconstruction of Fokker-Planck equations from observed time series data suffers strongly from finite sampling rates. We show that previously published results are degraded considerably by such effects. We present correction terms which yield a robust estimation of the diffusion terms, together with a novel method for one-dimensional problems. We apply these methods to time series data of local surface wind velocities, where the dependence of the diffusion constant on the state variable shows a different behavior than previously suggested.

Temperature calibration of amino acid racemization: age implications for the Yuha skeleton

USGS Publications Warehouse

Bischoff, J.L.; Childers, W.M.

1979-01-01

D/L of aspartic acid ranged from 0.52 to 0.56 for femur samples of the Yuha skeleton. Subsurface temperature measurements made at the burial site indicate average annual temperature is 18??C and diagenetic temperature is 21.6??C. These data and a relation derived for the dependence of the aspartic acid rate constant on diagenetic temperature indicate an age of 23,600. The result is consistent with 14C and 230Th dating of calcrete found coating the bones. ?? 1979.

Rapid-Equilibrium Enzyme Kinetics

ERIC Educational Resources Information Center

Alberty, Robert A.

2008-01-01

Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. II. ACID AND GENERAL BASE CATALYZED HYDROLYSIS

EPA Science Inventory

SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

The Rate Constant for Fluorescence Quenching

ERIC Educational Resources Information Center

Legenza, Michael W.; Marzzacco, Charles J.

1977-01-01

Describes an experiment that utilizes fluorescence intensity measurements from a Spectronic 20 to determine the rate constant for the fluorescence quenching of various aromatic hydrocarbons by carbon tetrachloride in an ethanol solvent. (MLH)

Donor-Acceptor Distance Sampling Enhances the Performance of "Better than Nature" Nicotinamide Coenzyme Biomimetics.

PubMed

Geddes, Alexander; Paul, Caroline E; Hay, Sam; Hollmann, Frank; Scrutton, Nigel S

2016-09-07

Understanding the mechanisms of enzymatic hydride transfer with nicotinamide coenzyme biomimetics (NCBs) is critical to enhancing the performance of nicotinamide coenzyme-dependent biocatalysts. Here the temperature dependence of kinetic isotope effects (KIEs) for hydride transfer between "better than nature" NCBs and several ene reductase biocatalysts is used to indicate transfer by quantum mechanical tunneling. A strong correlation between rate constants and temperature dependence of the KIE (ΔΔH(⧧)) for H/D transfer implies that faster reactions with NCBs are associated with enhanced donor-acceptor distance sampling. Our analysis provides the first mechanistic insight into how NCBs can outperform their natural counterparts and emphasizes the need to optimize donor-acceptor distance sampling to obtain high catalytic performance from H-transfer enzymes.

Hemoglobin in Frankia, a Nitrogen-Fixing Actinomycete†

PubMed Central

Tjepkema, John D.; Cashon, Robert E.; Beckwith, Jason; Schwintzer, Christa R.

2002-01-01

Frankia strain CcI3 grown in culture produced a hemoglobin which had optical absorption bands typical of a hemoglobin and a molecular mass of 14.1 kDa. Its equilibrium oxygen binding constant was 274 nM, the oxygen dissociation rate constant was 56 s−1, and the oxygen association rate constant was 206 μM−1 s−1. PMID:11976149

Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

PubMed

Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan

2017-10-01

Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (K sampler/soil ) and the uptake rate constant (k u ) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both K sampler/soil and k u values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both K sampler/soil and k u values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Terrestrial growth of lead-tin-telluride by techniques related to low G growth

NASA Technical Reports Server (NTRS)

Jesser, W. A.

1982-01-01

A modified Bridgman-Stockbarger furnace was constructed for a study of the solidification of silver, germanium and lead-tin-telluride. The melt-solid interface position with respect to the furnace and its temperature profile was determined by measuring the discontinuity in the slope of temperature as a function of position in the melt and in the solid. The results show that the interface position of the semiconductors germanium and lead-tin-telluride was essentially constant with respect to the furnace and hence the growth rate was constant and equal to the sample translation rate of 0.046 cm/min and 0.178 cm/min in each case. The metal, silver, on the other hand showed a continuous interface migration toward the hot zone of the furnace and always exhibited a growth rate which was higher than the ampoule translation rate. The K sub L/K sub S ratio of lead-tin-telluride was determined to be 2.33 + or - 0.06 where K sub L,S denotes the thermal conductivity of the liquid, solid respectively. The value of K sub L was calculated to be about 0.054 Watt 0.1 cm 0.1 K. The diffusion boundary layer thickness was calculated for lead-tin-telluride to be about 0.05 cm using a liquid diffusivity of .00007 sq cm/sec.

Mechanical impedance of soil crusts and water content in loamy soils

NASA Astrophysics Data System (ADS)

Josa March, Ramon; Verdú, Antoni M. C.; Mas, Maria Teresa

2013-04-01

Soil crust development affects soil water dynamics and soil aeration. Soil crusts act as mechanical barriers to fluid flow and, as their mechanical impedance increases with drying, they also become obstacles to seedling emergence. As a consequence, the emergence of seedling cohorts (sensitive seeds) might be reduced. However, this may be of interest to be used as an effective system of weed control. Soil crusting is determined by several factors: soil texture, rain intensity, sedimentation processes, etc. There are different ways to characterize the crusts. One of them is to measure their mechanical impedance (MI), which is linked to their moisture level. In this study, we measured the evolution of the mechanical impedance of crusts formed by three loamy soil types (clay loam, loam and sandy clay loam, USDA) with different soil water contents. The aim of this communication was to establish a mathematical relationship between the crust water content and its MI. A saturated soil paste was prepared and placed in PVC cylinders (50 mm diameter and 10 mm height) arranged on a plastic tray. Previously the plastic tray was sprayed with a hydrophobic liquid to prevent the adherence of samples. The samples on the plastic tray were left to air-dry under laboratory conditions until their IM was measured. To measure IM, a food texture analyzer was used. The equipment incorporates a mobile arm, a load cell to apply force and a probe. The arm moves down vertically at a constant rate and the cylindrical steel probe (4 mm diameter) penetrates the soil sample vertically at a constant rate. The equipment is provided with software to store data (time, vertical distance and force values) at a rate of up to 500 points per second. Water content in crust soil samples was determined as the loss of weight after oven-drying (105°C). From the results, an exponential regression between MI and the water content was obtained (determination coefficient very close to 1). This methodology allows the prediction of the potential mechanical behaviour of soil crusts generated during soil drying, from initial saturated soil conditions (e.g. waterlogging conditions).

Chlorine decay and bacterial inactivation kinetics in drinking water in the tropics.

PubMed

Thøgersen, J; Dahi, E

1996-09-01

The decay of free chlorine (Cl2) and combined chlorine (mostly monochloramine: NH2Cl) and the inactivation of bacteria was examined in Dar es Salaam, Tanzania. Batch experiments, pilot-scale pipe experiments and full-scale pipe experiments were carried out to establish the kinetics for both decay and inactivation, and to compare the two disinfectants for use under tropical conditions. The decay of both disinfectants closely followed first order kinetics, with respect to the concentration of both disinfectant and disinfectant-consuming substances. Bacterial densities exhibited a kinetic pattern consisting of first order inactivation with respect to the density of the bacteria and the concentration of the disinfectant, and first order growth with respect to the bacterial density. The disinfection kinetic model takes the decaying concentration of the disinfectant into account. The decay rate constant for free chlorine was 114 lg(-1)h(-1), while the decay rate constant for combined chlorine was 1.84 lg(-1)h(-1) (1.6% of the decay rate for free chlorine). The average concentration of disinfectant consuming substances in the water phase was 2.6 mg Cl2/l for free chlorine and 5.6 mg NH2Cl/l for combined chlorine. The decay rate constant and the concentration of disinfectant consuming substances when water was pumped through pipes, depended on whether or not chlorination was continuous. Combined chlorine especially could clean the pipes of disinfectant consuming substances. The inactivation rate constant λ, was estimated at 3.06×10(4) lg(-1)h(-1). Based on the inactivation rate constant, and a growth rate constant determined in a previous study, the critical concentration of free chlorine was found to be 0.08 mg Cl2/l. The critical concentration is a value below which growth rates dominate over inactivation.

Impact of transverse and longitudinal dispersion on first-order degradation rate constant estimation

NASA Astrophysics Data System (ADS)

Stenback, Greg A.; Ong, Say Kee; Rogers, Shane W.; Kjartanson, Bruce H.

2004-09-01

A two-dimensional analytical model is employed for estimating the first-order degradation rate constant of hydrophobic organic compounds (HOCs) in contaminated groundwater under steady-state conditions. The model may utilize all aqueous concentration data collected downgradient of a source area, but does not require that any data be collected along the plume centerline. Using a least squares fit of the model to aqueous concentrations measured in monitoring wells, degradation rate constants were estimated at a former manufactured gas plant (FMGP) site in the Midwest U.S. The estimated degradation rate constants are 0.0014, 0.0034, 0.0031, 0.0019, and 0.0053 day -1 for acenaphthene, naphthalene, benzene, ethylbenzene, and toluene, respectively. These estimated rate constants were as low as one-half those estimated with the one-dimensional (centerline) approach of Buscheck and Alcantar [Buscheck, T.E., Alcantar, C.M., 1995. Regression techniques and analytical solutions to demonstrate intrinsic bioremediation. In: Hinchee, R.E., Wilson, J.T., Downey, D.C. (Eds.), Intrinsic Bioremediation, Battelle Press, Columbus, OH, pp. 109-116] which does not account for transverse dispersivity. Varying the transverse and longitudinal dispersivity values over one order of magnitude for toluene data obtained from the FMGP site resulted in nearly a threefold variation in the estimated degradation rate constant—highlighting the importance of reliable estimates of the dispersion coefficients for obtaining reasonable estimates of the degradation rate constants. These results have significant implications for decision making and site management where overestimation of a degradation rate may result in remediation times and bioconversion factors that exceed expectations. For a complex source area or non-steady-state plume, a superposition of analytical models that incorporate longitudinal and transverse dispersion and time may be used at sites where the centerline method would not be applicable.

18 CFR 806.12 - Constant-rate aquifer testing.

Code of Federal Regulations, 2014 CFR

2014-04-01

... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

18 CFR 806.12 - Constant-rate aquifer testing.

Code of Federal Regulations, 2012 CFR

2012-04-01

... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

18 CFR 806.12 - Constant-rate aquifer testing.

Code of Federal Regulations, 2011 CFR

2011-04-01

... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

18 CFR 806.12 - Constant-rate aquifer testing.

Code of Federal Regulations, 2013 CFR

2013-04-01

... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

Oxidation of Benzoin by Hexacyanoferrate (III)

ERIC Educational Resources Information Center

Jarrar, Adil A.; El-Zaru, Ribhi

1977-01-01

Describes a kinetics experiment in which the student measures both a second-order rate constant and an overall third-order rate constant for the oxidation of benzoin to benzil in an alkaline medium. (MLH)

Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses

PubMed Central

Ballard, Andrew; Ahmad, Hiwa O.; Narduolo, Stefania; Rosa, Lucy; Chand, Nikki; Cosgrove, David A.; Varkonyi, Peter; Asaad, Nabil; Tomasi, Simone

2017-01-01

Abstract Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. PMID:29072355

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

PubMed

González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

2014-07-15

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.

A COMPARATIVE ANALYSIS OF THE SUPERNOVA LEGACY SURVEY SAMPLE WITH ΛCDM AND THE R{sub h}=ct UNIVERSE

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

Wei, Jun-Jie; Wu, Xue-Feng; Melia, Fulvio

The use of Type Ia supernovae (SNe Ia) has thus far produced the most reliable measurement of the expansion history of the universe, suggesting that ΛCDM offers the best explanation for the redshift–luminosity distribution observed in these events. However, analysis of other kinds of sources, such as cosmic chronometers, gamma-ray bursts, and high-z quasars, conflicts with this conclusion, indicating instead that the constant expansion rate implied by the R{sub h} = ct universe is a better fit to the data. The central difficulty with the use of SNe Ia as standard candles is that one must optimize three or fourmore » nuisance parameters characterizing supernova (SN) luminosities simultaneously with the parameters of an expansion model. Hence, in comparing competing models, one must reduce the data independently for each. We carry out such a comparison of ΛCDM and the R{sub h} = ct universe using the SN Legacy Survey sample of 252 SN events, and show that each model fits its individually reduced data very well. However, since R{sub h} = ct has only one free parameter (the Hubble constant), it follows from a standard model selection technique that it is to be preferred over ΛCDM, the minimalist version of which has three (the Hubble constant, the scaled matter density, and either the spatial curvature constant or the dark energy equation-of-state parameter). We estimate using the Bayes Information Criterion that in a pairwise comparison, the likelihood of R{sub h} = ct is ∼90%, compared with only ∼10% for a minimalist form of ΛCDM, in which dark energy is simply a cosmological constant. Compared to R{sub h} = ct, versions of the standard model with more elaborate parametrizations of dark energy are judged to be even less likely.« less

The response of excess 230Th and extraterrestrial 3He to sediment redistribution at the Blake Ridge, western North Atlantic

NASA Astrophysics Data System (ADS)

McGee, David; Marcantonio, Franco; McManus, Jerry F.; Winckler, Gisela

2010-10-01

The constant-flux proxies excess 230Th ( 230Th xs) and extraterrestrial 3He ( 3He ET) are commonly used to calculate sedimentary mass accumulation rates and to quantify lateral advection of sediment at core sites. In settings with significant lateral input or removal of sediment, these calculations depend on the assumption that concentrations of 230Th xs and 3He ET are the same in both advected sediment and sediment falling through the water column above the core site. Sediment redistribution is known to fractionate grain sizes, preferentially transporting fine grains; though relatively few studies have examined the grain size distribution of 230Th xs and 3He ET, presently available data indicate that both are concentrated in fine grains, suggesting that fractionation during advection may bias accumulation rate and lateral advection estimates based on these proxies. In this study, we evaluate the behavior of 230Th xs and 3He ET in Holocene and last glacial samples from two cores from the Blake Ridge, a drift deposit in the western North Atlantic. At the end of the last glacial period, both cores received large amounts of laterally transported sediment enriched in fine-grained material. We find that accumulation rates calculated by normalization to 230Th and 3He are internally consistent despite large spatial and temporal differences in sediment advection. Our analyses of grain size fractions indicate that ~ 70% of 3He ET-bearing grains are in the < 20 μm fraction, with roughly equal amounts in the < 4 and 4-20 μm fractions. 230Th xs is concentrated in <4-μm grains relative to 4- to 20-μm grains by approximately a factor of 2 in Holocene samples and by a much larger factor (averaging a factor of 10) in glacial samples. Despite these enrichments of both constant-flux proxies in fine particles, the fidelity of 230Th- and 3He-based accumulation rate estimates appears to be preserved even in settings with extreme sediment redistribution, perhaps due to the cohesive behavior of fine particles in marine settings.

