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

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

On determining dose rate constants spectroscopically.

PubMed

Rodriguez, M; Rogers, D W O

2013-01-01

To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of (125)I and (103)Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated (125)I and (103)Pd sources. Spectra generated by 14 (125)I and 6 (103)Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 × 2.7 × 0.05 cm(3) voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the (125)I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for (103)Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were ≤0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. The ratio of the intensity of the 31 keV line relative to that of the main peak in (125)I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The (103)Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when calculated with the TG-43U1 rather than the NNDC(2000) initial spectrum. The measured values from three different investigations are

On determining dose rate constants spectroscopically

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

Rodriguez, M.; Rogers, D. W. O.

2013-01-15

Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of {sup 125}I and {sup 103}Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated {sup 125}I and {sup 103}Pd sources. Methods: Spectra generated by 14 {sup 125}I and 6 {sup 103}Pd seedsmore » were calculated in vacuo at 10 cm from the source in a 2.7 Multiplication-Sign 2.7 Multiplication-Sign 0.05 cm{sup 3} voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the {sup 125}I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for {sup 103}Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were Less-Than-Or-Slanted-Equal-To 0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in {sup 125}I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The {sup 103}Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak

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

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

Thermal degradation of deoxynivalenol during maize bread baking.

PubMed

Numanoglu, E; Gökmen, V; Uygun, U; Koksel, H

2012-01-01

The thermal degradation of deoxynivalenol (DON) was determined at isothermal baking conditions within the temperature range of 100-250°C, using a crust-like model, which was prepared with naturally contaminated maize flour. No degradation was observed at 100°C. For the temperatures of 150, 200 and 250°C, thermal degradation rate constants (k) were calculated and temperature dependence of DON degradation was observed by using Arrhenius equation. The degradation of DON obeyed Arrhenius law with a regression coefficient of 0.95. A classical bread baking operation was also performed at 250°C for 70 min and the rate of DON degradation in the bread was estimated by using the kinetic data derived from the model study. The crust and crumb temperatures recorded during bread baking were used to calculate the thermal degradation rate constants (k) and partial DON degradations at certain time intervals. Using these data, total degradation at the end of the entire baking process was predicted for both crust and crumb. This DON degradation was consistent with the experimental degradation data, confirming the accuracy of kinetic constants determined by means of the crust-like model.

Biotransformation of trace organic chemicals during groundwater recharge: How useful are first-order rate constants?

PubMed

Regnery, J; Wing, A D; Alidina, M; Drewes, J E

2015-08-01

This study developed relationships between the attenuation of emerging trace organic chemicals (TOrC) during managed aquifer recharge (MAR) as a function of retention time, system characteristics, and operating conditions using controlled laboratory-scale soil column experiments simulating MAR. The results revealed that MAR performance in terms of TOrC attenuation is primarily determined by key environmental parameters (i.e., redox, primary substrate). Soil columns with suboxic and anoxic conditions performed poorly (i.e., less than 30% attenuation of moderately degradable TOrC) in comparison to oxic conditions (on average between 70-100% attenuation for the same compounds) within a residence time of three days. Given this dependency on redox conditions, it was investigated if key parameter-dependent rate constants are more suitable for contaminant transport modeling to properly capture the dynamic TOrC attenuation under field-scale conditions. Laboratory-derived first-order removal kinetics were determined for 19 TOrC under three different redox conditions and rate constants were applied to MAR field data. Our findings suggest that simplified first-order rate constants will most likely not provide any meaningful results if the target compounds exhibit redox dependent biotransformation behavior or if the intention is to exactly capture the decline in concentration over time and distance at field-scale MAR. However, if the intention is to calculate the percent removal after an extended time period and subsurface travel distance, simplified first-order rate constants seem to be sufficient to provide a first estimate on TOrC attenuation during MAR. Copyright © 2015 Elsevier B.V. All rights reserved.

Degradation Kinetics of VX

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

Gary S. Groenewold

2010-12-01

O-ethyl S-(2-diisopropylaminoethyl)phosphonothiolate (VX) is the most toxic of the conventional chemical warfare agents. It is a persistent compound, an attribute derived from its relative involatility and slow rates of hydrolysis. These properties suggest that VX can linger in an exposed environment for extended periods of time long after the air has cleared. Concern over prolonged risk from VX exposure is exacerbated by the fact that it poses a dermal contact hazard. Hence a detailed understanding of volatilization rates, and degradation pathways and rates occurring in various environments is needed. Historically, volatilization has not been considered to be an important mechanismmore » for VX depletion, but recent studies have shown that a significant fraction of VX may volatilize, depending on the matrix. A significant body of research has been conducted over the years to unravel VX degradation reaction pathways and to quantify the rates at which they proceed. Rigorous measurement of degradation rates is frequently difficult, and thus in many cases the degradation of VX has been described in terms of half lives, while in fewer instances rate constants have been measured. This variable approach to describing degradation kinetics reflects uncertainty regarding the exact nature of the degradation mechanisms. In this review, rates of VX degradation are compared on the basis of pseudo-first order rate constants, in order to provide a basis for assessing likelihood of VX persistence in a given environment. An issue of specific concern is that one VX degradation pathway produces S-2-(diisopropylaminoethyl) methylphosphonothioic acid (known as EA2192), which is a degradation product that retains much of the original toxicity of VX. Consequently degradation pathways and rates for EA2192 are also discussed.« less

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.

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)

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.

Determination of a Degradation Constant for CYP3A4 by Direct Suppression of mRNA in a Novel Human Hepatocyte Model, HepatoPac.

PubMed

Ramsden, Diane; Zhou, Jin; Tweedie, Donald J

2015-09-01

Accurate determination of rates of de novo synthesis and degradation of cytochrome P450s (P450s) has been challenging. There is a high degree of variability in the multiple published values of turnover for specific P450s that is likely exacerbated by differences in methodologies. For CYP3A4, reported half-life values range from 10 to 140 hours. An accurate value for kdeg has been identified as a major limitation for prediction of drug interactions involving mechanism-based inhibition and/or induction. Estimation of P450 half-life from in vitro test systems, such as human hepatocytes, is complicated by differential decreased enzyme function over culture time, attenuation of the impact of enzyme loss through inclusion of glucocorticoids in media, and viability limitations over long-term culture times. HepatoPac overcomes some of these challenges by providing extended stability of enzymes (2.5 weeks in our hands). As such it is a unique tool for studying rates of enzyme degradation achieved through modulation of enzyme levels. CYP3A4 mRNA levels were rapidly depleted by >90% using either small interfering RNA or addition of interleukin-6, which allowed an estimation of the degradation rate constant for CYP3A protein over an incubation time of 96 hours. The degradation rate constant of 0.0240 ± 0.005 hour(-1) was reproducible in hepatocytes from five different human donors. These donors also reflected the overall population with respect to CYP3A5 genotype. This methodology can be applied to additional enzymes and may provide a more accurate in vitro derived kdeg value for predicting clinical drug-drug interaction outcomes. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

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.

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.

Kinetic study and mechanism of Niclosamide degradation.

PubMed

Zaazaa, Hala E; Abdelrahman, Maha M; Ali, Nouruddin W; Magdy, Maimana A; Abdelkawy, M

2014-11-11

A spectrophotometric kinetic study of Niclosamide alkaline degradation as a function of drug concentration, alkaline concentration and temperature has been established utilizing double divisor-ratio spectra spectrophotometric method. The developed method allowed determination of Niclosamide in presence of its alkaline degradation products; namely; 2-chloro-4-nitro aniline (DEG I) and 5-chloro salicylic acid (DEG II) with characterization of its degradation mechanism. It was found that degradation kinetic of Niclosamide followed pseudo-first order under the established experimental conditions with a degradation rate constant (k) of 0.0829 mol/h and half life (t1/2) of 8.35 h. The overall degradation rate constant as a function of the temperature under the given conditions obeyed Arrhenius equation where the activation energy was calculated to be 3.41 kcal/mol. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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

Precisely and Accurately Inferring Single-Molecule Rate Constants

PubMed Central

Kinz-Thompson, Colin D.; Bailey, Nevette A.; Gonzalez, Ruben L.

2017-01-01

The kinetics of biomolecular systems can be quantified by calculating the stochastic rate constants that govern the biomolecular state versus time trajectories (i.e., state trajectories) of individual biomolecules. To do so, the experimental signal versus time trajectories (i.e., signal trajectories) obtained from observing individual biomolecules are often idealized to generate state trajectories by methods such as thresholding or hidden Markov modeling. Here, we discuss approaches for idealizing signal trajectories and calculating stochastic rate constants from the resulting state trajectories. Importantly, we provide an analysis of how the finite length of signal trajectories restrict the precision of these approaches, and demonstrate how Bayesian inference-based versions of these approaches allow rigorous determination of this precision. Similarly, we provide an analysis of how the finite lengths and limited time resolutions of signal trajectories restrict the accuracy of these approaches, and describe methods that, by accounting for the effects of the finite length and limited time resolution of signal trajectories, substantially improve this accuracy. Collectively, therefore, the methods we consider here enable a rigorous assessment of the precision, and a significant enhancement of the accuracy, with which stochastic rate constants can be calculated from single-molecule signal trajectories. PMID:27793280

Efforts to estimate pesticide degradation rates in subsurface ...

EPA Pesticide Factsheets

When pesticides are used in real-world settings, the objective is to be effective in pest eradication at the site of application, but also it is desired that the pesticide have minimal persistence and mobility as it migrates away from the application site. At the site of application, sorption on soil and surface-soil degradation rates both factor into the pesticides' persistence. But once it migrates to the subsurface vadose zone and/or aquifers, subsurface degradation rate is a factor as well. Unfortunately, numerous soil properties that might affect pesticide degradation rate vary by orders of magnitude in the subsurface environment, both spatially and temporally, e.g., organic-carbon concentration, oxygen concentration, redox conditions, pH and soil mineralogy. Consequently, estimation of subsurface pesticide degradation rates and, in tum, pesticide persistence and mobility in the environment, has remained a challenge. To address this intransigent uncertainty, we surveyed peer-reviewed literature to identify > 100 data pairs in which investigators reported pesticide degradation rates in both surface and subsurface soils, using internally consistent experimental methods. These > 100 data pairs represented >30 separate pesticides. When the > 100 subsurface half-lives were plotted against surface half-lives, a limiting line could be defined for which all subsurface half-lives but three fe ll below the line. Of the three data points plotting above the limiting li

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.

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor.

PubMed

Oliveira, A G; Cuccovia, I M; Chaimovich, H

1990-01-01

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the framework of the pseudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Rate of antioxidant degradation and color variations in dehydrated apples as related to water activity.

PubMed

Lavelli, Vera; Vantaggi, Claudia

2009-06-10

Dehydrated apples were studied to evaluate the effects of water activity on the stability of their antioxidants and color. Apples were freeze-dried, ground, then equilibrated, and stored at eight water activity levels, ranging from 0.058 to 0.747, at 40 degrees C. Their contents of hydroxycinnamic acids, dihydrochalcones, catechin, epicatechin, polymeric flavan-3-ols, and hydroxymethylfurfural, their antioxidant activity values, and their Hunter colorimetric parameters were analyzed at different storage times. Antioxidant degradation followed pseudo-first-order kinetics and was accelerated by increasing the water activity. The order of antioxidant stability in the products at water activity levels below 0.316 was catechin, epicatechin, and ascorbic acid < total procyanidins < dihydrochalcones and p-coumaric acid < chlorogenic acid; however, in the products at water activity levels above 0.316, the degradation of all antioxidants was very fast. The hydroxymethylfurfural formation rate increased exponentially during storage, especially at high water activity levels. The antioxidant activity of the dehydrated apples decreased during storage, consistent with antioxidant loss. The variations of the colorimetric parameters, namely, lightness (L*), redness (a*), and yellowness (b*), followed pseudo-zero-order kinetics and were accelerated by increasing water activity. All analytical indices indicated that the dehydrated apples were stable at water activity levels below 0.316, with the degradation rate accelerating upon exposure to higher relative humidities. Above 0.316, a small increase in water activity of the product would sharply increase the degradation rate constants for both antioxidant and color variations.

Degradation properties of protein and carbohydrate during sludge anaerobic digestion.