Constant Flux of Spatial Niche Partitioning through High-Resolution Sampling of Magnetotactic Bacteria.

PubMed

He, Kuang; Gilder, Stuart A; Orsi, William D; Zhao, Xiangyu; Petersen, Nikolai

2017-10-15

Magnetotactic bacteria (MTB) swim along magnetic field lines in water. They are found in aquatic habitats throughout the world, yet knowledge of their spatial and temporal distribution remains limited. To help remedy this, we took MTB-bearing sediment from a natural pond, mixed the thoroughly homogenized sediment into two replicate aquaria, and then counted three dominant MTB morphotypes (coccus, spirillum, and rod-shaped MTB cells) at a high spatiotemporal sampling resolution: 36 discrete points in replicate aquaria were sampled every ∼30 days over 198 days. Population centers of the MTB coccus and MTB spirillum morphotypes moved in continual flux, yet they consistently inhabited separate locations, displaying significant anticorrelation. Rod-shaped MTB were initially concentrated toward the northern end of the aquaria, but at the end of the experiment, they were most densely populated toward the south. The finding that the total number of MTB cells increased over time during the experiment argues that population reorganization arose from relative changes in cell division and death and not from migration. The maximum net growth rates were 10, 3, and 1 doublings day -1 and average net growth rates were 0.24, 0.11, and 0.02 doublings day -1 for MTB cocci, MTB spirilla, and rod-shaped MTB, respectively; minimum growth rates for all three morphotypes were -0.03 doublings day -1 Our results suggest that MTB cocci and MTB spirilla occupy distinctly different niches: their horizontal positioning in sediment is anticorrelated and under constant flux. IMPORTANCE Little is known about the horizontal distribution of magnetotactic bacteria in sediment or how the distribution changes over time. We therefore measured three dominant magnetotactic bacterium morphotypes at 36 places in two replicate aquaria each month for 7 months. We found that the spatial positioning of population centers changed over time and that the two most abundant morphotypes (MTB cocci and MTB spirilla) occupied distinctly different niches in the aquaria. Maximum and average growth and death rates were quantified for each of the three morphotypes based on 72 sites that were measured six times. The findings provided novel insight into the differential behavior of noncultured magnetotactic bacteria. Copyright © 2017 American Society for Microbiology.

Effects of air temperature and velocity on the drying kinetics and product particle size of starch from arrowroot (Maranta arundinacae)

NASA Astrophysics Data System (ADS)

Caparanga, Alvin R.; Reyes, Rachael Anne L.; Rivas, Reiner L.; De Vera, Flordeliza C.; Retnasamy, Vithyacharan; Aris, Hasnizah

2017-11-01

This study utilized the 3k factorial design with k as the two varying factors namely, temperature and air velocity. The effects of temperature and air velocity on the drying rate curves and on the average particle diameter of the arrowroot starch were investigated. Extracted arrowroot starch samples were dried based on the designed parameters until constant weight was obtained. The resulting initial moisture content of the arrowroot starch was 49.4%. Higher temperatures correspond to higher drying rates and faster drying time while air velocity effects were approximately negligible or had little effect. Drying rate is a function of temperature and time. The constant rate period was not observed for the drying rate of arrowroot starch. The drying curves were fitted against five mathematical models: Lewis, Page, Henderson and Pabis, Logarithmic and Midili. The Midili Model was the best fit for the experimental data since it yielded the highest R2 and the lowest RSME values for all runs. Scanning electron microscopy (SEM) was used for qualitative analysis and for determination of average particle diameter of the starch granules. The starch granules average particle diameter had a range of 12.06 - 24.60 μm. The use of ANOVA proved that particle diameters for each run varied significantly with each other. And, the Taguchi Design proved that high temperatures yield lower average particle diameter, while high air velocities yield higher average particle diameter.

ESTIMATION OF MICROBIAL REDUCTIVE TRANSFORMATION RATES FOR CHLORINATED BENZENES AND PHENOLS USING A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP APPROACH

EPA Science Inventory

A set of literature data was used to derive several quantitative structure-activity relationships (QSARs) to predict the rate constants for the microbial reductive dehalogenation of chlorinated aromatics. Dechlorination rate constants for 25 chloroaromatics were corrected for th...

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, A.B. Jr.; Levy, I.S.; Trimble, D.J.; Lanning, D.D.; Gerber, F.S.

1990-04-10

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-based materials is disclosed. Samples of zirconium-based materials having different compositions and/or fabrication methods are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280 to 316 C). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hydriding for the same materials when subject to in-reactor (irradiated) corrosion. 1 figure.

Effect of surface curvature on diffusion-limited reactions on a curved surface

NASA Astrophysics Data System (ADS)

Eun, Changsun

2017-11-01

To investigate how the curvature of a reactive surface can affect reaction kinetics, we use a simple model in which a diffusion-limited bimolecular reaction occurs on a curved surface that is hollowed inward, flat, or extended outward while keeping the reactive area on the surface constant. By numerically solving the diffusion equation for this model using the finite element method, we find that the rate constant is a non-linear function of the surface curvature and that there is an optimal curvature providing the maximum value of the rate constant, which indicates that a spherical reactant whose entire surface is reactive (a uniformly reactive sphere) is not the most reactive species for a given reactive surface area. We discuss how this result arises from the interplay between two opposing effects: the exposedness of the reactive area to its partner reactants, which causes the rate constant to increase as the curvature increases, and the competition occurring on the reactive surface, which decreases the rate constant. This study helps us to understand the role of curvature in surface reactions and allows us to rationally design reactants that provide a high reaction rate.

Biodegradation testing of chemicals with high Henry's constants - Separating mass and effective concentration reveals higher rate constants.

PubMed

Birch, Heidi; Andersen, Henrik R; Comber, Mike; Mayer, Philipp

2017-05-01

During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects test results and (2) can be accounted for by combining equilibrium partition and dynamic biodegradation models. An aqueous mixture of 9 (semi)volatile chemicals was first generated using passive dosing and then diluted with environmental surface water producing concentrations in the ng/L to μg/L range. After incubation for 2 h to 4 weeks, automated Headspace Solid Phase Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relatively to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Biodegradation rate constants relating to the chemical in the water phase, k water , were generally a factor 1 to 11 times higher than biodegradation rate constants relating to the total mass of chemical in the test system, k system , with one exceptional factor of 72 times for a long chain alkane. True water phase degradation rate constants were found (i) more appropriate for risk assessment than test system rate constants, (ii) to facilitate extrapolation to other air-water systems and (iii) to be better defined input parameters for aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

Leaching kinetics of bottom ash waste as a source of calcium ions.

PubMed

Koech, Lawrence; Everson, Ray; Neomagus, Hein; Rutto, Hilary

2015-02-01

Bottom ash is a waste material from coal-fired power plants, and it is known to contain elements that are potentially toxic at high concentration levels when disposed in landfills. This study investigates the use of bottom ash as a partial substitute sorbent for wet flue gas desulfurization (FGD) processes by focusing on its leaching kinetics in adipic acid. This was studied basing on the shrinking core model that was applied to the experimental data obtained by the authors presented at the International Conference on Industrial, Manufacturing, Automation and Mechanical Engineering, Johannesburg, South Africa, November 27-28, 2013) on dissolution of bottom ash. The leaching rate constant was obtained from different reaction variables, namely, temperature, pH, acid concentration, and solid-to-liquid ratio, that could affect the leaching process. The solid sample of bottom ash was characterized at different leaching periods using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that solid-to-liquid ratio had a significant effect on the leaching rate constant when compared with other variables. The leaching kinetics showed that diffusion through the product layer was the rate-controlling step during leaching, and the activation energy for the process was found to be 18.92 kJ/mol.

Electrical properties of Apollo 17 rock and soil samples and a summary of the electrical properties of lunar material at 450 MHz frequency

NASA Technical Reports Server (NTRS)

Gold, T.; Bilson, E.; Baron, R. L.

1976-01-01

The dielectric constant and the voltage absorption length was measured for four Apollo 17 soil samples (73241, 74220, 75061, 76501) and for two Apollo 17 rock samples (76315 and 79135) at 450 MHz frequency. The dielectric constant and absorption length measurements made on the lunar samples are reviewed and related to the transition element concentration in these samples. The significance of the laboratory measurements for radar observations is discussed.

Calcite dissolution rate spectra measured by in situ digital holographic microscopy.

PubMed

Brand, Alexander S; Feng, Pan; Bullard, Jeffrey W

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ , real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s -1 . Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates ( e.g. , 0.1 µmol m -2 s -1 to 0.3 µmol m -2 s -1 ). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

Calcite dissolution rate spectra measured by in situ digital holographic microscopy

NASA Astrophysics Data System (ADS)

Brand, Alexander S.; Feng, Pan; Bullard, Jeffrey W.

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ, real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s-1. Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates (e.g., 0.1 μmol m-2 s-1 to 0.3 μmol m-2 s-1). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis. [quantitative structure-activity relationship, complete neglect of differential overlap

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Enhancement of dielectric constant at percolation threshold in CaCu3 Ti4 O12 ceramic fabricated by both solid state and sol-gel process

NASA Astrophysics Data System (ADS)

Mukherjee, Rupam; Garcia, Lucia; Lawes, Gavin; Nadgorny, Boris

2014-03-01

We have investigated the large dielectric enhancement at the percolation threshold by introducing metallic RuO2 grains into a matrix of CaCu3Ti4O12 (CCTO). The intrinsic response of the pure CCTO samples prepared by solid state and sol-gel processes results in a dielectric constant on the order of 104 and 103 respectively with low loss. Scanning electron microscopy and energy dispersive x-ray spectroscopy indicate that a difference in the thickness of the copper oxide enriched grain boundary is the main reason for the different dielectric properties between these two samples. Introducing RuO2 metallic fillers in these CCTO samples yields a sharp increase of the dielectric constant at percolation threshold fc, by a factor of 6 and 3 respectively. The temperature dependence of the dielectric constant shows that the dipolar relaxation plays an important role in enhancing dielectric constant in composite systems.

A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

ERIC Educational Resources Information Center

Sattar, Simeen

2011-01-01

Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

Tracking the entry routes of hepatitis C virus as a surrogate of HIV in an HIV-low prevalence country, the Philippines.

PubMed

Kageyama, Seiji; Agdamag, Dorothy May D; Alesna, Evelyn T; Abellanosa-Tac-An, Ilya P; Corpuz, Aura C; Telan, Elizabeth Freda O; Que, Ernesto R; Leaño, Prisca Susan A; Jereza, Lourdes D; Emphasis, Yvonne Ethyl E; Prasetyo, Afiono A; Tanimoto, Tomoaki; Ichimura, Hiroshi

2009-07-01

From 2002 to 2007, 1,590 individuals were enrolled in an active surveillance program conducted in Metro Cebu, Philippines, where the anti-HCV-positive rate was significantly and constantly high among injecting drug users (83%, 793/960; 71-88%), especially among those living in downtown (89%, 683/770; 87-100%), despite the extremely low percentage of anti-HIV-positives (0.34%, 3/874). Sampling areas were then enlarged nationwide and the number of samples increased to 2,645 at the end of 2007. A total of 444 samples were positive for HCV RNA. Phylogenetic analysis based on NS5B and E1-E2 regions revealed that the most dominant HCV subtype was 1a, and followed by 2b, 2a, and 1b, and that the HCV strains had the largest variety in Metro Manila and its vicinity (P < 0.01). Interestingly, subtype 1b was detected solely in Metro Manila, and four HCV strains collected in this area showed higher homology to specific foreign strains retrieved from the Genbank/EMBL/DDBJ database with bootstrap values of 68-95% comparing with other strains analyzed in this nationwide study. These data suggest that HCV strains may be introduced occasionally into the Philippines possibly through Metro Manila as a main entry point. Considering the fact that an HIV epidemic started primarily via contaminated needle sharing in Asia, the constantly high rate of HCV infections and the newly introduced foreign HCV strains in the absence of HIV epidemic warrant further investigation on HCV entry and spread for early detection of an HIV epidemic in the Philippines. Copyright 2009 Wiley-Liss, Inc.

DCE-MRI-Derived Volume Transfer Constant (Ktrans) and DWI Apparent Diffusion Coefficient as Predictive Markers of Short- and Long-Term Efficacy of Chemoradiotherapy in Patients With Esophageal Cancer.

PubMed

Ye, Zhi-Min; Dai, Shu-Jun; Yan, Feng-Qin; Wang, Lei; Fang, Jun; Fu, Zhen-Fu; Wang, Yue-Zhen

2018-01-01

This study aimed to evaluate both the short- and long-term efficacies of chemoradiotherapy in relation to the treatment of esophageal cancer . This was achieved through the use of dynamic contrast-enhanced magnetic resonance imaging-derived volume transfer constant and diffusion weighted imaging-derived apparent diffusion coefficient . Patients with esophageal cancer were assigned into the sensitive and resistant groups based on respective efficacies in chemoradiotherapy. Dynamic contrast-enhanced magnetic resonance imaging and diffusion weighted imaging were used to measure volume transfer constant and apparent diffusion coefficient, while computed tomography was used to calculate tumor size reduction rate. Pearson correlation analyses were conducted to analyze correlation between volume transfer constant, apparent diffusion coefficient, and the tumor size reduction rate. Receiver operating characteristic curve was constructed to analyze the short-term efficacy of volume transfer constant and apparent diffusion coefficient, while Kaplan-Meier curve was employed for survival rate analysis. Cox proportional hazard model was used for the risk factors for prognosis of patients with esophageal cancer. Our results indicated reduced levels of volume transfer constant, while increased levels were observed in ADC min , ADC mean , and ADC max following chemoradiotherapy. A negative correlation was determined between ADC min , ADC mean , and ADC max , as well as in the tumor size reduction rate prior to chemoradiotherapy, whereas a positive correlation was uncovered postchemoradiotherapy. Volume transfer constant was positively correlated with tumor size reduction rate both before and after chemoradiotherapy. The 5-year survival rate of patients with esophageal cancer having high ADC min , ADC mean , and ADC max and volume transfer constant before chemoradiotherapy was greater than those with respectively lower values. According to the Cox proportional hazard model, ADC mean , clinical stage, degree of differentiation, and tumor stage were all confirmed as being independent risk factors in regard to the prognosis of patients with EC. The findings of this study provide evidence suggesting that volume transfer constant and apparent diffusion coefficient as being tools allowing for the evaluation of both the short- and long-term efficacies of chemoradiotherapy esophageal cancer treatment.