PubMed

Yang, Guang; Zhang, Panyue; Zhang, Guangming; Wang, Yuanyuan; Yang, Anqi

2015-09-01

Degradation of protein and carbohydrate is vital for sludge anaerobic digestion performance. However, few studies focused on degradation properties of protein and carbohydrate. This study investigated detailed degradation properties of sludge protein and carbohydrate in order to gain insight into organics removal during anaerobic digestion. Results showed that carbohydrate was more efficiently degraded than protein and was degraded prior to protein. The final removal efficiencies of carbohydrate and protein were 49.7% and 32.2%, respectively. The first 3 days were a lag phase for protein degradation since rapid carbohydrate degradation in this phase led to repression of protease formation. Kinetics results showed that, after initial lag phase, protein degradation followed the first-order kinetic with rate constants of 0.0197 and 0.0018 d(-1) during later rapid degradation phase and slow degradation phase, respectively. Carbohydrate degradation also followed the first-order kinetics with a rate constant of 0.007 d(-1) after initial quick degradation phase. Copyright © 2015 Elsevier Ltd. All rights reserved.

Computer Calculation of First-Order Rate Constants

ERIC Educational Resources Information Center

Williams, Robert C.; Taylor, James W.

1970-01-01

Discusses the computer program used to calculate first-order rate constants. Discussion includes data preparation, weighting options, comparison techniques, infinity point adjustment, least-square fit, Guggenheim calculation, and printed outputs. Exemplifies the utility of the computer program by two experiments: (1) the thermal decomposition of…

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.

Hydrolysis of VX on Concrete: Rate of Degradation by Direct Surface Interrogation using an Ion Trap Secondary Ion Mass Spectrometer

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

Groenewold, Gary Steven; Appelhans, Anthony David; Gresham, Garold Linn

2002-09-01

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease inmore » an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min-1 at 25 C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol-1. This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.« less

Hydrolysis of VX on concrete: rate of degradation by direct surface interrogation using an ion trap secondary ion mass spectrometer.

PubMed

Groenewold, Gary S; Williams, John M; Appelhans, Anthony D; Gresham, Garold L; Olson, John E; Jeffery, Mark T; Rowland, Brad

2002-11-15

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min(-1) at 25 degrees C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 degrees C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol(-1). This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.

Influences of brain tissue poroelastic constants on intracranial pressure (ICP) during constant-rate infusion.

PubMed

Li, Xiaogai; von Holst, Hans; Kleiven, Svein

2013-01-01

A 3D finite element (FE) model has been developed to study the mean intracranial pressure (ICP) response during constant-rate infusion using linear poroelasticity. Due to the uncertainties in the poroelastic constants for brain tissue, the influence of each of the main parameters on the transient ICP infusion curve was studied. As a prerequisite for transient analysis, steady-state simulations were performed first. The simulated steady-state pressure distribution in the brain tissue for a normal cerebrospinal fluid (CSF) circulation system showed good correlation with experiments from the literature. Furthermore, steady-state ICP closely followed the infusion experiments at different infusion rates. The verified steady-state models then served as a baseline for the subsequent transient models. For transient analysis, the simulated ICP shows a similar tendency to that found in the experiments, however, different values of the poroelastic constants have a significant effect on the infusion curve. The influence of the main poroelastic parameters including the Biot coefficient α, Skempton coefficient B, drained Young's modulus E, Poisson's ratio ν, permeability κ, CSF absorption conductance C(b) and external venous pressure p(b) was studied to investigate the influence on the pressure response. It was found that the value of the specific storage term S(ε) is the dominant factor that influences the infusion curve, and the drained Young's modulus E was identified as the dominant parameter second to S(ε). Based on the simulated infusion curves from the FE model, artificial neural network (ANN) was used to find an optimised parameter set that best fit the experimental curve. The infusion curves from both the FE simulation and using ANN confirmed the limitation of linear poroelasticity in modelling the transient constant-rate infusion.

Effect of height and orientation ( microclimate) on geomorphic degradation rates and processes, late-glacial terrace scarps in central Idaho

USGS Publications Warehouse

Pierce, K.L.; Colman, Steven M.

1986-01-01

Examines the effects of scarp size (height) and orientation (microclimate) by keeping constant variables such as age, lithology, and regional climate. For scarps 2m high, the degradation rate on S-facing scarps is 2 times that on N-facing scarps; for 10-m scarps, it is 5 times. Scarp morphology may be used to estimate age. -from Authors

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

PubMed

Liu, Yu-Hai; Ye, Zhao-Lian; Wen, Ying-Pin; Bi, Cheng-Lu

2014-06-01

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

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...

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.

Determination of LEDs degradation with entropy generation rate

NASA Astrophysics Data System (ADS)

Cuadras, Angel; Yao, Jiaqiang; Quilez, Marcos

2017-10-01

We propose a method to assess the degradation and aging of light emitting diodes (LEDs) based on irreversible entropy generation rate. We degraded several LEDs and monitored their entropy generation rate ( S ˙ ) in accelerated tests. We compared the thermoelectrical results with the optical light emission evolution during degradation. We find a good relationship between aging and S ˙ (t), because S ˙ is both related to device parameters and optical performance. We propose a threshold of S ˙ (t) as a reliable damage indicator of LED end-of-life that can avoid the need to perform optical measurements to assess optical aging. The method lays beyond the typical statistical laws for lifetime prediction provided by manufacturers. We tested different LED colors and electrical stresses to validate the electrical LED model and we analyzed the degradation mechanisms of the devices.

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...

On the Determination of Magnesium Degradation Rates under Physiological Conditions.

PubMed

Nidadavolu, Eshwara Phani Shubhakar; Feyerabend, Frank; Ebel, Thomas; Willumeit-Römer, Regine; Dahms, Michael

2016-07-28

The current physiological in vitro tests of Mg degradation follow the procedure stated according to the ASTM standard. This standard, although useful in predicting the initial degradation behavior of an alloy, has its limitations in interpreting the same for longer periods of immersion in cell culture media. This is an important consequence as the alloy's degradation is time dependent. Even if two different alloys show similar corrosion rates in a short term experiment, their degradation characteristics might differ with increased immersion times. Furthermore, studies concerning Mg corrosion extrapolate the corrosion rate from a single time point measurement to the order of a year (mm/y), which might not be appropriate because of time dependent degradation behavior. In this work, the above issues are addressed and a new methodology of performing long-term immersion tests in determining the degradation rates of Mg alloys was put forth. For this purpose, cast and extruded Mg-2Ag and powder pressed and sintered Mg-0.3Ca alloy systems were chosen. DMEM Glutamax +10% FBS (Fetal Bovine Serum) +1% Penicillin streptomycin was used as cell culture medium. The advantages of such a method in predicting the degradation rates in vivo deduced from in vitro experiments are discussed.

On the Determination of Magnesium Degradation Rates under Physiological Conditions

PubMed Central

Nidadavolu, Eshwara Phani Shubhakar; Feyerabend, Frank; Ebel, Thomas; Willumeit-Römer, Regine; Dahms, Michael

2016-01-01

The current physiological in vitro tests of Mg degradation follow the procedure stated according to the ASTM standard. This standard, although useful in predicting the initial degradation behavior of an alloy, has its limitations in interpreting the same for longer periods of immersion in cell culture media. This is an important consequence as the alloy’s degradation is time dependent. Even if two different alloys show similar corrosion rates in a short term experiment, their degradation characteristics might differ with increased immersion times. Furthermore, studies concerning Mg corrosion extrapolate the corrosion rate from a single time point measurement to the order of a year (mm/y), which might not be appropriate because of time dependent degradation behavior. In this work, the above issues are addressed and a new methodology of performing long-term immersion tests in determining the degradation rates of Mg alloys was put forth. For this purpose, cast and extruded Mg-2Ag and powder pressed and sintered Mg-0.3Ca alloy systems were chosen. DMEM Glutamax +10% FBS (Fetal Bovine Serum) +1% Penicillin streptomycin was used as cell culture medium. The advantages of such a method in predicting the degradation rates in vivo deduced from in vitro experiments are discussed. PMID:28773749

EVALUATING DEGRADATION RATES OF CHLORINATED ORGANICS IN GROUNDWATER USING ANALYTICAL MODELS

EPA Science Inventory

The persistence and fate of organic contaminants in the environment largely depends on their rate of degradation. Most studies of degradation rate are performed in the lab where chemical conditions can be controlled precisely. Unfortunately, literature values for lab degradation ...

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.

Flame Chemiluminescence Rate Constants for Quantitative Microgravity Combustion Diagnostics

NASA Technical Reports Server (NTRS)

Luque, Jorge; Smith, Gregory P.; Jeffries, Jay B.; Crosley, David R.; Weiland, Karen (Technical Monitor)

2001-01-01

Absolute excited state concentrations of OH(A), CH(A), and C2(d) were determined in three low pressure premixed methane-air flames. Two dimensional images of chemiluminescence from these states were recorded by a filtered CCD camera, processed by Abel inversion, and calibrated against Rayleigh scattering, Using a previously validated 1-D flame model with known chemistry and excited state quenching rate constants, rate constants are extracted for the reactions CH + O2 (goes to) OH(A) + CO and C2H + O (goes to) CH(A) + CO at flame temperatures. Variations of flame emission intensities with stoichiometry agree well with model predictions.

Anthocyanins degradation during storage of Hibiscus sabdariffa extract and evolution of its degradation products.

PubMed

Sinela, André; Rawat, Nadirah; Mertz, Christian; Achir, Nawel; Fulcrand, Hélène; Dornier, Manuel

2017-01-01

Degradation parameters of two main anthocyanins from roselle extract (Hibiscus sabdariffa L.) stored at different temperatures (4-37°C) over 60days were determined. Anthocyanins and some of their degradation products were monitored and quantified using HPLC-MS and DAD. Degradation of anthocyanins followed first-order kinetics and reaction rate constants (k values), which were obtained by non-linear regression, showed that the degradation rate of delphinidin 3-O-sambubioside was higher than that of cyanidin 3-O-sambubioside with k values of 9.2·10(-7)s(-1) and 8.4·10(-7)s(-1) at 37°C respectively. The temperature dependence of the rate of anthocyanin degradation was modeled by the Arrhenius equation. Degradation of delphinidin 3-O-sambubioside (Ea=90kJmol(-1)) tended to be significantly more sensitive to an increase in temperature than cyanidin 3-O-sambubioside (Ea=80kJmol(-1)). Degradation of these anthocyanins formed scission products (gallic and protocatechuic acids respectively) and was accompanied by an increase in polymeric color index. Copyright © 2016 Elsevier Ltd. All rights reserved.

Study of stiffness and bearing capacity degradation of reinforced concrete beams under constant-amplitude fatigue

PubMed Central

Zhou, Jianting; Yan, Lei

2018-01-01

For a reinforced concrete beam subjected to fatigue loads, the structural stiffness and bearing capacity will gradually undergo irreversible degeneration, leading to damage. Moreover, there is an inherent relationship between the stiffness and bearing capacity degradation and fatigue damage. In this study, a series of fatigue tests are performed to examine the degradation law of the stiffness and bearing capacity. The results pertaining to the stiffness show that the stiffness degradation of a reinforced concrete beam exhibits a very clear monotonic decreasing "S" curve, i.e., the stiffness of the beam decreases significantly at the start of the fatigue loading, it undergoes a linear decline phase in the middle for a long loading period, and before the failure, the bearing capacity decreases drastically again. The relationship between the residual stiffness and residual bearing capacity is determined based on the assumption that the residual stiffness and residual bearing capacity depend on the same damage state, and then, the bearing capacity degradation model of the reinforced concrete beam is established based on the fatigue stiffness. Through the established model and under the premise of the known residual stiffness degradation law, the degradation law of the bearing capacity is determined by using at least one residual bearing capacity test data, for which the parameters of the stiffness degradation function are considered as material constants. The results of the bearing capacity show that the bearing capacity degradation of the reinforced concrete beam also exhibits a very clear monotonic decreasing "S" curve, which is consistent with the stiffness degradation process and in good agreement with the experiment. In this study, the stiffness and bearing capacity degradation expressions are used to quantitatively describe their occurrence in reinforced concrete beams. In particular, the expression of the bearing capacity degradation can mitigate numerous

Study of stiffness and bearing capacity degradation of reinforced concrete beams under constant-amplitude fatigue.