Numerical Solution of Dyson Brownian Motion and a Sampling Scheme for Invariant Matrix Ensembles

NASA Astrophysics Data System (ADS)

Li, Xingjie Helen; Menon, Govind

2013-12-01

The Dyson Brownian Motion (DBM) describes the stochastic evolution of N points on the line driven by an applied potential, a Coulombic repulsion and identical, independent Brownian forcing at each point. We use an explicit tamed Euler scheme to numerically solve the Dyson Brownian motion and sample the equilibrium measure for non-quadratic potentials. The Coulomb repulsion is too singular for the SDE to satisfy the hypotheses of rigorous convergence proofs for tamed Euler schemes (Hutzenthaler et al. in Ann. Appl. Probab. 22(4):1611-1641, 2012). Nevertheless, in practice the scheme is observed to be stable for time steps of O(1/ N 2) and to relax exponentially fast to the equilibrium measure with a rate constant of O(1) independent of N. Further, this convergence rate appears to improve with N in accordance with O(1/ N) relaxation of local statistics of the Dyson Brownian motion. This allows us to use the Dyson Brownian motion to sample N× N Hermitian matrices from the invariant ensembles. The computational cost of generating M independent samples is O( MN 4) with a naive scheme, and O( MN 3log N) when a fast multipole method is used to evaluate the Coulomb interaction.

Creep of trabecular bone from the human proximal tibia

PubMed Central

Novitskaya, Ekaterina; Zin, Carolyn; Chang, Neil; Cory, Esther; Chen, Peter; D'Lima, Darryl; Sah, Robert L.; McKittrick, Joanna

2014-01-01

Creep is the deformation that occurs under a prolonged, sustained load and can lead to permanent damage in bone. Creep in bone is a complex phenomenon and varies with type of loading and local mechanical properties. Human trabecular bone samples from proximal tibia were harvested from a 71-year old female cadaver with osteoporosis. The samples were initially subjected to one cycle load up to 1% strain to determine the creep load. Samples were then loaded in compression under a constant stress for two hours and immediately unloaded. All tests were conducted with the specimens soaked in phosphate buffered saline with proteinase inhibitors at 37°C. Steady state creep rate and final creep strain were estimated from mechanical testing and compared with published data. The steady state creep rate correlated well with values obtained from bovine tibial and human vertebral trabecular bone, and was higher for lower density samples. Tissue architecture was analyzed by micro-computed tomography (μCT) both before and after creep testing to assess creep deformation and damage accumulated. Quantitative morphometric analysis indicated that creep induced changes in trabecular separation and the structural model index. A main mode of deformation was bending of trabeculae. PMID:24857486

Determination of the kinetics of guanine nucleotide exchange on EF-Tu and EF-Ts: continuing uncertainties.

PubMed

Manchester, Keith L

2004-01-30

An analysis is made of the rate constants for the reactions involving the interactions of EF-Tu, EF-Ts, GDP, and GTP recently derived by Gromadski et al. [Biochemistry 41 (2002) 162]. Though their measured values appear to allow a reasonable rate of nucleotide exchange sufficient to support rates of protein synthesis in vivo, their data underestimate the thermodynamic barrier involved in nucleotide exchange and therefore cannot be considered definitive. A kinetic scheme consistent with the thermodynamic barrier can be achieved by modification of various rate constants, particularly of those involving the release of EF-Ts from EF-Tu.GTP.EF-Ts, but such constants are markedly different from what are experimentally observed. It thus remains impossible at present satisfactorily to model guanine nucleotide exchange on EF-Tu, catalysed by EF-Ts by a double displacement mechanism, with experimentally derived rate constants. Metabolic control analysis has been applied to determine the degree of flux control of the different steps in the pathway.

Revised estimates for ozone reduction by shuttle operation

NASA Technical Reports Server (NTRS)

Potter, A. E.

1978-01-01

Previous calculations by five different modeling groups of the effect of space shuttle operations on the ozone layer yielded an estimate of 0.2 percent ozone reduction for the Northern Hemisphere at 60 launches per year. Since these calculations were made, the accepted rate constant for the reaction between hydroperoxyl and nitric oxide to yield hydroxyl and nitrogen dioxide, HO2 + NO yields OH + NO2, was revised upward by more than an order of magnitude, with a resultant increase in the predicted ozone reduction for chlorofluoromethanes by a factor of approximately 2. New calculations of the shuttle effect were made with use of the new rate constant data, again by five different modeling groups. The new value of the shuttle effect on the ozone layer was found to be 0.25 percent. The increase resulting from the revised rate constant is considerably less for space shuttle operations than for chlorofluoromethane production, because the new rate constant also increases the calculated rate of downward transport of shuttle exhaust products out of the stratosphere.

Comparative Studies on the Toxicokinetics of Benzo[a]pyrene in Pinctada martensii and Perna viridis.

PubMed

Wang, Haihua; Cui, Lili; Cheng, Huamin; Zhang, Yu; Diao, Xiaoping; Wang, Jun

2017-05-01

Research on the kinetics of Benzo[a]pyrene (B[a]P) bioaccumulation in the clam Pinctada martensii and mussel Perna viridis showed that the initial rate of uptake was directly related to the PAH concentrations in the ambient environment. The uptake and depuration rate constants were different at the four B[a]P exposure levels, which indicated that the toxicokinetic rate constants mainly depended on the exposure levels of pollutants to the environment. In addition, the uptake rate constants of B[a]P were higher than the depuration rate constants in the entire experiment. The comparison demonstrated that mussels release B[a]P more rapidly than clams. The bioconcentration factors (BCFs) of B[a]P varied from 3335 to 12892 in the clam and 2373-6235 in the mussel. These findings on the bioaccumulation kinetics for petroleum hydrocarbons, in association with the critical body residue, will be valuable when choosing sensitive organisms to assess the potential ecotoxicological risk to the marine environment.

Electronic polarizability of light crude oil from optical and dielectric studies

NASA Astrophysics Data System (ADS)

George, A. K.; Singh, R. N.

2017-07-01

In the present paper we report the temperature dependence of density, refractive indices and dielectric constant of three samples of crude oils. The API gravity number estimated from the temperature dependent density studies revealed that the three samples fall in the category of light oil. The measured data of refractive index and the density are used to evaluate the polarizability of these fluids. Molar refractive index and the molar volume are evaluated through Lorentz-Lorenz equation. The function of the refractive index, FRI , divided by the mass density ρ, is a constant approximately equal to one-third and is invariant with temperature for all the samples. The measured values of the dielectric constant decrease linearly with increasing temperature for all the samples. The dielectric constant estimated from the refractive index measurements using Lorentz-Lorentz equation agrees well with the measured values. The results are promising since all the three measured properties complement each other and offer a simple and reliable method for estimating crude oil properties, in the absence of sufficient data.

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.

Post Quench Ductility Evaluation of Zircaloy-4 and Select Iron Alloys under Design Basis and Extended LOCA Conditions

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

Yan, Yong; Keiser, James R; Terrani, Kurt A

2014-01-01

Oxidation experiments were conducted at 1200 C in flowing steam with tubing specimens of Zircaloy-4, 317, 347 stainless steels, and the commercial FeCrAl alloy APMT. The purpose was to determine the oxidation behavior and post quench ductility of these alloys under postulated loss-of-coolant accident conditions. The parabolic rate constant for Zircaloy-4 tubing samples at 1200 were determined to be k = 2.173 107 g2/cm4/s C, in excellent agreement with the Cathcart-Pawel correlation. The APMT alloy experienced the slowest oxidation rate among all materials examined in this work. The ductility of post quenched samples was evaluated by ring compression tests atmore » 135 C. For Zircaloy-4, the ductile to brittle transition occurs at an equivalent cladding reacted (ECR) of 19.3%. SS-347 was still ductile after being oxidized for 2400 s (CP-ECR 50%), but the maximum load was reduced significantly owing to the metal layer thickness reduction. No ductility decrease was observed for the post-quenched APMT samples oxidized up to four hours.« less

Post-quench ductility evaluation of Zircaloy-4 and select iron alloys under design basis and extended LOCA conditions

NASA Astrophysics Data System (ADS)

Yan, Y.; Keiser, J. R.; Terrani, K. A.; Bell, G. L.; Snead, L. L.

2014-05-01

Oxidation experiments were conducted at 1200 °C in flowing steam with tubing specimens of Zircaloy-4, 317, 347 stainless steels, and the commercial FeCrAl alloy APMT. The purpose was to determine the oxidation behavior and post-quench ductility under postulated and extended LOCA conditions. The parabolic rate constant for Zircaloy-4 tubing samples at 1200 °C was determined to be k = 2.173 × 107 g2/cm4/s, in excellent agreement with the Cathcart-Pawel correlation. The APMT alloy experienced the slowest oxidation rate among all materials examined in this work. The ductility of post-quenched samples was evaluated by ring compression tests at 135 °C. For Zircaloy-4, the ductile to brittle transition occurs at an equivalent cladding reacted (ECR) of 19.3%. SS-347 was still ductile after being oxidized for 2400 s (CP-ECR ≈ 50%), but the maximum load was reduced significantly owing to the metal layer thickness reduction. No ductility decrease was observed for the post-quenched APMT samples oxidized up to 4 h.

Guided-wave approaches to spectrally selective energy absorption

NASA Technical Reports Server (NTRS)

Stegeman, G. I.; Burke, J. J.

1987-01-01

Results of experiments designed to demonstrate spectrally selective absorption in dielectric waveguides on semiconductor substrates are reported. These experiments were conducted with three waveguides formed by sputtering films of PSK2 glass onto silicon-oxide layers grown on silicon substrates. The three waveguide samples were studied at 633 and 532 nm. The samples differed only in the thickness of the silicon-oxide layer, specifically 256 nm, 506 nm, and 740 nm. Agreement between theoretical predictions and measurements of propagation constants (mode angles) of the six or seven modes supported by these samples was excellent. However, the loss measurements were inconclusive because of high scattering losses in the structures fabricated (in excess of 10 dB/cm). Theoretical calculations indicated that the power distribution among all the modes supported by these structures will reach its steady state value after a propagation length of only 1 mm. Accordingly, the measured loss rates were found to be almost independent of which mode was initially excited. The excellent agreement between theory and experiment leads to the conclusion that low loss waveguides confirm the predicted loss rates.

Multivariate curve resolution-alternating least squares and kinetic modeling applied to near-infrared data from curing reactions of epoxy resins: mechanistic approach and estimation of kinetic rate constants.

PubMed

Garrido, M; Larrechi, M S; Rius, F X

2006-02-01

This study describes the combination of multivariate curve resolution-alternating least squares with a kinetic modeling strategy for obtaining the kinetic rate constants of a curing reaction of epoxy resins. The reaction between phenyl glycidyl ether and aniline is monitored by near-infrared spectroscopy under isothermal conditions for several initial molar ratios of the reagents. The data for all experiments, arranged in a column-wise augmented data matrix, are analyzed using multivariate curve resolution-alternating least squares. The concentration profiles recovered are fitted to a chemical model proposed for the reaction. The selection of the kinetic model is assisted by the information contained in the recovered concentration profiles. The nonlinear fitting provides the kinetic rate constants. The optimized rate constants are in agreement with values reported in the literature.

Rate constant for the reaction of atomic chlorine with methane

NASA Technical Reports Server (NTRS)

Lin, C. L.; Leu, M. T.; Demore, W. B.

1978-01-01

The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295 K

NASA Astrophysics Data System (ADS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-02-01

When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.

Predicting DNA hybridization kinetics from sequence

NASA Astrophysics Data System (ADS)

Zhang, Jinny X.; Fang, John Z.; Duan, Wei; Wu, Lucia R.; Zhang, Angela W.; Dalchau, Neil; Yordanov, Boyan; Petersen, Rasmus; Phillips, Andrew; Zhang, David Yu

2018-01-01

Hybridization is a key molecular process in biology and biotechnology, but so far there is no predictive model for accurately determining hybridization rate constants based on sequence information. Here, we report a weighted neighbour voting (WNV) prediction algorithm, in which the hybridization rate constant of an unknown sequence is predicted based on similarity reactions with known rate constants. To construct this algorithm we first performed 210 fluorescence kinetics experiments to observe the hybridization kinetics of 100 different DNA target and probe pairs (36 nt sub-sequences of the CYCS and VEGF genes) at temperatures ranging from 28 to 55 °C. Automated feature selection and weighting optimization resulted in a final six-feature WNV model, which can predict hybridization rate constants of new sequences to within a factor of 3 with ∼91% accuracy, based on leave-one-out cross-validation. Accurate prediction of hybridization kinetics allows the design of efficient probe sequences for genomics research.

Direct Determination of the Base-Pair Force Constant of DNA from the Acoustic Phonon Dispersion of the Double Helix

NASA Astrophysics Data System (ADS)

van Eijck, L.; Merzel, F.; Rols, S.; Ollivier, J.; Forsyth, V. T.; Johnson, M. R.

2011-08-01

Quantifying the molecular elasticity of DNA is fundamental to our understanding of its biological functions. Recently different groups, through experiments on tailored DNA samples and numerical models, have reported a range of stretching force constants (0.3 to 3N/m). However, the most direct, microscopic measurement of DNA stiffness is obtained from the dispersion of its vibrations. A new neutron scattering spectrometer and aligned, wet spun samples have enabled such measurements, which provide the first data of collective excitations of DNA and yield a force constant of 83N/m. Structural and dynamic order persists unchanged to within 15 K of the melting point of the sample, precluding the formation of bubbles. These findings are supported by large scale phonon and molecular dynamics calculations, which reconcile hard and soft force constants.

Immersion freezing of internally and externally mixed mineral dust species analyzed by stochastic and deterministic models

NASA Astrophysics Data System (ADS)

Wong, B.; Kilthau, W.; Knopf, D. A.

2017-12-01

Immersion freezing is recognized as the most important ice crystal formation process in mixed-phase cloud environments. It is well established that mineral dust species can act as efficient ice nucleating particles. Previous research has focused on determination of the ice nucleation propensity of individual mineral dust species. In this study, the focus is placed on how different mineral dust species such as illite, kaolinite and feldspar, initiate freezing of water droplets when present in internal and external mixtures. The frozen fraction data for single and multicomponent mineral dust droplet mixtures are recorded under identical cooling rates. Additionally, the time dependence of freezing is explored. Externally and internally mixed mineral dust droplet samples are exposed to constant temperatures (isothermal freezing experiments) and frozen fraction data is recorded based on time intervals. Analyses of single and multicomponent mineral dust droplet samples include different stochastic and deterministic models such as the derivation of the heterogeneous ice nucleation rate coefficient (J­­het), the single contact angle (α) description, the α-PDF model, active sites representation, and the deterministic model. Parameter sets derived from freezing data of single component mineral dust samples are evaluated for prediction of cooling rate dependent and isothermal freezing of multicomponent externally or internally mixed mineral dust samples. The atmospheric implications of our findings are discussed.

Evidence for a Terpene-Based Food Chain in the Gulf of Alaska

PubMed Central

Button, D. K.