PubMed

Liu, Fangping; Zhou, Jianting; Yan, Lei

2018-01-01

For a reinforced concrete beam subjected to fatigue loads, the structural stiffness and bearing capacity will gradually undergo irreversible degeneration, leading to damage. Moreover, there is an inherent relationship between the stiffness and bearing capacity degradation and fatigue damage. In this study, a series of fatigue tests are performed to examine the degradation law of the stiffness and bearing capacity. The results pertaining to the stiffness show that the stiffness degradation of a reinforced concrete beam exhibits a very clear monotonic decreasing "S" curve, i.e., the stiffness of the beam decreases significantly at the start of the fatigue loading, it undergoes a linear decline phase in the middle for a long loading period, and before the failure, the bearing capacity decreases drastically again. The relationship between the residual stiffness and residual bearing capacity is determined based on the assumption that the residual stiffness and residual bearing capacity depend on the same damage state, and then, the bearing capacity degradation model of the reinforced concrete beam is established based on the fatigue stiffness. Through the established model and under the premise of the known residual stiffness degradation law, the degradation law of the bearing capacity is determined by using at least one residual bearing capacity test data, for which the parameters of the stiffness degradation function are considered as material constants. The results of the bearing capacity show that the bearing capacity degradation of the reinforced concrete beam also exhibits a very clear monotonic decreasing "S" curve, which is consistent with the stiffness degradation process and in good agreement with the experiment. In this study, the stiffness and bearing capacity degradation expressions are used to quantitatively describe their occurrence in reinforced concrete beams. In particular, the expression of the bearing capacity degradation can mitigate numerous

Enhanced sonochemical degradation of azure B dye by the electroFenton process.

PubMed

Martínez, Susana Silva; Uribe, Edgar Velasco

2012-01-01

The degradation of azure B dye (C15H16ClN3S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H2O2 at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe2+, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton>Fenton>sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes. Copyright © 2011 Elsevier B.V. All rights reserved.

The cellular growth rate controls overall mRNA turnover, and modulates either transcription or degradation rates of particular gene regulons.

PubMed

García-Martínez, José; Delgado-Ramos, Lidia; Ayala, Guillermo; Pelechano, Vicent; Medina, Daniel A; Carrasco, Fany; González, Ramón; Andrés-León, Eduardo; Steinmetz, Lars; Warringer, Jonas; Chávez, Sebastián; Pérez-Ortín, José E

2016-05-05

We analyzed 80 different genomic experiments, and found a positive correlation between both RNA polymerase II transcription and mRNA degradation with growth rates in yeast. Thus, in spite of the marked variation in mRNA turnover, the total mRNA concentration remained approximately constant. Some genes, however, regulated their mRNA concentration by uncoupling mRNA stability from the transcription rate. Ribosome-related genes modulated their transcription rates to increase mRNA levels under fast growth. In contrast, mitochondria-related and stress-induced genes lowered mRNA levels by reducing mRNA stability or the transcription rate, respectively. We also detected these regulations within the heterogeneity of a wild-type cell population growing in optimal conditions. The transcriptomic analysis of sorted microcolonies confirmed that the growth rate dictates alternative expression programs by modulating transcription and mRNA decay.The regulation of overall mRNA turnover keeps a constant ratio between mRNA decay and the dilution of [mRNA] caused by cellular growth. This regulation minimizes the indiscriminate transmission of mRNAs from mother to daughter cells, and favors the response capacity of the latter to physiological signals and environmental changes. We also conclude that, by uncoupling mRNA synthesis from decay, cells control the mRNA abundance of those gene regulons that characterize fast and slow growth. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

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...

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

Theoretical Evaluation of the Transient Response of Constant Head and Constant Flow-Rate Permeability Tests

USGS Publications Warehouse

Zhang, M.; Takahashi, M.; Morin, R.H.; Esaki, T.

1998-01-01

A theoretical analysis is presented that compares the response characteristics of the constant head and the constant flowrate (flow pump) laboratory techniques for quantifying the hydraulic properties of geologic materials having permeabilities less than 10-10 m/s. Rigorous analytical solutions that describe the transient distributions of hydraulic gradient within a specimen are developed, and equations are derived for each method. Expressions simulating the inflow and outflow rates across the specimen boundaries during a constant-head permeability test are also presented. These solutions illustrate the advantages and disadvantages of each method, including insights into measurement accuracy and the validity of using Darcy's law under certain conditions. The resulting observations offer practical considerations in the selection of an appropriate laboratory test method for the reliable measurement of permeability in low-permeability geologic materials.

Increased degradation rate of nitrososureas in media containing carbonate.

PubMed

Seidegård, Janeric; Grönquist, Lena; Tuvesson, Helen; Gunnarsson, Per-Olov

2009-01-01

The stability of two nitrosoureas, tauromustine and lomustine, has been investigated in different media and buffers. All media tested, except Leibovitz's L-15 medium, significantly increased the degradation rate of the investigated nitrosoureas at pH 7.4. Sodium bicarbonate seems to be the cause of the observed increase of the degradation rate, since it provides the main buffering capacity of all the media except for Leibovitz's L-15 medium, which is based on phosphate buffer. Other ingredients in the media, such as amino acids, vitamins, and inorganic salts, or the ionic strength of a buffer, did not have any major effect on the degradation rate of the nitrosoureas. These results suggest that media containing carbonated buffer should be avoided when the anti-tumor effect of nitrosoureas is to be investigated in different cell cultures.

18 CFR 806.12 - Constant-rate aquifer testing.

Code of Federal Regulations, 2010 CFR

2010-04-01

... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Constant-rate aquifer testing. 806.12 Section 806.12 Conservation of Power and Water Resources SUSQUEHANNA RIVER BASIN...

BACTERIAL METHYLMERCURY DEGRADATION IN FLORIDA EVERGLADES PEAT SEDIMENT

EPA Science Inventory

Methylmercury (MeHg) degradation was investigated along an eutrophication gradient in the Florida Everglades by quantifying 14CH4 and 14CO2 production after incubation of anaerobic sediments with [14C]MeHg. Degradation rate constants (k) were consistently <=0.1 d-1 and decreased ...

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...

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.

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

Influence of humic acid addition on the degradation of pharmaceuticals by biofilms in effluent wastewater.