1984-01-01

A mixture of 14C-terpenes was prepared from conifer seedlings and introduced into fresh seawater samples taken near Seward, Alaska. Initial rates of oxidation by the indigenous bacteria were linear and faster than the rates of toluene oxidation. Turnover times were 4 to 19 days. Autoradiographic measurements with 3H-terpenes indicated that at least 10% of the 0.6 × 109 to 2.7 × 109 bacteria per liter present could catabolize terpenes. The rate of terpene oxidation, 24 μg of terpenes per g of cells per h with 3 μg of terpenes added per liter, was a constant function of bacterial biomass. The specific affinity of the process was estimated to be between 8.1 and 81 liters/g of cells per h, indicating a high state of induction and the probable presence of terpenes. Terpene-oxidizing bacteria were grown on [14C]alanine and added to fresh seawater samples. Transfer of the bacterial radioactivity into larger particles at a rate of 146 pg/liter per h from the 2.3 × 109 organisms added indicated that any terpenes present would participate in the food chain. PMID:16346658

An investigation on polycyclic aromatic hydrocarbon emissions from pulverized coal combustion systems

PubMed

Pisupati; Wasco; Scaroni

2000-05-29

Results from a series of tests conducted to study the emission of polynuclear or polycyclic aromatic hydrocarbons (PAHs) from bench-scale and small industrial, water-tube boiler are discussed. A Middle Kittanning, and Upper Freeport seam coals were used in the study. Samples were extracted from the reactor outlet and from the inlet and outlet sides of the research boiler's (RB) baghouse using EPA promulgated methods.Only acenaphthene and fluoranthene were detected in down-fired combustor (DFC) samples. In addition to these two, naphthalene was detected in the RB samples. Emission factors ranged from 80 to 320 &mgr;g/kg of fuel fired. Although there were minor trends in the emissions' data, given the reproducibility limits for PAH compounds, no significant differences were found in the emissions with respect to the fuel type or form (pulverized coal (PC) vs. coal-water slurry fuel (CWSF), and raw vs. cleaned coal) and firing conditions (high and low excess air). The PAH emissions showed a decrease with increase in the firing rate.A bench-scale drop-tube reactor (DTR) was used to study the effects of temperature and residence time on PAH formation. The results revealed near constant PAH concentrations in the solid-phase samples, while the PAH concentrations in the vapor-phase samples increased as a function of temperature. At a temperature of around 1300 degrees C, the rate of PAH formation was exceeded by the rate of PAH oxidation, and PAH concentrations in the vapor phase began to decrease.

Modular Aero-Propulsion System Simulation

NASA Technical Reports Server (NTRS)

Parker, Khary I.; Guo, Ten-Huei

2006-01-01

The Modular Aero-Propulsion System Simulation (MAPSS) is a graphical simulation environment designed for the development of advanced control algorithms and rapid testing of these algorithms on a generic computational model of a turbofan engine and its control system. MAPSS is a nonlinear, non-real-time simulation comprising a Component Level Model (CLM) module and a Controller-and-Actuator Dynamics (CAD) module. The CLM module simulates the dynamics of engine components at a sampling rate of 2,500 Hz. The controller submodule of the CAD module simulates a digital controller, which has a typical update rate of 50 Hz. The sampling rate for the actuators in the CAD module is the same as that of the CLM. MAPSS provides a graphical user interface that affords easy access to engine-operation, engine-health, and control parameters; is used to enter such input model parameters as power lever angle (PLA), Mach number, and altitude; and can be used to change controller and engine parameters. Output variables are selectable by the user. Output data as well as any changes to constants and other parameters can be saved and reloaded into the GUI later.

Atmospheric fallout radionuclides in peatland from Southern Poland.

PubMed

Mróz, Tomasz; Łokas, Edyta; Kocurek, Justyna; Gąsiorek, Michał

2017-09-01

Two peat profiles were collected in a peat bog located in Southern Poland and their geochronology were determined using 210 Pb, 238,239+240 Pu and 137 Cs radiometric techniques. The 210 Pb chronologies were established using the constant rate of supply model (CRS) and are in good agreement with the Pu isotopes and 137 Cs time markers. Maximum activities of Pu isotopes were found at a depth corresponding to the early 1960s, which is the period characterized by the maximum nuclear weapon tests. The results showed that the 210 Pb method is the most accurate technique for the determination age and accumulation rate of a peat. The next part of this study calculated linear accumulation rates by analyzing 238,239+240 Pu and 137 Cs vertical distributions in the profiles. Activities of fallout isotopes were also measured in plants covering the peatland. The highest activities of 137 Cs and 210 Pb were found in Calluna vulgaris samples, and 239+240 Pu were found only in two samples (C. vulgaris and leaves of Oxycoccus quadripelatus). Copyright © 2017 Elsevier Ltd. All rights reserved.

Time-dependent brittle deformation (creep) at Mt. Etna volcano

NASA Astrophysics Data System (ADS)

Heap, M. J.; Baud, P.; Meredith, P. G.; Vinciguerra, S.; Bell, A. F.; Main, I. G.

2009-04-01

Mt. Etna is the largest and most active volcano in Europe. Time-dependent weakening mechanisms, leading to slow fracturing, have been shown to act during pre-eruptive patterns of flank eruptions at Mt. Etna volcano. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts one of the biggest hydrogeologic reservoirs of Sicily (Ogniben, 1966). The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as ‘brittle creep'. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short-term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data not only demonstrates that basalt creeps in the brittle regime but also that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Furthermore, stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time-to-failure properties of the basaltic volcanic pile.

Time-dependent Brittle Deformation in Etna Basalt

NASA Astrophysics Data System (ADS)

Heap, M. J.; Baud, P.; Meredith, P. G.; Vinciguerra, S.; Bell, A. F.; Main, I. G.

2008-12-01

Mt Etna is the largest and most active volcano in Europe. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts one of the biggest hydrogeologic reservoirs of Sicily (Ogniben, 1966). Pre-eruptive patterns of flank eruptions, closely monitored by means of ground deformation and seismicity, revealed the slow development of fracture systems at different altitudes, marked by repeated bursts of seismicity and accelerating/decelerating deformation patterns acting over the scale of months to days. The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as 'brittle creep'. Stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short- term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data demonstrate that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time- to-failure properties of the basaltic volcanic pile.

Time-dependent brittle deformation at Mt. Etna volcano

NASA Astrophysics Data System (ADS)

Baud, Patrick; Heap, Michael; Meredith, Philip; Vinciguerra, Sergio; Bell, Andrew; Main, Ian

2010-05-01

Time-dependent weakening mechanisms, leading to slow fracturing, are likely to act during the build up to flank eruptions at Mt. Etna volcano and are potentially a primary control on pre-eruptive patterns of seismicity and deformation. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts a large water reservoir (Ogniben, 1966). The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as ‘brittle creep'. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short-term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data not only demonstrates that basalt creeps in the brittle regime but also that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Furthermore, stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations and inverse seismicity plots using our experimental AE data. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time-to-failure properties of the basaltic volcanic pile.

Sampling frequency for water quality variables in streams: Systems analysis to quantify minimum monitoring rates.

PubMed

Chappell, Nick A; Jones, Timothy D; Tych, Wlodek

2017-10-15

Insufficient temporal monitoring of water quality in streams or engineered drains alters the apparent shape of storm chemographs, resulting in shifted model parameterisations and changed interpretations of solute sources that have produced episodes of poor water quality. This so-called 'aliasing' phenomenon is poorly recognised in water research. Using advances in in-situ sensor technology it is now possible to monitor sufficiently frequently to avoid the onset of aliasing. A systems modelling procedure is presented allowing objective identification of sampling rates needed to avoid aliasing within strongly rainfall-driven chemical dynamics. In this study aliasing of storm chemograph shapes was quantified by changes in the time constant parameter (TC) of transfer functions. As a proportion of the original TC, the onset of aliasing varied between watersheds, ranging from 3.9-7.7 to 54-79 %TC (or 110-160 to 300-600 min). However, a minimum monitoring rate could be identified for all datasets if the modelling results were presented in the form of a new statistic, ΔTC. For the eight H + , DOC and NO 3 -N datasets examined from a range of watershed settings, an empirically-derived threshold of 1.3(ΔTC) could be used to quantify minimum monitoring rates within sampling protocols to avoid artefacts in subsequent data analysis. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Effects of constant and fluctuating temperature on the development of the oriental fruit moth, Grapholita molesta (Lepidoptera: Tortricidae).

PubMed

Chen, Z-Z; Xu, L-X; Li, L-L; Wu, H-B; Xu, Y-Y

2018-06-21

The oriental fruit moth, Grapholita molesta, is an important pest in many commercial orchards including apple, pear and peach orchards, and responsible for substantial economic losses every year. To help in attaining a comprehensive and thorough understanding of the ecological tolerances of G. molesta, we collected life history data of individuals reared on apples under different constant temperature regimes and compared the data with moths reared under a variable outdoor temperature environment. Because G. molesta individuals reared at a constant 25°C had the heaviest pupal weight, the highest survival rate from egg to adult, highest finite rate of increase, and greatest fecundity, 25°C was considered as the optimum developmental temperature. The G. molesta population reared at a constant 31°C had the shortest development time, lowest survival rate and fecundity, resulting in population parameters of r < 0, λ < 1, lead to negative population growth. The population parameters r and λ reared under fluctuating temperature were higher than that reared under constant temperatures, the mean generation time (T) was shorter than it was in all of the constant temperatures treatments. This would imply that the outdoor G. molesta population would have a higher population growth potential and faster growth rate than indoor populations raised at constant temperatures. G. molesta moths reared under fluctuating temperature also had a higher fertility than moths reared under constant temperatures (except at 25°C). Our findings indicated that the population raised under outdoor fluctuating temperature conditions had strong environment adaptiveness.

Does phenomenological kinetics provide an adequate description of heterogeneous catalytic reactions?

PubMed

Temel, Burcin; Meskine, Hakim; Reuter, Karsten; Scheffler, Matthias; Metiu, Horia

2007-05-28

Phenomenological kinetics (PK) is widely used in the study of the reaction rates in heterogeneous catalysis, and it is an important aid in reactor design. PK makes simplifying assumptions: It neglects the role of fluctuations, assumes that there is no correlation between the locations of the reactants on the surface, and considers the reacting mixture to be an ideal solution. In this article we test to what extent these assumptions damage the theory. In practice the PK rate equations are used by adjusting the rate constants to fit the results of the experiments. However, there are numerous examples where a mechanism fitted the data and was shown later to be erroneous or where two mutually exclusive mechanisms fitted well the same set of data. Because of this, we compare the PK equations to "computer experiments" that use kinetic Monte Carlo (kMC) simulations. Unlike in real experiments, in kMC the structure of the surface, the reaction mechanism, and the rate constants are known. Therefore, any discrepancy between PK and kMC must be attributed to an intrinsic failure of PK. We find that the results obtained by solving the PK equations and those obtained from kMC, while using the same rate constants and the same reactions, do not agree. Moreover, when we vary the rate constants in the PK model to fit the turnover frequencies produced by kMC, we find that the fit is not adequate and that the rate constants that give the best fit are very different from the rate constants used in kMC. The discrepancy between PK and kMC for the model of CO oxidation used here is surprising since the kMC model contains no lateral interactions that would make the coverage of the reactants spatially inhomogeneous. Nevertheless, such inhomogeneities are created by the interplay between the rate of adsorption, of desorption, and of vacancy creation by the chemical reactions.

A new approach using coagulation rate constant for evaluation of turbidity removal

NASA Astrophysics Data System (ADS)

Al-Sameraiy, Mukheled

2017-06-01

Coagulation-flocculation-sedimentation processes for treating three levels of bentonite synthetic turbid water using date seeds (DS) and alum (A) coagulants were investigated in the previous research work. In the current research, the same experimental results were used to adopt a new approach on a basis of using coagulation rate constant as an investigating parameter to identify optimum doses of these coagulants. Moreover, the performance of these coagulants to meet (WHO) turbidity standard was assessed by introducing a new evaluating criterion in terms of critical coagulation rate constant (kc). Coagulation rate constants (k2) were mathematically calculated in second order form of coagulation process for each coagulant. The maximum (k2) values corresponded to doses, which were obviously to be considered as optimum doses. The proposed criterion to assess the performance of coagulation process of these coagulants was based on the mathematical representation of (WHO) turbidity guidelines in second order form of coagulation process stated that (k2) for each coagulant should be ≥ (kc) for each level of synthetic turbid water. For all tested turbid water, DS coagulant could not satisfy it. While, A coagulant could satisfy it. The results obtained in the present research are exactly in agreement with the previous published results in terms of finding optimum doses for each coagulant and assessing their performances. On the whole, it is recommended considering coagulation rate constant to be a new approach as an indicator for investigating optimum doses and critical coagulation rate constant to be a new evaluating criterion to assess coagulants' performance.

[Grades evaluation of Phellodendri chinensis cortex pieces based on quality constant].

PubMed

Deng, Zhe; Jiao, Meng-Jiao; Zhang, Jun; Zhang, Qing; Cui, Wen-Jin; Shen, Li; Cheng, Jin-Tang; Liu, An

2017-09-01

Quality constant is a comprehensive grades evaluation method for traditional Chinese medicine decoction pieces, which is better but based on traditional way. In this paper, a new grading mode for Phellodendri chinensis pieces was established based on quality constant evaluation method. The results showed that the range of relative quality constant for 15 batches of different samples was from 0.41 to 0.96. As customary, if these samples were divided into three grades: the relative quality constant shall be ≥0.77 for first grade; <0.77 but ≥0.48 for the second grade; and ＜0.48 for the third grade. This research indicated that the quality constant mode can be used to effectively grade the P. chinensis pieces in a scientific, reasonable, objective and specific way. Simultaneously, it provided a beneficial reference for grading cortex herbal pieces or medicines. Copyright© by the Chinese Pharmaceutical Association.

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

Shyam, Amit; Lara-Curzio, Edgar

This paper reports on the langatate (LGT) elastic constants measured from room temperature (25 C) to 1100 C using resonant ultrasound spectroscopy (RUS). The constants were extracted by fitting the resonant peaks with those calculated by Lagrangian mechanics at each temperature where the RUS measurements were taken. In addition, the RUS technique was used to extract the piezoelectric constants in the 25 C to 120 C temperature range. This work also publishes a set of temperature coefficients for the elastic constants up to 1100 C. For the measurements, six parallelepiped LGT samples were aligned, cut, ground, and polished at themore » University of Maine. The samples were aligned to two different crystal orientations, to increase the reliability of the constant fitting. The extraction of LGT elastic constants up to 1100 C presented in this paper represents a critical step towards the design and fabrication of LGT acoustic wave devices for high temperature and harsh environment applications.« less

A new experimental correlation for non-Newtonian behavior of COOH-DWCNTs/antifreeze nanofluid

NASA Astrophysics Data System (ADS)

Izadi, Farhad; Ranjbarzadeh, Ramin; Kalbasi, Rasool; Afrand, Masoud

2018-04-01

In this paper, the rheological behavior of nano-antifreeze consisting of 50%vol. water, 50%vol. ethylene glycol and different quantities of functionalized double walled carbon nanotubes has been investigated experimentally. Initially, nano-antifreeze samples were prepared with solid volume fractions of 0.05, 0.1, 0.2, 0.4, 0.6, 0.8 and 1% using two-step method. Then, the dynamic viscosity of the nano-antifreeze samples was measured at different shear rates and temperatures. At this stage, the results showed that base fluid had the Newtonian behavior, while the behavior of all nano-antifreeze samples was non-Newtonian. Since the behavior of the samples was similar to power law model, it was attempted to find the constants of this model including consistency index and power law index. Therefore, using the measured viscosity and shear rates, consistency index and power law index were obtained by curve-fitting method. The obtained values showed that consistency index amplified with increasing volume fraction, while reduced with enhancing temperature. Besides, the obtained values for power law index were less than 1 for all samples which means shear thinning behavior. Lastly, new correlations were suggested to estimate the consistency index and power law index using curve-fitting.