PubMed

Tang, Kai; Escola Casas, Monica; Ooi, Gordon T H; Kaarsholm, Kamilla M S; Bester, Kai; Andersen, Henrik R

2017-05-01

The degradation of organic micropollutants in wastewater treatment is suspected to depend on co-degradation i.e. be dependent on concentrations of substrate. This complicates predicting and modelling their fate. The effect of humic acid, as a model for complex organic substrate, was investigated in relation to the biodegradation of pharmaceuticals by suspended biofilm carriers adapted to polishing effluent water from a tertiary sewage treatment plant. Twelve out of 22 investigated pharmaceuticals were significantly biodegradable. The biodegradation rate constants of ten of those compounds were increasing with increased humic acid concentrations. At the highest humic acid concentration (30mgC/L), the biodegradation rate constants were four times higher than the biodegradation rate constants without added humic acid. This shows that the presence of complex substrate stimulates degradation via a co-metabolism-like mechanism and competitive inhibition does not occur. Increases of rate constant per mgC/L are tentatively calculated. Copyright © 2017 Elsevier GmbH. All rights reserved.

Degradation kinetics of ptaquiloside in soil and soil solution.

PubMed

Ovesen, Rikke Gleerup; Rasmussen, Lars Holm; Hansen, Hans Christian Bruun

2008-02-01

Ptaquiloside (PTA) is a carcinogenic norsesquiterpene glycoside produced in bracken (Pteridium aquilinum (L.) Kuhn), a widespread, aggressive weed. Transfer of PTA to soil and soil solution eventually may contaminate groundwater and surface water. Degradation rates of PTA were quantified in soil and soil solutions in sandy and clayey soils subjected to high natural PTA loads from bracken stands. Degradation kinetics in moist soil could be fitted with the sum of a fast and a slow first-order reaction; the fast reaction contributed 20 to 50% of the total degradation of PTA. The fast reaction was similar in all horizons, with the rate constant k(1F) ranging between 0.23 and 1.5/h. The slow degradation, with the rate constant k(1S) ranging between 0.00067 and 0.029/ h, was more than twice as fast in topsoils compared to subsoils, which is attributable to higher microbial activity in topsoils. Experiments with sterile controls confirmed that nonmicrobial degradation processes constituted more than 90% of the fast degradation and 50% of the slow degradation. The lower nonmicrobial degradation rate observed in the clayey compared with the sandy soil is attributed to a stabilizing effect of PTA by clay silicates. Ptaquiloside appeared to be stable in all soil solutions, in which no degradation was observed within a period of 28 d, in strong contrast to previous studies of hydrolysis rates in artificial aqueous electrolytes. The present study predicts that the risk of PTA leaching is controlled mainly by the residence time of pore water in soil, soil microbial activity, and content of organic matter and clay silicates.

Steady-State Computation of Constant Rotational Rate Dynamic Stability Derivatives

NASA Technical Reports Server (NTRS)

Park, Michael A.; Green, Lawrence L.

2000-01-01

Dynamic stability derivatives are essential to predicting the open and closed loop performance, stability, and controllability of aircraft. Computational determination of constant-rate dynamic stability derivatives (derivatives of aircraft forces and moments with respect to constant rotational rates) is currently performed indirectly with finite differencing of multiple time-accurate computational fluid dynamics solutions. Typical time-accurate solutions require excessive amounts of computational time to complete. Formulating Navier-Stokes (N-S) equations in a rotating noninertial reference frame and applying an automatic differentiation tool to the modified code has the potential for directly computing these derivatives with a single, much faster steady-state calculation. The ability to rapidly determine static and dynamic stability derivatives by computational methods can benefit multidisciplinary design methodologies and reduce dependency on wind tunnel measurements. The CFL3D thin-layer N-S computational fluid dynamics code was modified for this study to allow calculations on complex three-dimensional configurations with constant rotation rate components in all three axes. These CFL3D modifications also have direct application to rotorcraft and turbomachinery analyses. The modified CFL3D steady-state calculation is a new capability that showed excellent agreement with results calculated by a similar formulation. The application of automatic differentiation to CFL3D allows the static stability and body-axis rate derivatives to be calculated quickly and exactly.

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.

Degradation rate of lyophilized insulin, exhibiting an apparent Arrhenius behavior around glass transition temperature regardless of significant contribution of molecular mobility.

PubMed

Yoshioka, Sumie; Miyazaki, Tamaki; Aso, Yukio

2006-12-01

The relative influences of chemical activation energy and molecular mobility in determining chemical reactivity were evaluated for insulin lyophilized with alpha,beta-poly(N-hydroxyethyl)-L-aspartamide (PHEA), and compared with that for insulin lyophilized with trehalose, which had been found to have the ability to decrease the molecular mobility of insulin at low humidity. The ratio of the observed rate constant k(obs) to the chemical activation energy-controlled rate constant k(act) (k(obs)/k(act)) at glass transition temperature (T(g)) was estimated to be approximately 0.6 and 0.8 at 6% RH and 12% RH, respectively, indicating that the degradation rate is significantly affected by molecular mobility at lower humidity conditions. However, these k(obs)/k(act) values at T(g) were larger than those for the insulin-trehalose system, and changes in the temperature-dependent slope around T(g) were less obvious than those for the insulin-trehalose system. Thus, the contribution of molecular mobility to the degradation rate in the insulin-PHEA system appeared to be less intense than that in the insulin-trehalose system. The subtle change in the temperature-dependent slope around T(g) observed in the insulin-PHEA system brought about a significant bias in shelf-life estimation when the reaction rate was extrapolated from temperatures above T(g) according to the Arrhenius equation. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association

Multiple Transcript Properties Related to Translation Affect mRNA Degradation Rates in Saccharomyces cerevisiae

PubMed Central

Neymotin, Benjamin; Ettorre, Victoria; Gresham, David

2016-01-01

Degradation of mRNA contributes to variation in transcript abundance. Studies of individual mRNAs have shown that both cis and trans factors affect mRNA degradation rates. However, the factors underlying transcriptome-wide variation in mRNA degradation rates are poorly understood. We investigated the contribution of different transcript properties to transcriptome-wide degradation rate variation in the budding yeast, Saccharomyces cerevisiae, using multiple regression analysis. We find that multiple transcript properties are significantly associated with variation in mRNA degradation rates, and that a model incorporating these properties explains ∼50% of the genome-wide variance. Predictors of mRNA degradation rates include transcript length, ribosome density, biased codon usage, and GC content of the third position in codons. To experimentally validate these factors, we studied individual transcripts expressed from identical promoters. We find that decreasing ribosome density by mutating the first translational start site of a transcript increases its degradation rate. Using coding sequence variants of green fluorescent protein (GFP) that differ only at synonymous sites, we show that increased GC content of the third position of codons results in decreased rates of mRNA degradation. Thus, in steady-state conditions, a large fraction of genome-wide variation in mRNA degradation rates is determined by inherent properties of transcripts, many of which are related to translation, rather than specific regulatory mechanisms. PMID:27633789

Rapid and accurate prediction of degradant formation rates in pharmaceutical formulations using high-performance liquid chromatography-mass spectrometry.