Pharmacokinetics of doxycycline in laying hens after intravenous and oral administration.

PubMed

Yang, F; Si, H B; Wang, Y Q; Zhao, Z S; Zhou, B H; Hao, X Q

2016-08-01

The pharmacokinetics of doxycycline in laying hens was investigated after a single intravenous (IV) or an oral (PO) dose at 20 mg/kg body weight. The concentrations of doxycycline in plasma samples were determined by high-performance liquid chromatography with an ultraviolet detector, and pharmacokinetic parameters were calculated using a compartmental model method. The disposition of doxycycline after one single IV injection was best described by a two-compartment open model and the main pharmacokinetic parameters were as follows: volume of distribution (Vd) was 865.15 ± 127.64 ml/kg, distribution rate constant (α) was (2.28 ± 0.38) 1/h, elimination rate constant (β) was 0.08 ± 0.02 1/h and total body clearance (Cl) was104.11 ± 18.32 ml/h/kg, while after PO administration, the concentration versus time curve was best described by a one-compartment open model and absorption rate constant (Ka), peak concentration (Cmax), time to reach Cmax (tmax) and absolute bioavailability (F) were 2.55 ± 1.40 1/h, 5.88 ± 0.70 μg/ml, 1.73 ± 0.75 h and 52.33%, respectively. The profile of doxycycline exhibited favourable pharmacokinetic characteristics in laying hens, such as quick absorption and slow distribution and elimination, though oral bioavailability was relatively low. A multiple-dosing regimen (a dose of 20 mg/kg/d for 3 consecutive days) of doxycycline was recommended to treat infections in laying hens. But a further study should be conducted to determine the withdrawal time of doxycycline in eggs.

A real-time bioluminescent HTS method for measuring protein kinase activity influenced neither by ATP concentration nor by luciferase inhibition.

PubMed

Lundin, Arne; Eriksson, Jonas

2008-08-01

The firefly luciferin-luciferase reaction has been used to set up an assay for protein kinase based on measuring ATP consumption rate as the first-order rate constant for the kinase reaction. The assay obviates the problems encountered with previous bioluminescent protein kinase assays such as interference with the luciferase reaction from library compounds, nonlinear standard curves, and limited dynamic ranges. In the assay described in the present paper luciferase and luciferin are present during the entire kinase reaction, and the light emission can be measured continuously. In an HTS situation the light emission is measured only twice, i.e., initially and after a predetermined time. After a fivefold reduction of the ATP concentration a Z' value of 0.96 was obtained. Light emission data from samples with kinase are normalized with light emission data from blanks without kinase. First-order rate constants for the kinase reaction calculated from normalized light emission are not affected by a moderate degree of inactivation of luciferase and luciferin during the measuring time. The constants have the same value at all ATP concentrations much lower than the K(m) of the luciferase and the kinase. These factors make the assay very robust and influenced neither by ATP concentration nor by luciferase inhibition. The measuring time depends on the kinase activity and can be varied from minutes to more than 8 h provided the kinase is stable and the evaporation of water from the wells is acceptable. The assay is linear with respect to kinase activity over three orders of magnitude. The new reagents also allowed us to determine K(m) values for ATP and for Kemptide.

Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

PubMed

Stloukal, Petr; Pekařová, Silvie; Kalendova, Alena; Mattausch, Hannelore; Laske, Stephan; Holzer, Clemens; Chitu, Livia; Bodner, Sabine; Maier, Guenther; Slouf, Miroslav; Koutny, Marek

2015-08-01

The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

Field Programmable Gate Array Based Parallel Strapdown Algorithm Design for Strapdown Inertial Navigation Systems

PubMed Central

Li, Zong-Tao; Wu, Tie-Jun; Lin, Can-Long; Ma, Long-Hua

2011-01-01

A new generalized optimum strapdown algorithm with coning and sculling compensation is presented, in which the position, velocity and attitude updating operations are carried out based on the single-speed structure in which all computations are executed at a single updating rate that is sufficiently high to accurately account for high frequency angular rate and acceleration rectification effects. Different from existing algorithms, the updating rates of the coning and sculling compensations are unrelated with the number of the gyro incremental angle samples and the number of the accelerometer incremental velocity samples. When the output sampling rate of inertial sensors remains constant, this algorithm allows increasing the updating rate of the coning and sculling compensation, yet with more numbers of gyro incremental angle and accelerometer incremental velocity in order to improve the accuracy of system. Then, in order to implement the new strapdown algorithm in a single FPGA chip, the parallelization of the algorithm is designed and its computational complexity is analyzed. The performance of the proposed parallel strapdown algorithm is tested on the Xilinx ISE 12.3 software platform and the FPGA device XC6VLX550T hardware platform on the basis of some fighter data. It is shown that this parallel strapdown algorithm on the FPGA platform can greatly decrease the execution time of algorithm to meet the real-time and high precision requirements of system on the high dynamic environment, relative to the existing implemented on the DSP platform. PMID:22164058

Collisional excitation of CO by H2O - An astrophysicist's guide to obtaining rate constants from coherent anti-Stokes Raman line shape data

NASA Technical Reports Server (NTRS)

Green, Sheldon

1993-01-01

Rate constants for excitation of CO by collisions with H2O are needed to understand recent observations of comet spectra. These collision rates are closely related to spectral line shape parameters, especially those for Raman Q-branch spectra. Because such spectra have become quite important for thermometry applications, much effort has been invested in understanding this process. Although it is not generally possible to extract state-to-state rate constants directly from the data as there are too many unknowns, if the matrix of state-to-state rates can be expressed in terms of a rate-law model which depends only on rotational quantum numbers plus a few parameters, the parameters can be determined from the data; this has been done with some success for many systems, especially those relevant to combustion processes. Although such an analysis has not yet been done for CO-H2O, this system is expected to behave similarly to N2-H2O which has been well studies; modifications of parameters for the latter system are suggested which should provide a reasonable description of rate constants for the former.

The influence of testing apparatus stiffness on the source properties of laboratory stick-slip

NASA Astrophysics Data System (ADS)

Kilgore, B. D.; McGarr, A.; Beeler, N. M.; Lockner, D. A.

2016-12-01

Stick-slip experiments were performed to determine the influence of the testing apparatus stiffness on source properties, to develop methods to relate stick-slip to natural earthquakes, and to examine the hypothesis of McGarr [2012] that the product of unloading stiffness, k, and slip duration, T, is both scale-independent and approximately constant for both laboratory and natural earthquakes. A double-direct shear load frame was used with Sierra White Granite samples at 2 MPa normal stress, and a remote loading rate of 0.2 µm/s. The stiffness of the test apparatus was varied by more than an order of magnitude by inserting disk springs into the shear loading column adjacent to the granite samples. Servo-controlling slip at a point between the forcing ram and the shear force load cell, produced repeatable slip events. Slip and slip duration decrease as k increases, as they do for natural earthquakes. In contrast to earthquakes, stress drop and slip rate decrease with increasing k, and the product kT for these experiments is not constant, but decreases with k. These data, collected over a range of k, do not conform to McGarr's [2012] hypothesis. However, analysis of stick-slip studies from other testing apparatuses is consistent with McGarr's hypothesis; kT is scale-independent, similar to that of earthquakes, equal to the ratio of static stress drop to average slip velocity, and similar to the ratio of shear modulus to wavespeed of rock. These properties result from conducting experiments over a range of sample sizes, using rock samples with the same elastic properties as the Earth, and using testing machines whose stiffnesses decrease, and characteristic periods increase with scale. A consequence of our experiments and analysis is that extrapolation of lab scale earthquake source properties to the Earth is more difficult than previously thought, requiring an accounting for the properties of the testing machines and additional research beyond that reported here.

Nanoindentation of dry and fluid-saturated micro-porous rocks

NASA Astrophysics Data System (ADS)

Mighani, S.; Bernabe, Y.; Schwartzman, A. F.; Evans, J. B.

2017-12-01

In this report we explore the ability of nanoindentation technique to evaluate the pore-scale solid-fluid interactions in micro-porous rocks. We measure the creep deformation of a porous rock sample over a period of 3 minutes under a constant maximum force. The indentation tip is instrumented with a nano-DMA transducer which efficiently compensates for the thermal drifts. The candidate rock is a carbonate with micro-porous micritic cement. Secondary Electron (SE) images revealed a bimodal pore structure for this rock-type: regions (A) of micritic cement with micropores, and (B) with large grains and vuggy pores. The experiments were performed on dry rock samples as well as saturated with water (1 cp and buffered with 30 ppm calcite powder) and silicone oil (100 cp). Thus, the fluids presented a wide variation in viscosity and chemical reactivity. We then explored the size (maximum forces of 2, 4, and 8 mN) and loading rate (0.2-2 mN/sec) dependency of the observed creep behavior. The amount of total deformation within the 3 minutes of creep showed a uniform increase with a tendency to reach an equilibrium depth with creep rates (dh/h) below 5×10-3. The indentations in the water-saturated carbonate showed a 6-fold decrease in the Young's modulus (from 38 to 6 GPa) and 2-fold increase in creep magnitude (from 59 to 119 nm) compared with the dry indentations. We attribute these large differences to the possible chemical reaction of water and carbonate. This is further confirmed by comparing the hardness values, which showed that water softened the rock matrix by a factor of 4 (from 0.87 to 0.22 GPa). The carbonate sample saturated with oil, on the other hand, showed a higher modulus (47 GPa) and greater hardness (1.39 GPa), while the creep magnitude (31 nm) was half that observed in dry rock. We attribute this behavior to the viscous displacement of the pore fluid during consolidation of the poroelastic matrix. The loading rate-dependency and size (maximum load) sensitivity of the observed creep appear consistent with poroelasticity. We used Agbezuge and Deresiewicz's (1974) solution to derive poroelastic constants based on the recorded amount of creep. The analysis yields estimates of the diffusivity constant of the rock and the equilibrium creep depth. (We would like to acknowledge The U.S. Department of Energy (DOE) for their support)

Reconstructing genealogies of serial samples under the assumption of a molecular clock using serial-sample UPGMA.

PubMed

Drummond, A; Rodrigo, A G

2000-12-01

Reconstruction of evolutionary relationships from noncontemporaneous molecular samples provides a new challenge for phylogenetic reconstruction methods. With recent biotechnological advances there has been an increase in molecular sequencing throughput, and the potential to obtain serial samples of sequences from populations, including rapidly evolving pathogens, is fast being realized. A new method called the serial-sample unweighted pair grouping method with arithmetic means (sUPGMA) is presented that reconstructs a genealogy or phylogeny of sequences sampled serially in time using a matrix of pairwise distances. The resulting tree depicts the terminal lineages of each sample ending at a different level consistent with the sample's temporal order. Since sUPGMA is a variant of UPGMA, it will perform best when sequences have evolved at a constant rate (i.e., according to a molecular clock). On simulated data, this new method performs better than standard cluster analysis under a variety of longitudinal sampling strategies. Serial-sample UPGMA is particularly useful for analysis of longitudinal samples of viruses and bacteria, as well as ancient DNA samples, with the minimal requirement that samples of sequences be ordered in time.

Electron attachment to CF3 and CF3Br at temperatures up to 890 K: experimental test of the kinetic modeling approach.

PubMed

Shuman, Nicholas S; Miller, Thomas M; Viggiano, Albert A; Troe, Jürgen

2013-05-28

Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br(-), with a rate constant increasing from 1.1 × 10(-8) cm(3) s(-1) at 300 K to 5.3 × 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3 (-) and dissociative attachment yielding F(-). Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ~5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

Assessment of chloroethene degradation rates based on ratios of daughter/parent compounds in groundwater plumes

NASA Astrophysics Data System (ADS)

Höhener, Patrick

2014-05-01

Chlorinated solvent spills at industrial and urban sites create groundwater plumes where tetrachloro- and trichloroethene may degrade to their daughter compounds, dichloroethenes, vinyl chloride and ethane. The assessment of degradation and natural attenuation at such sites may be based on the analysis and inverse modelling of concentration data, on the calculation of mass fluxes in transsects, and/or on the analysis of stable isotope ratios in the ethenes. Relatively few work has investigated the possibility of using ratio of concentrations for gaining information on degradation rates. The use of ratios bears the advantage that dilution of a single sample with contaminant-free water does not matter. It will be shown that molar ratios of daughter to parent compounds measured along a plume streamline are a rapid and robust mean of determining whether degradation rates increase or decrease along the degradation chain, and allow furthermore a quantitation of the relative magnitude of degradation rates compared to the rate of the parent compound. Furthermore, ratios of concentration will become constant in zones where degradation is absent, and this allows to sketching the extension of actively degrading zones. The assessment is possible for pure sources and also for mixed sources. A quantification method is proposed in order to estimate first-order degradation rates in zones of constant degradation activity. This quantification method includes corrections that are needed due to longitudinal and transversal dispersivity. The method was tested on a number of real field sites from literature. At the majority of these sites, the first-order degradation rates were decreasing along the degradation chain from tetrachloroethene to vinyl chloride, meaning that the latter was often reaching important concentrations. This is bad news for site owners due to the increased toxicity of vinyl chloride compared to its parent compounds.

Continental collision slowing due to viscous mantle lithosphere rather than topography.

PubMed

Clark, Marin Kristen

2012-02-29

Because the inertia of tectonic plates is negligible, plate velocities result from the balance of forces acting at plate margins and along their base. Observations of past plate motion derived from marine magnetic anomalies provide evidence of how continental deformation may contribute to plate driving forces. A decrease in convergence rate at the inception of continental collision is expected because of the greater buoyancy of continental than oceanic lithosphere, but post-collisional rates are less well understood. Slowing of convergence has generally been attributed to the development of high topography that further resists convergent motion; however, the role of deforming continental mantle lithosphere on plate motions has not previously been considered. Here I show that the rate of India's penetration into Eurasia has decreased exponentially since their collision. The exponential decrease in convergence rate suggests that contractional strain across Tibet has been constant throughout the collision at a rate of 7.03 × 10(-16) s(-1), which matches the current rate. A constant bulk strain rate of the orogen suggests that convergent motion is resisted by constant average stress (constant force) applied to a relatively uniform layer or interface at depth. This finding follows new evidence that the mantle lithosphere beneath Tibet is intact, which supports the interpretation that the long-term strain history of Tibet reflects deformation of the mantle lithosphere. Under conditions of constant stress and strength, the deforming continental lithosphere creates a type of viscous resistance that affects plate motion irrespective of how topography evolved.