PubMed

Darrington, Richard T; Jiao, Jim

2004-04-01

Rapid and accurate stability prediction is essential to pharmaceutical formulation development. Commonly used stability prediction methods include monitoring parent drug loss at intended storage conditions or initial rate determination of degradants under accelerated conditions. Monitoring parent drug loss at the intended storage condition does not provide a rapid and accurate stability assessment because often <0.5% drug loss is all that can be observed in a realistic time frame, while the accelerated initial rate method in conjunction with extrapolation of rate constants using the Arrhenius or Eyring equations often introduces large errors in shelf-life prediction. In this study, the shelf life prediction of a model pharmaceutical preparation utilizing sensitive high-performance liquid chromatography-mass spectrometry (LC/MS) to directly quantitate degradant formation rates at the intended storage condition is proposed. This method was compared to traditional shelf life prediction approaches in terms of time required to predict shelf life and associated error in shelf life estimation. Results demonstrated that the proposed LC/MS method using initial rates analysis provided significantly improved confidence intervals for the predicted shelf life and required less overall time and effort to obtain the stability estimation compared to the other methods evaluated. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

NASA Technical Reports Server (NTRS)

Cardelino, Beatriz H.

2002-01-01

There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

Carbon tetrachloride degradation: Effect of microbial growth substrate and vitamin B{sub 12} content

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

Zou, S.; Stensel, H.D.; Ferguson, J.F.

2000-05-01

Microbial degradation kinetics of carbon tetrachloride (CT) under reducing conditions were investigated for different cultures, fed with 1,2-propanediol, dextrose, propionalde-hyde, or acetate and nitrate, in the anaerobic step of an anaerobic/aerobic operation sequence. Methanogenesis was inhibited due to the aerobic step. CT biodegradation rates followed first-order kinetics with respect to CT concentration and biomass and were not affected by the presence of growth substrate. CT degradation rates increased linearly with higher intracellular vitamin B{sub 12} content. The culture fed 1,2-propanediol had the highest vitamin B{sub 12} content, which was 3.8, 4.7, and 16 times that of the propionaldehyde-,dextrose-, and acetate-fedmore » cultures, respectively, and its first-order degradation rate constant was 2.8, 4.5, 6.0 times that for those cultures, respectively. No CT degradation occurred with culture liquid, suggesting that intracellular factors were responsible for CT degradation. The propanediol culture was able to sustain a constant CT degradation rate for a 16-day test period without substrate addition. Compared to a propanediol-fed culture grown only under anaerobic conditions, the propanediol culture grown under the sequential anaerobic/aerobic condition resulted in more biomass growth and a greater CT degradation rate per unit of propanediol fed, although its CT degradation rate per unit of biomass was lower.« less

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

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.

The degradation of the antitumor agent gemcitabine hydrochloride in an acidic aqueous solution at pH 3.2 and identification of degradation products.

PubMed

Jansen, P J; Akers, M J; Amos, R M; Baertschi, S W; Cooke, G G; Dorman, D E; Kemp, C A; Maple, S R; McCune, K A

2000-07-01

A study of the degradation kinetics of gemcitabine hydrochloride (2'-deoxy-2',2'-difluorocytidine) in aqueous solution at pH 3.2 was conducted. The degradation of gemcitabine followed pseudo first-order kinetics, and rate constants were determined at four different temperatures. These rates were used to construct an Arrhenius plot from which degradation rates at lower temperatures were extrapolated and activation energy calculated. Four major degradation products were identified. Only one of these degradation products, the uridine analogue of gemcitabine, was a known degradation product of gemcitabine and was identified by comparison with synthesized material. The other three degradation products were isolated and characterized by spectroscopic techniques. Two of these products were determined to be the diastereomeric 6-hydroxy-5, 6-dihydro-2'-deoxy-2',2'-difluorouridines, and the other product was determined to be O(6),5'-cyclo-5,6-dihydro-2'-deoxy-2', 2'-difluorouridine. The mechanisms of formation of these degradation products are discussed.

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.

Phototransformation rate constants of PAHs associated with soot particles.

PubMed

Kim, Daekyun; Young, Thomas M; Anastasio, Cort

2013-01-15

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

Phototransformation Rate Constants of PAHs Associated with Soot Particles

PubMed Central

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

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].

Charring rate of wood exposed to a constant heat flux

Treesearch

R. H. White; H. C. Tran

1996-01-01

A critical factor in the fire endurance of a wood member is its rate of charring. Most available charring rate data have been obtained using the time-temperature curves of the standard fire resistance tests (ASTM E 119 and ISO 834) to define the fire exposure. The increased use of heat release calorimeters using exposures of constant heat flux levels has broadened the...

Pathway and rate-limiting step of glyphosate degradation by Aspergillus oryzae A-F02.

PubMed

Fu, Gui-Ming; Chen, Yan; Li, Ru-Yi; Yuan, Xiao-Qiang; Liu, Cheng-Mei; Li, Bin; Wan, Yin

2017-09-14

Aspergillus oryzae A-F02, a glyphosate-degrading fungus, was isolated from an aeration tank in a pesticide factory. The pathway and rate-limiting step of glyphosate (GP) degradation were investigated through metabolite analysis. GP, aminomethylphosphonic acid (AMPA), and methylamine were detected in the fermentation liquid of A. oryzae A-F02, whereas sarcosine and glycine were not. The pathway of GP degradation in A. oryzae A-F02 was revealed: GP was first degraded into AMPA, which was then degraded into methylamine. Finally, methylamine was further degraded into other products. Investigating the effects of the exogenous addition of substrates and metabolites showed that the degradation of GP to AMPA is the rate-limiting step of GP degradation by A. oryzae A-F02. In addition, the accumulation of AMPA and methylamine did not cause feedback inhibition in GP degradation. Results showed that degrading GP to AMPA was a crucial step in the degradation of GP, which determines the degradation rate of GP by A. oryzae A-F02.