Seasonal variation in natural abundance of 2H and 18O in urine samples from rural Nigeria

PubMed Central

Dugas, Lara R.; Brieger, William; Tayo, Bamidele O.; Alabi, Tunrayo; Schoeller, Dale A.; Luke, Amy

2015-01-01

The doubly labeled water (DLW) method is used to measure free-living energy expenditure in humans. Inherent to this technique is the assumption that natural abundances of stable isotopes 2H and 18O in body water remain constant over the course of the measurement period and after elimination of the loading dose of DLW will return to the same predose level. To determine variability in the natural abundances of 2H and 18O in humans living in a region with seasonal shifts in rain patterns and sources of drinking water, over the course of 12 mo we collected weekly urine samples from four individuals living in southwest Nigeria as well as samples of their drinking water. From ongoing regional studies of hypertension, obesity, and energy expenditure, we estimated average water turnover rate, urine volumes, and sodium and potassium excretion. Results suggest that 2H and 18O in urine, mean concentrations of urinary sodium and potassium, urine volume, and total body turnover differed significantly from dry to rainy season. Additionally, seasonal weather variables (mean monthly maximum temperatures, total monthly rainfall, and minimum relative humidity) were all significantly associated with natural abundances in urine. No seasonal difference was observed in drinking water samples. Findings suggest that natural abundances in urine may not remain constant as assumed, and studies incorporating DLW measurements across the transition of seasons should interpret results with caution unless appropriate doses of the tracers are used. PMID:25977450

A magnetic resonance study of MoS(2) fullerene-like nanoparticles.

PubMed

Panich, A M; Shames, A I; Rosentsveig, R; Tenne, R

2009-09-30

We report on the first nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) investigation of inorganic fullerene-like MoS(2) nanoparticles. Spectra of bulk 2H-MoS(2) samples have also been measured for comparison. The similarity between the measured quadrupole coupling constants and chemical shielding anisotropy parameters for bulk and fullerene-like MoS(2) reflects the nearly identical local crystalline environments of the Mo atoms in these two materials. EPR measurements show that fullerene-like MoS(2) exhibits a larger density of dangling bonds carrying unpaired electrons, indicative of them having a more defective structure than the bulk sample. The latter observation explains the increase in the spin-lattice relaxation rate observed in the NMR measurements for this sample in comparison with the bulk 2H- MoS(2) ones.

A magnetic resonance study of MoS2 fullerene-like nanoparticles

NASA Astrophysics Data System (ADS)

Panich, A. M.; Shames, A. I.; Rosentsveig, R.; Tenne, R.

2009-09-01

We report on the first nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) investigation of inorganic fullerene-like MoS2 nanoparticles. Spectra of bulk 2H-MoS2 samples have also been measured for comparison. The similarity between the measured quadrupole coupling constants and chemical shielding anisotropy parameters for bulk and fullerene-like MoS2 reflects the nearly identical local crystalline environments of the Mo atoms in these two materials. EPR measurements show that fullerene-like MoS2 exhibits a larger density of dangling bonds carrying unpaired electrons, indicative of them having a more defective structure than the bulk sample. The latter observation explains the increase in the spin-lattice relaxation rate observed in the NMR measurements for this sample in comparison with the bulk 2H- MoS2 ones.

Radioactive contamination of arthropods from different trophic levels in hilly and mountainous areas after the Fukushima Daiichi nuclear power plant accident.

PubMed

Tanaka, Sota; Hatakeyama, Kaho; Takahashi, Sentaro; Adati, Tarô

2016-11-01

In order to understand the influence of the Fukushima Daiichi nuclear power plant accident on the ecosystem in hilly and mountainous areas of Fukushima Prefecture, chronological changes in the levels of radiocesium in arthropod species were investigated. From 2012 to 2014, arthropods from different trophic levels were sampled and the air radiation dose rates at the sampling sites were analyzed. The air radiation dose rates showed a significant and constant reduction over the 2 years at the sampling sites in Fukushima. The median radiocesium concentration ( 134 Cs +  137 Cs) detected in the rice grasshopper, Oxya yezoensis, and the Emma field cricket, Teleogryllus emma, dropped continuously to 0.080 and 0.078 Bq/g fresh weight, respectively, in 2014. In contrast, no significant reduction in radioactive contamination was observed in the Jorô spider, Nephila clavata, in which the level remained at 0.204 Bq/g in 2014. A significant positive correlation between radiocesium concentration and the air radiation dose rate was observed in the rice grasshopper, the Emma field cricket and the Jorô spider. The highest correlation coefficient (ρ = 0.946) was measured in the grasshopper. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Data acquisition system for chemical kinetic studies

PubMed Central

Zhu, Yu-zhen; Zhou, Xin; Zang, Xiang-sheng

1989-01-01

A microcomputer-interfaced data acquisition system for chemical kinetics (interfacing with laboratory analogue instruments) has been developed. Analogue signals from instruments used in kinetics experiments are amplifed by a wide-range adjustable high-gain operational amplifier and smoothed by an op-based filter, and then digitized at rates of up to 104 samples per channel by an ADC 0816 digitizer. The ADC data transfer and manipulation routine was written in Assembler code and in high-level language; the graphics package and data treatment package is in Basic. For the various sampling speeds, all of the program can be written using Basic-Assembler or completely in Assembler if a high sampling rate is needed. Several numerical treatment methods for chemical kinetics have been utilized to smooth the data from experiments. The computer-interfaced system for second-order chemical kinetic studies was applied to the determination of the rate constant of the saponification of ethyl acetate at 35°C. For this specific problem, an averaging treatment was used which can be called an interval method. The use of this method avoids the diffcully of measuring the starting time of the reaction. Two groups of experimental data and results were used to evaluate the systems performance. All of the results obtained are in agreement with the reference value. PMID:18925219

Short-term standard litter decomposition across three different ecosystems in middle taiga zone of West Siberia

NASA Astrophysics Data System (ADS)

Filippova, Nina V.; Glagolev, Mikhail V.

2018-03-01

The method of standard litter (tea) decomposition was implemented to compare decomposition rate constants (k) between different peatland ecosystems and coniferous forests in the middle taiga zone of West Siberia (near Khanty-Mansiysk). The standard protocol of TeaComposition initiative was used to make the data usable for comparisons among different sites and zonobiomes worldwide. This article sums up the results of short-term decomposition (3 months) on the local scale. The values of decomposition rate constants differed significantly between three ecosystem types: it was higher in forest compared to bogs, and treed bogs had lower decomposition constant compared to Sphagnum lawns. In general, the decomposition rate constants were close to ones reported earlier for similar climatic conditions and habitats.

ESTIMATION OF CARBOXYLIC ACID ESTER HYDROLYSIS RATE CONSTANTS

EPA Science Inventory

SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external...

High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

NASA Astrophysics Data System (ADS)

Nguyen, Thanh Lam; Stanton, John F.

2017-10-01

Hydrogen abstraction from NH3 by OH to produce H2O and NH2—an important reaction in combustion of NH3 fuel—was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K.

PubMed

Nguyen, Thanh Lam; Stanton, John F

2017-10-21

Hydrogen abstraction from NH 3 by OH to produce H 2 O and NH 2 -an important reaction in combustion of NH 3 fuel-was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

Experimental and theoretical study of the sec-C[sub 4]H[sub 9] [r reversible] CH[sub 3] + C[sub 3]H[sub 6] reaction

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

Knyazev, V.D.; Dubinsky, I.A.; Slagle, I.R.

1994-10-27

The kinetics of the unimolecular decomposition of the sec-C[sub 4]H[sub 9] radical has been studied experimentally in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were determined in time-resolved experiments as a function of temperature (598-680 K) and bath gas density (3-18) [times] 10[sup 16] molecules cm[sup [minus]3] in three bath gases: He, Ar, and N[sub 2]. The rate constants are in the falloff region under the conditions of the experiments. The results of earlier studies of the reverse reaction were reanalyzed and used to create a transition state model of themore » reaction. This transition state model was used to obtain values of the microcanonical rate constants, k (E). Falloff behavior was reproduced using master equation modeling with the energy barrier height for decomposition (necessary to calculate k(E)) obtained from optimization of the agreement between experimental and calculated rate constants. The resulting model of the reaction provides the high-pressure limit rate constants for the decomposition reaction and the reverse reaction. 52 refs., 7 figs., 3 tabs.« less

Propagation rate constants for the peroxidation of sterols on the biosynthetic pathway to cholesterol.

PubMed

Lamberson, Connor R; Muchalski, Hubert; McDuffee, Kari B; Tallman, Keri A; Xu, Libin; Porter, Ned A

2017-10-01

The free radical chain autoxidation of cholesterol and the oxidation products formed, i.e. oxysterols, have been the focus of intensive study for decades. The peroxidation of sterol precursors to cholesterol such as 7-dehydrocholesterol (7-DHC) and desmosterol as well as their oxysterols has received less attention. The peroxidation of these sterol precursors can become important under circumstances in which genetic conditions or exposures to small molecules leads to an increase of these biosynthetic intermediates in tissues and fluids. 7-DHC, for example, has a propagation rate constant for peroxidation some 200 times that of cholesterol and this sterol is found at elevated levels in a devastating human genetic condition, Smith-Lemli-Opitz syndrome (SLOS). The propagation rate constants for peroxidation of sterol intermediates on the biosynthetic pathway to cholesterol were determined by a competition kinetic method, i.e. a peroxyl radical clock. In this work, propagation rate constants for lathosterol, zymostenol, desmosterol, 7-dehydrodesmosterol and other sterols in the Bloch and Kandutsch-Russell pathways are assigned and these rate constants are related to sterol structural features. Furthermore, potential oxysterols products are proposed for sterols whose oxysterol products have not been determined. Copyright © 2017 Elsevier B.V. All rights reserved.

The role of multivalency in the association kinetics of patchy particle complexes.

PubMed

Newton, Arthur C; Groenewold, Jan; Kegel, Willem K; Bolhuis, Peter G

2017-06-21

Association and dissociation of particles are elementary steps in many natural and technological relevant processes. For many such processes, the presence of multiple binding sites is essential. For instance, protein complexes and regular structures such as virus shells are formed from elementary building blocks with multiple binding sites. Here we address a fundamental question concerning the role of multivalency of binding sites in the association kinetics of such complexes. Using single replica transition interface sampling simulations, we investigate the influence of the multivalency on the binding kinetics and the association mechanism of patchy particles that form polyhedral clusters. When the individual bond strength is fixed, the kinetics naturally is very dependent on the multivalency, with dissociation rate constants exponentially decreasing with the number of bonds. In contrast, we find that when the total bond energy per particle is kept constant, association and dissociation rate constants turn out rather independent of multivalency, although of course still very dependent on the total energy. The association and dissociation mechanisms, however, depend on the presence and nature of the intermediate states. For instance, pathways that visit intermediate states are less prevalent for particles with five binding sites compared to the case of particles with only three bonds. The presence of intermediate states can lead to kinetic trapping and malformed aggregates. We discuss implications for natural forming complexes such as virus shells and for the design of artificial colloidal patchy particles.

The role of multivalency in the association kinetics of patchy particle complexes

NASA Astrophysics Data System (ADS)

Newton, Arthur C.; Groenewold, Jan; Kegel, Willem K.; Bolhuis, Peter G.

2017-06-01

Association and dissociation of particles are elementary steps in many natural and technological relevant processes. For many such processes, the presence of multiple binding sites is essential. For instance, protein complexes and regular structures such as virus shells are formed from elementary building blocks with multiple binding sites. Here we address a fundamental question concerning the role of multivalency of binding sites in the association kinetics of such complexes. Using single replica transition interface sampling simulations, we investigate the influence of the multivalency on the binding kinetics and the association mechanism of patchy particles that form polyhedral clusters. When the individual bond strength is fixed, the kinetics naturally is very dependent on the multivalency, with dissociation rate constants exponentially decreasing with the number of bonds. In contrast, we find that when the total bond energy per particle is kept constant, association and dissociation rate constants turn out rather independent of multivalency, although of course still very dependent on the total energy. The association and dissociation mechanisms, however, depend on the presence and nature of the intermediate states. For instance, pathways that visit intermediate states are less prevalent for particles with five binding sites compared to the case of particles with only three bonds. The presence of intermediate states can lead to kinetic trapping and malformed aggregates. We discuss implications for natural forming complexes such as virus shells and for the design of artificial colloidal patchy particles.

Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

USGS Publications Warehouse

Cranor, W.L.; Alvarez, D.A.; Huckins, J.N.; Petty, J.D.

2009-01-01

To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (kua) and no SPMD air partitioning coefficient (Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m3??g-1??d-1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m3??g-1??d-1 with relative standard deviations of 8.4% and 8.6% respectively.

Environmental Fate Studies on Certain Munition Wastewater Constituents - Literature Review

DTIC Science & Technology

1980-03-01

gram-negative bacteria , actinaycetes, yeasts, and fungi. They found that TNT at 50 Mgtter severely inhibited the growth of these organisms in wost...i , conditions . I Biodegradation ,. Chambers et al. (1963) reported evidence of degradation of 2,4-DNT with phenol-adapted bacteria and 100 mg/liter...coefficient based on organic carbon contentoc H - Henry’s Law constant kA - Hydrolysis rate constant under acidic conditions k.M - Hydrolysis rate constant

Theory of bi-molecular association dynamics in 2D for accurate model and experimental parameterization of binding rates

PubMed Central

Yogurtcu, Osman N.; Johnson, Margaret E.

2015-01-01

The dynamics of association between diffusing and reacting molecular species are routinely quantified using simple rate-equation kinetics that assume both well-mixed concentrations of species and a single rate constant for parameterizing the binding rate. In two-dimensions (2D), however, even when systems are well-mixed, the assumption of a single characteristic rate constant for describing association is not generally accurate, due to the properties of diffusional searching in dimensions d ≤ 2. Establishing rigorous bounds for discriminating between 2D reactive systems that will be accurately described by rate equations with a single rate constant, and those that will not, is critical for both modeling and experimentally parameterizing binding reactions restricted to surfaces such as cellular membranes. We show here that in regimes of intrinsic reaction rate (ka) and diffusion (D) parameters ka/D > 0.05, a single rate constant cannot be fit to the dynamics of concentrations of associating species independently of the initial conditions. Instead, a more sophisticated multi-parametric description than rate-equations is necessary to robustly characterize bimolecular reactions from experiment. Our quantitative bounds derive from our new analysis of 2D rate-behavior predicted from Smoluchowski theory. Using a recently developed single particle reaction-diffusion algorithm we extend here to 2D, we are able to test and validate the predictions of Smoluchowski theory and several other theories of reversible reaction dynamics in 2D for the first time. Finally, our results also mean that simulations of reactive systems in 2D using rate equations must be undertaken with caution when reactions have ka/D > 0.05, regardless of the simulation volume. We introduce here a simple formula for an adaptive concentration dependent rate constant for these chemical kinetics simulations which improves on existing formulas to better capture non-equilibrium reaction dynamics from dilute to dense systems. PMID:26328828

Molecular Rayleigh Scattering Diagnostic for Dynamic Temperature, Velocity, and Density Measurements

NASA Technical Reports Server (NTRS)

Mielke, Amy R.; Elam, Kristie A.; Sung, Chi-Jen

2006-01-01

A molecular Rayleigh scattering technique is developed to measure dynamic gas temperature, velocity, and density in unseeded turbulent flows at sampling rates up to 16 kHz. A high power CW laser beam is focused at a point in an air jet plume and Rayleigh scattered light is collected and spectrally resolved. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. The circular interference fringe pattern is divided into four concentric regions and sampled at 1 and 16 kHz using photon counting electronics. Monitoring the relative change in intensity within each region allows for measurement of gas temperature and velocity. Independently monitoring the total scattered light intensity provides a measure of gas density. A low speed heated jet is used to validate the measurement of temperature fluctuations and an acoustically excited nozzle flow is studied to validate velocity fluctuation measurements. Power spectral density calculations of the property fluctuations, as well as mean and fluctuating quantities are presented. Temperature fluctuation results are compared with constant current anemometry measurements and velocity fluctuation results are compared with constant temperature anemometry measurements at the same locations.

Radionuclide activities and metal concentrations in sediments of the Sebou Estuary, NW Morocco, following a flooding event.

PubMed

Laissaoui, A; Mas, J L; Hurtado, S; Ziad, N; Villa, M; Benmansour, M

2013-06-01

This study presents metal concentrations (Fe, Mg, Mn, Co, Cu, Zn, Pb, As, Sr and V) and radionuclide activities ((40)K, (137)Cs, (210)Pb, (226)Ra, (228)Ac, (234)Th and (212)Pb) in surface deposits and a sediment core from the Sebou Estuary, Northwest Morocco. Samples were collected in April 2009, about 2 months after a flooding event, and analysed using a well-type coaxial gamma-ray detector and inductively coupled plasma-quadrupole mass spectrometry. Activities of radionuclides and concentrations of almost all elements in surface samples displayed only moderate spatial variation, suggesting homogenous deposition of eroded local soil in response to intense precipitation. Excess (210)Pb displayed relatively constant activity throughout the sediment core, preventing dating and precluding determination of the historical accumulation rates of pollutants at the core site. Some elements showed non-systematic trends with depth and displayed local maxima and minima. Other elements presented relatively systematic concentration trends or relatively constant levels with discrete maxima and/or minima. Except for Mn, Sr and Cr, all metal concentrations in sediment were below levels typical of polluted systems, suggesting little human impact or losses of metals from sediment particles.

Experimental wear behavioral studies of as-cast and 5 hr homogenized Al25Mg2Si2Cu4Ni alloy at constant load based on taguchi method

NASA Astrophysics Data System (ADS)

Harlapur, M. D.; Mallapur, D. G.; Udupa, K. Rajendra

2018-04-01

In the present study, an experimental study of the volumetric wear behaviour of Aluminium (Al-25Mg2Si2Cu4Ni) alloy in as cast and 5Hr homogenized with T6 heat treatment is carried out at constant load. The Pin on disc apparatus was used to carry out the sliding wear test. Taguchi method based on L-16 orthogonal array was employed to evaluate the data on the wear behavior. Signal-to-noise ratio among the objective of smaller the better and mean of means results were used. General regression model is obtained by correlation. Lastly confirmation test was completed to compose a comparison between the experimental results foreseen from the mention correlation. The mathematical model reveals the load has maximum contribution on the wear rate compared to speed. Scanning Electron Microscope was used to analyze the worn-out wear surfaces. Wear results show that 5Hr homogenized Al-25Mg2Si2Cu4Ni alloy samples with T6 treated had better volumetric wear resistance as compared to as cast samples.

KABAM Version 1.0 User's Guide and Technical Documentation - Appendix H - Methods for Estimating Metabolism Rate Constant

EPA Pesticide Factsheets

Appendix H of KABAM Version 1.0 documentation related to estimating the metabolism rate constant. KABAM is a simulation model used to predict pesticide concentrations in aquatic regions for use in exposure assessments.

Freshwater aquatic macrophytes as heavy metal monitors - the Ottawa River experience.

PubMed

Mortimer, D C

1985-09-01

The ability of freshwater aquatic vascular plants to accumulate heavy metals was examined in some detail during a five year study. Differences in uptake rate were found to depend on the species of plant, the seasonal growth rate changes and the metal ion being absorbed. Lead and mercury were concentrated to a greater extent than the lighter nickel and copper. Laboratory experiments were designed to establish uptake rate constants which were used to calculate water concentrations of mercury from the analyses of plant samples from the river. 'Background' levels of mercury in aquatic plants of 35-50 ng g(-1) dry weight corresponded to a water concentration near 15 ng L(-1) of total mercury of which 25-30% was methylmercury. Higher concentrations of mercury in the plants indicated a proportional increase in the mercury level in the water.

Processing Ti-25Ta-5Zr Bioalloy via Anodic Oxidation Procedure at High Voltage

NASA Astrophysics Data System (ADS)

Ionita, Daniela; Grecu, Mihaela; Dilea, Mirela; Cojocaru, Vasile Danut; Demetrescu, Ioana

2011-12-01

The current paper reports the processing of Ti-25Ta-5Zr bioalloy via anodic oxidation in NH4BF4 solution under constant potentiostatic conditions at high voltage to obtain more suitable properties for biomedical application. The maximum efficiency of the procedure is reached at highest applied voltage, when the corrosion rate in Hank's solution is decreased approxomately six times. The topography of the anodic layer has been studied using atomic force microscopy (AFM), and the results indicated that the anodic oxidation process increases the surface roughness. The AFM images indicated a different porosity for the anodized surfaces as well. After anodizing, the hydrophilic character of Ti-25Ta-5Zr samples has increased. A good correlation between corrosion rate obtained from potentiodynamic curves and corrosion rate from ions release analysis was obtained.

Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research

NASA Technical Reports Server (NTRS)

Neveu, M. C.; Stocker, D. P.

1985-01-01

High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.

Close encounters and collisions of comets with the earth

NASA Technical Reports Server (NTRS)

Sekanina, Z.; Yeomans, D. K.

1984-01-01

A computer search for earth-approaching comets among those listed in Marsden's (1983) updated orbit catalog has identified 36 cases at which minimum separation distance was less than 2500 earth radii. A strong representation of short period comets in the sample is noted, and the constant rate of the close approaching comets in the last 300 years is interpreted to suggest the lack of long-period comets intrinsically fainter than an absolute magnitude of about 11. A comet-earth collision rate derived from the statistics of these close encounters implies an average period of 33-64 million years between any two events. This rate is comparable with the frequency of geologically recent global catastrophes which appear to be associated with extraterrestrial object impacts, such as the Cretaceous-Tertiary extinction 65 million years ago and the late Eocene event 34 million years ago.

Time-weighted average sampling of airborne propylene glycol ethers by a solid-phase microextraction device.

PubMed

Shih, H C; Tsai, S W; Kuo, C H

2012-01-01

A solid-phase microextraction (SPME) device was used as a diffusive sampler for airborne propylene glycol ethers (PGEs), including propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and dipropylene glycol monomethyl ether (DPGME). Carboxen-polydimethylsiloxane (CAR/PDMS) SPME fiber was selected for this study. A polytetrafluoroethylene (PTFE) tubing was used as the holder, and the SPME fiber assembly was inserted into the tubing as a diffusive sampler. The diffusion path length and area of the sampler were 0.3 cm and 0.00086 cm(2), respectively. The theoretical sampling constants at 30°C and 1 atm for PGME, PGMEA, and DPGME were 1.50 × 10(-2), 1.23 × 10(-2) and 1.14 × 10(-2) cm(3) min(-1), respectively. For evaluations, known concentrations of PGEs around the threshold limit values/time-weighted average with specific relative humidities (10% and 80%) were generated both by the air bag method and the dynamic generation system, while 15, 30, 60, 120, and 240 min were selected as the time periods for vapor exposures. Comparisons of the SPME diffusive sampling method to Occupational Safety and Health Administration (OSHA) organic Method 99 were performed side-by-side in an exposure chamber at 30°C for PGME. A gas chromatography/flame ionization detector (GC/FID) was used for sample analysis. The experimental sampling constants of the sampler at 30°C were (6.93 ± 0.12) × 10(-1), (4.72 ± 0.03) × 10(-1), and (3.29 ± 0.20) × 10(-1) cm(3) min(-1) for PGME, PGMEA, and DPGME, respectively. The adsorption of chemicals on the stainless steel needle of the SPME fiber was suspected to be one of the reasons why significant differences between theoretical and experimental sampling rates were observed. Correlations between the results for PGME from both SPME device and OSHA organic Method 99 were linear (r = 0.9984) and consistent (slope = 0.97 ± 0.03). Face velocity (0-0.18 m/s) also proved to have no effects on the sampler. However, the effects of temperature and humidity have been observed. Therefore, adjustments of experimental sampling constants at different environmental conditions will be necessary.

Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex.

PubMed

Zhao, Yong; Kan, Zhong-yuan; Zeng, Zhi-xiong; Hao, Yu-hua; Chen, Hua; Tan, Zheng

2004-10-20

Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.

Mechanism of Kinetically Controlled Capillary Condensation in Nanopores: A Combined Experimental and Monte Carlo Approach.

PubMed

Hiratsuka, Tatsumasa; Tanaka, Hideki; Miyahara, Minoru T

2017-01-24

We find the rule of capillary condensation from the metastable state in nanoscale pores based on the transition state theory. The conventional thermodynamic theories cannot achieve it because the metastable capillary condensation inherently includes an activated process. We thus compute argon adsorption isotherms on cylindrical pore models and atomistic silica pore models mimicking the MCM-41 materials by the grand canonical Monte Carlo and the gauge cell Monte Carlo methods and evaluate the rate constant for the capillary condensation by the transition state theory. The results reveal that the rate drastically increases with a small increase in the chemical potential of the system, and the metastable capillary condensation occurs for any mesopores when the rate constant reaches a universal critical value. Furthermore, a careful comparison between experimental adsorption isotherms and the simulated ones on the atomistic silica pore models reveals that the rate constant of the real system also has a universal value. With this finding, we can successfully estimate the experimental capillary condensation pressure over a wide range of temperatures and pore sizes by simply applying the critical rate constant.

Kinetic rate constant prediction supports the conformational selection mechanism of protein binding.

PubMed

Moal, Iain H; Bates, Paul A

2012-01-01

The prediction of protein-protein kinetic rate constants provides a fundamental test of our understanding of molecular recognition, and will play an important role in the modeling of complex biological systems. In this paper, a feature selection and regression algorithm is applied to mine a large set of molecular descriptors and construct simple models for association and dissociation rate constants using empirical data. Using separate test data for validation, the predicted rate constants can be combined to calculate binding affinity with accuracy matching that of state of the art empirical free energy functions. The models show that the rate of association is linearly related to the proportion of unbound proteins in the bound conformational ensemble relative to the unbound conformational ensemble, indicating that the binding partners must adopt a geometry near to that of the bound prior to binding. Mirroring the conformational selection and population shift mechanism of protein binding, the models provide a strong separate line of evidence for the preponderance of this mechanism in protein-protein binding, complementing structural and theoretical studies.

Microbial degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in soils.

PubMed Central

Mergaert, J; Webb, A; Anderson, C; Wouters, A; Swings, J

1993-01-01

The microbial degradation of tensile test pieces made of poly(3-hydroxybutyrate) [P(3HB)] or a copolymer of 90% 3-hydroxybutyric acid and 10% 3-hydroxyvaleric acid was studied in soils incubated at a constant temperature of 15, 28, or 40 degrees C for up to 200 days. In addition, hydrolytic degradation in sterile buffer at temperatures ranging from 4 to 55 degrees C was monitored for 98 days. Degradation was measured through loss of weight (surface erosion), molecular weight, and mechanical strength. While no weight loss was recorded in sterile buffer, samples incubated in soils were degraded at an erosion rate of 0.03 to 0.64% weight loss per day, depending on the polymer, the soil, and the incubation temperature. The erosion rate was enhanced by incubation at higher temperatures, and in most cases the copolymer lost weight at a higher rate than the homopolymer. The molecular weights of samples incubated at 40 degrees C in soils and those incubated at 40 degrees C in sterile buffer decreased at similar rates, while the molecular weights of samples incubated at lower temperatures remained almost unaffected, indicating that molecular weight decrease is due to simple hydrolysis and not to the action of biodegrading microorganisms. The degradation resulted in loss of mechanical properties. From the samples used in the biodegradation studies, 295 dominant microbial strains capable of degrading P (3HB) and the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer in vitro were isolated and identified.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8250550

Frequency-Domain Multiplexing Readout with a Self-Trigger System for Pulse Signals from Kinetic Inductance Detectors

NASA Astrophysics Data System (ADS)

Yamada, Y.; Ishino, H.; Kibayashi, A.; Kida, Y.; Hidehira, N.; Komatsu, K.; Hazumi, M.; Sato, N.; Sakai, K.; Yamamori, H.; Hirayama, F.; Kohjiro, S.

2018-04-01

We present the development of a frequency-domain multiplexing readout of kinetic inductance detectors (KIDs) for pulse signals with a self-trigger system. The KIDs consist of an array of superconducting resonators that have different resonant frequencies individually, allowing us to read out multiple channels in the frequency domain with a single wire using a microwave-frequency comb. The energy deposited to the resonators break Cooper pairs, changing the kinetic inductance and, hence, the amplitude and the phase of the probing microwaves. For some applications such as X-ray detections, the deposited energy is detected as a pulse signal shaped by the time constants of the quasiparticle lifetime, the resonator quality factor, and the ballistic phonon lifetime in the substrate, ranging from microseconds to milliseconds. A readout system commonly used converts the frequency-domain data to the time-domain data. For the short pulse signals, the data rate may exceed the data transfer bandwidth, as the short time constant pulses require us to have a high sampling rate. In order to overcome this circumstance, we have developed a KID readout system that contains a self-trigger system to extract relevant signal data and reduces the total data rate with a commercial off-the-shelf FPGA board. We have demonstrated that the system can read out pulse signals of 15 resonators simultaneously with about 10 Hz event rate by irradiating α particles from ^{241} Am to the silicon substrate on whose surface aluminum KID resonators are formed.

Rate constants and mechanisms for the crystallization of Al nano-goethite under environmentally relevant conditions

NASA Astrophysics Data System (ADS)

Bazilevskaya, Ekaterina; Archibald, Douglas D.; Martínez, Carmen Enid

2012-07-01

Mobile inorganic and organic nanocolloidal particles originate-from and interact-with bulk solid phases in soil and sediment environments, and as such, they contribute to the dynamic properties of environmental systems. In particular, ferrihydrite and (nano)goethite are the most abundant of nanocolloidal Fe oxy(hydr)oxides in these environments. We therefore investigated the ferrihydrite to goethite phase transformation using experimental reaction conditions that mimicked environmental conditions where the formation of nanocolloidal Fe oxy(hydr)oxides may occur: slow titration of dilute solutions to pH 5 at 25 °C with and without 2 mol% Al. Subsequently, the rate constants from 54-d nano-goethite aging/crystallization experiments at 50 °C were determined using aliquots pulled for vibrational spectroscopy (including multivariate curve resolution, MCR, analyses of infrared spectra) and synchrotron-based X-ray diffraction (XRD). We also present a mechanistic model that accounts for the nano-goethite crystallization observed by the aforementioned techniques, and particle structural characteristics observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In contrast to the common assumption that metastable ferrihydrite precipitates first, before it transforms to goethite, the presence of characteristic infrared bands in freshly synthesized nanoparticle suspensions indicate goethite can precipitate directly from solution under environmentally relevant conditions: low Fe concentration, ambient temperature, and pH maintained at 5. However, the presence of 2 mol% Al prevented direct goethite precipitation. Rate constants obtained by fitting the contributions from the MCR-derived goethite-like component to the OH-stretching region were (7.4 ± 1.1) × 10-7 s-1 for 0% Al and (4.2 ± 0.4) × 10-7 s-1 for 2 mol% Al suspensions. Rate constants derived from intensities of OH-bending infrared vibrations (795 and 895 cm-1) showed similar values, within error, for both 0 and 2 mol% Al nanoparticle suspensions. Thus, the presence of 2 mol% Al decreased the rate constants determined from analyses of infrared OH-stretching and OH-bending vibrations by 43-57%. We postulate that dissolution re-precipitation reactions are accelerated in aggregate microenvironments by locally increased supersaturation, yielding the dominant mechanism for transformation of ferrihydrite to goethite and goethite crystal growth when bulk ion concentrations are low. Although we did observe growth of a population of prismatic goethite single crystals by TEM, there was more substantial growth of a population of polycrystalline goethite needles that appeared to retain some defects from a preceding aggregation step that we detected with DLS. Since the presence of Al hinders the dissolution of ferrihydrite, it too reduces the rate of crystallization to goethite and its crystal growth. As exemplified in this nano-particle crystallization study, the combination of advanced spectral-curve-resolution algorithms and sensitive and quantitative infrared sampling techniques opens future opportunities for the quantification of mineral phase dynamics in nanocolloidal suspensions, which is important for many aspects of environmental studies.

Shear enhanced compaction in a porous basalt from San Miguel Island, Azores

NASA Astrophysics Data System (ADS)

Loaiza, S.; Fortin, J.; Schubnel, A. J.; Vinciguerra, S.; Moreira, M.; Gueguen, Y.

2011-12-01

Basaltic rocks are the main component of the oceanic upper crust. This is of potential interest for water and geothermal resources, or for storage of CO2. The aim of our work is to investigate experimentally the mechanical behavior and the failure modes of porous basalt as well its permeability evolution during deformation. Cylindrical basalt samples, from the Azores, of 30 mm in diameter and 60 mm in length were deformed the triaxial cell at room temperature and at a constant axial strain rate of 10-5 s-1. The initial porosity of the sample was 18%. In our study, a set of experiments were performed at confining pressure in the range of 25-290 MPa. The samples were deformed under saturated conditions at a constant pore pressure of 5MPa. Two volumetric pumps kept the pore pressure constant, and the pore volume variations were recorded. The evolution of the porosity was calculated from the total volume variation inside the volumetric pumps. Permeability measurements were performed using the steady-state technique. Our result shows that two modes of deformation can be highlighted in this basalt. At low confining pressure (Pc < 50 MPa), the differential stress attains a peak before the sample undergoes strain softening; failure occurs by shear localization. The experiments performed at confining pressure higher than 50 MPa, show a totally different mode of deformation. In this second mode of deformation, an appreciable inelastic porosity reduction is observed. Comparing to the hydrostatic loading, the rock sample started to compact beyond a critical stress state; and from then, strain hardening, with stress drops are observed. Such a behavior is characteristic of the formation of compaction localization, due to grain crushing and pore collapse. In addition, this inelastic compaction is accompanied by a decrease of permeability, indicating that these compaction bands or zones act as barrier for fluid flow, in agreement with observations done in sandstone. Further studies, including Acoustic Emission locations and microstructural observations will be carried out in order to map the compaction bands or zones and confirm or infirm the formation of compaction localization, and the micromechanisms (pore collapse and grain crushing) taking place in this second mode of deformation.

A novel frame-level constant-distortion bit allocation for smooth H.264/AVC video quality

NASA Astrophysics Data System (ADS)

Liu, Li; Zhuang, Xinhua

2009-01-01

It is known that quality fluctuation has a major negative effect on visual perception. In previous work, we introduced a constant-distortion bit allocation method [1] for H.263+ encoder. However, the method in [1] can not be adapted to the newest H.264/AVC encoder directly as the well-known chicken-egg dilemma resulted from the rate-distortion optimization (RDO) decision process. To solve this problem, we propose a new two stage constant-distortion bit allocation (CDBA) algorithm with enhanced rate control for H.264/AVC encoder. In stage-1, the algorithm performs RD optimization process with a constant quantization QP. Based on prediction residual signals from stage-1 and target distortion for smooth video quality purpose, the frame-level bit target is allocated by using a close-form approximations of ratedistortion relationship similar to [1], and a fast stage-2 encoding process is performed with enhanced basic unit rate control. Experimental results show that, compared with original rate control algorithm provided by H.264/AVC reference software JM12.1, the proposed constant-distortion frame-level bit allocation scheme reduces quality fluctuation and delivers much smoother PSNR on all testing sequences.

A single mutation in a tunnel to the active site changes the mechanism and kinetics of product release in haloalkane dehalogenase LinB.

PubMed

Biedermannová, Lada; Prokop, Zbyněk; Gora, Artur; Chovancová, Eva; Kovács, Mihály; Damborsky, Jiří; Wade, Rebecca C

2012-08-17

Many enzymes have buried active sites. The properties of the tunnels connecting the active site with bulk solvent affect ligand binding and unbinding and also the catalytic properties. Here, we investigate ligand passage in the haloalkane dehalogenase enzyme LinB and the effect of replacing leucine by a bulky tryptophan at a tunnel-lining position. Transient kinetic experiments show that the mutation significantly slows down the rate of product release. Moreover, the mechanism of bromide ion release is changed from a one-step process in the wild type enzyme to a two-step process in the mutant. The rate constant of bromide ion release corresponds to the overall steady-state turnover rate constant, suggesting that product release became the rate-limiting step of catalysis in the mutant. We explain the experimental findings by investigating the molecular details of the process computationally. Analysis of trajectories from molecular dynamics simulations with a tunnel detection software reveals differences in the tunnels available for ligand egress. Corresponding differences are seen in simulations of product egress using a specialized enhanced sampling technique. The differences in the free energy barriers for egress of a bromide ion obtained using potential of mean force calculations are in good agreement with the differences in rates obtained from the transient kinetic experiments. Interactions of the bromide ion with the introduced tryptophan are shown to affect the free energy barrier for its passage. The study demonstrates how the mechanism of an enzymatic catalytic cycle and reaction kinetics can be engineered by modification of protein tunnels.

An Analytic Form for the Interresponse Time Analysis of Shull, Gaynor, and Grimes with Applications and Extensions

ERIC Educational Resources Information Center

Kessel, Robert; Lucke, Robert L.

2008-01-01

Shull, Gaynor and Grimes advanced a model for interresponse time distribution using probabilistic cycling between a higher-rate and a lower-rate response process. Both response processes are assumed to be random in time with a constant rate. The cycling between the two processes is assumed to have a constant transition probability that is…

An investigation of the kinetics of hydrogen chemisorption on iron metal surfaces

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1982-01-01

The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.

Effects of alteration product precipitation on glass dissolution

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

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H 4SiO 4) with higher [H 4SiO 4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H 4SiO 4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alterationmore » products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi 2O 6)∙H 2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH) 3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.« less

Role of Silver Salts Lattice Energy on Conductivity Drops in Chitosan Based Solid Electrolyte: Structural, Morphological and Electrical Characteristics

NASA Astrophysics Data System (ADS)

Aziz, Shujahadeen B.; Abdullah, Omed Gh.; Hussein, Sarkawt A.

2018-03-01

The influence of anion type on silver ion reduction and drop in direct current (DC) conductivity was investigated experimentally. The structural, optical, morphological and electrical properties of the samples were investigated using x-ray diffraction (XRD), ultraviolet-visible (UV-Vis), optical micrographs (OM) and impedance spectroscopy. The XRD results reveal significant disruption in the crystalline structure of chitosan (CS) for different concentrations of silver nitrate (AgNt) salt. The localized surface resonance plasmonic (LSRP) peaks that were observed for CS:AgNt samples, along with the white silver specs detected by OM technique confirm the formation of Ag nanoparticles. The appearance of obvious dark regions in the CS:AgNt system reveals the existence of a large percentage of amorphous domains. The nonexistence of spherulitic texture confirms the amorphous nature of the samples. The second semicircle in an impedance plot can be attributed to an Ag nanoparticle grain boundary. The established relationships between dielectric constant and carrier concentration and the behavior of dielectric constant versus salt concentration were used to explain the phenomenon of ion-ion association. The continuous increase of DC conductivity was noticed at high temperatures, which was then explained on the basis of lattice energy of silver salts. The influences of anion size on the rate of silver ion reductions are also interpreted.

The impact of thermal treatment on the stability of freeze-dried amorphous pharmaceuticals: II. Aggregation in an IgG1 fusion protein.

PubMed

Wang, Bingquan; Cicerone, Marcus T; Aso, Yukio; Pikal, Michael J

2010-02-01

The objective of this research was to investigate the impact of thermal treatment on storage stability of an IgG1 fusion protein. IgG1 protein formulations were prepared by freeze-drying the protein with sucrose. Some samples were used as controls, and others were subjected to a further heat treatment (annealing). The protein structure was investigated with Fourier transform infrared spectroscopy (FTIR), and protein aggregation was monitored with size exclusion HPLC. Enthalpy recovery was studied using DSC, and global mobility represented by the structural relaxation time constant (tau(beta)) was characterized by a thermal activity monitor (TAM). The local mobility of the protein system was monitored by both (13)C solid-state NMR and neutron backscattering. Annealing increased the storage stability of the protein, as shown by the smaller aggregation rate and less total aggregation at the end of a storage period. The structural relaxation time constant of an annealed sample was significantly higher than the unannealed control sample, suggesting a decrease in global mobility of the protein system upon annealing. However, annealing does not significantly impact the protein secondary structure or the local mobility. Given the similar protein native structure and specific surface area, the improved stability upon annealing is mainly a result of reduced global molecular mobility. (c) 2009 Wiley-Liss, Inc. and the American Pharmacists Association.

Kinetic Characterisation of a Single Chain Antibody against the Hormone Abscisic Acid: Comparison with Its Parental Monoclonal

PubMed Central

Badescu, George O.; Marsh, Andrew; Smith, Timothy R.; Thompson, Andrew J.; Napier, Richard M.

2016-01-01

A single-chain Fv fragment antibody (scFv) specific for the plant hormone abscisic acid (ABA) has been expressed in the bacterium Escherichia coli as a fusion protein. The kinetics of ABA binding have been measured using surface plasmon resonance spectrometry (BIAcore 2000) using surface and solution assays. Care was taken to calculate the concentration of active protein in each sample using initial rate measurements under conditions of partial mass transport limitation. The fusion product, parental monoclonal antibody and the free scFv all have low nanomolar affinity constants, but there is a lower dissociation rate constant for the parental monoclonal resulting in a three-fold greater affinity. Analogue specificity was tested and structure-activity binding preferences measured. The biologically-active (+)-ABA enantiomer is recognised with an affinity three orders of magnitude higher than the inactive (-)-ABA. Metabolites of ABA including phaseic acid, dihydrophaseic acid and deoxy-ABA have affinities over 100-fold lower than that for (+)-ABA. These properties of the scFv make it suitable as a sensor domain in bioreporters specific for the naturally occurring form of ABA. PMID:27023768

Real-time spectroscopic monitoring of photocatalytic activity promoted by graphene in a microfluidic reactor

PubMed Central

Li, Yifan; Lin, Beichen; Ge, Likai; Guo, Hongchen; Chen, Xinyi; Lu, Miao

2016-01-01

Photocatalytic microreactors have been utilized as rapid, versatile platforms for the characterization of photocatalysts. In this work, a photocatalytic microreactor integrated with absorption spectroscopy was proposed for the real-time monitoring of photocatalytic activity using different catalysts. The validity of this method was investigated by the rapid screening on the photocatalytic performance of a titanium oxide (TiO2)-decorated graphene oxide (GO) sheet for the degradation of methylene blue under monochromatic visible irradiation. The sampling interval time could be minimized to 10 s for achieving real-time detection. The best photocatalytic activity was observed for an optimized TiO2/GO weight mixing ratio of 7:11, with a reaction rate constant up to 0.067 min−1. The addition of GO into TiO2 enhances photocatalytic activity and adsorption of MB molecules. The synthetic reaction rate constant was up to approximately 0.11 min−1, which was also the highest among the catalysts. The microreactor exhibited good sensitivity and reproducibility without weakening the performance of the photocatalysts. Consequently, the photocatalytic microreactor is promising as a simple, portable, and rapid screening tool for new photocatalysts. PMID:27346555

Real-time spectroscopic monitoring of photocatalytic activity promoted by graphene in a microfluidic reactor

NASA Astrophysics Data System (ADS)

Li, Yifan; Lin, Beichen; Ge, Likai; Guo, Hongchen; Chen, Xinyi; Lu, Miao

2016-06-01

Photocatalytic microreactors have been utilized as rapid, versatile platforms for the characterization of photocatalysts. In this work, a photocatalytic microreactor integrated with absorption spectroscopy was proposed for the real-time monitoring of photocatalytic activity using different catalysts. The validity of this method was investigated by the rapid screening on the photocatalytic performance of a titanium oxide (TiO2)-decorated graphene oxide (GO) sheet for the degradation of methylene blue under monochromatic visible irradiation. The sampling interval time could be minimized to 10 s for achieving real-time detection. The best photocatalytic activity was observed for an optimized TiO2/GO weight mixing ratio of 7:11, with a reaction rate constant up to 0.067 min-1. The addition of GO into TiO2 enhances photocatalytic activity and adsorption of MB molecules. The synthetic reaction rate constant was up to approximately 0.11 min-1, which was also the highest among the catalysts. The microreactor exhibited good sensitivity and reproducibility without weakening the performance of the photocatalysts. Consequently, the photocatalytic microreactor is promising as a simple, portable, and rapid screening tool for new photocatalysts.