Study on improving the turbidity measurement of the absolute coagulation rate constant.

PubMed

Sun, Zhiwei; Liu, Jie; Xu, Shenghua

2006-05-23

The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.

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

Solar photocatalytic degradation of mono azo methyl orange and diazo reactive green 19 in single and binary dye solutions: adsorbability vs photodegradation rate.

PubMed

Ong, Soon-An; Min, Ohm-Mar; Ho, Li-Ngee; Wong, Yee-Shian

2013-05-01

The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir-Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.

Exploring the mechanical behavior of degrading swine neural tissue at low strain rates via the fractional Zener constitutive model.

PubMed

Bentil, Sarah A; Dupaix, Rebecca B

2014-02-01

The ability of the fractional Zener constitutive model to predict the behavior of postmortem swine brain tissue was examined in this work. Understanding tissue behavior attributed to degradation is invaluable in many fields such as the forensic sciences or cases where only cadaveric tissue is available. To understand how material properties change with postmortem age, the fractional Zener model was considered as it includes parameters to describe brain stiffness and also the parameter α, which quantifies the viscoelasticity of a material. The relationship between the viscoelasticity described by α and tissue degradation was examined by fitting the model to data collected in a previous study (Bentil, 2013). This previous study subjected swine neural tissue to in vitro unconfined compression tests using four postmortem age groups (<6h, 24h, 3 days, and 1 week). All samples were compressed to a strain level of 10% using two compressive rates: 1mm/min and 5mm/min. Statistical analysis was used as a tool to study the influence of the fractional Zener constants on factors such as tissue degradation and compressive rate. Application of the fractional Zener constitutive model to the experimental data showed that swine neural tissue becomes less stiff with increased postmortem age. The fractional Zener model was also able to capture the nonlinear viscoelastic features of the brain tissue at low strain rates. The results showed that the parameter α was better correlated with compressive rate than with postmortem age. © 2013 Published by Elsevier Ltd.

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.

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 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.

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.

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.

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.

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media.

PubMed

Hamdaoui, Oualid; Naffrechoux, Emmanuel

2008-09-01

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.

Modeling rates of DOC degradation using DOM composition and hydroclimatic variables

NASA Astrophysics Data System (ADS)

Moody, C. S.; Worrall, F.

2017-05-01

The fluvial fluxes of dissolved organic carbon (DOC) from peatlands form an important part of that ecosystem's carbon cycle, contributing approximately 35% of the overall peatland carbon budget. The in-stream processes acting on the DOC, such as photodegradation and biodegradation, can lead to DOC loss and thus contribute CO2 to the atmosphere. The aim of this study was to understand what controls the rates of DOC degradation. Water samples from a headwater, peat-covered catchment, were collected over a 23 month period and analyzed for the DOC degradation rate and dissolved organic matter (DOM) composition in the context of hydroclimatic monitoring. Measures of DOM composition included 13C solid-state nuclear magnetic resonance spectroscopy, bomb calorimetry, and elemental analysis. Regression analysis showed that there was a significant role for the composition of the DOM in controlling degradation with degradation rates significantly increasing with the proportion of aldehyde and carboxylic acid functional groups but decreasing with the proportion of N-alkyl functional groups. The highest rates of DOC degradation occurred when aldehyde functionality was at its greatest and this occurred on the recession limb of storm hydrographs. Including this knowledge into models of fluvial carbon fate for an 818 km2 catchment gave an annual average DOC removal rate of 67% and 50% for total organic carbon, slightly lower than previously predicted. The compositional controls suggest that DOM is primarily being used as a ready energy source to the aquatic ecosystem rather than as a nutrient source.

Photochemical degradation of triazine herbicides - comparison of homogeneous and heterogeneous photocatalysis.

PubMed

Klementova, Sarka; Zlamal, Martin

2013-04-01

Photochemical degradation of atrazine under different conditions was studied and compared, namely degradation via photocatalysis on TiO2, UV C photolysis, and homogeneous photocatalysis in the presence of added ferric ions. The reaction rate constants in heterogeneous photocatalytic reactions on TiO2 and of photolytic degradation by means of UV C light are similar, 0.018 min(-1) and 0.020 min(-1), respectively. The reaction rate constants in homogeneous photocatalytic reactions with Fe(III) added depend strongly on the Fe(III) concentration, 0.0017 min(-1) for 1.6 × 10(-6) mol l(-1) Fe(III) to 0.105 min(-1) for 3.3 × 10(-4) mol l(-1) Fe(III). In all types of reactions, dechlorination was observed; in homogeneous photocatalytic reactions and in UV C (250-300 nm) photolysis, dechlorination proceeds with a 1 : 1 stoichiometry to atrazine degradation, in photocatalytic reactions on TiO2, dechlorination measured as chloride ion release reaches only 1/5 of the substrate degradation. In photocatalytic reactions on TiO2, mineralisation of 40% carbon was observed.

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

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.

Rate constants for proteins binding to substrates with multiple binding sites using a generalized forward flux sampling expression

NASA Astrophysics Data System (ADS)

Vijaykumar, Adithya; ten Wolde, Pieter Rein; Bolhuis, Peter G.

2018-03-01

To predict the response of a biochemical system, knowledge of the intrinsic and effective rate constants of proteins is crucial. The experimentally accessible effective rate constant for association can be decomposed in a diffusion-limited rate at which proteins come into contact and an intrinsic association rate at which the proteins in contact truly bind. Reversely, when dissociating, bound proteins first separate into a contact pair with an intrinsic dissociation rate, before moving away by diffusion. While microscopic expressions exist that enable the calculation of the intrinsic and effective rate constants by conducting a single rare event simulation of the protein dissociation reaction, these expressions are only valid when the substrate has just one binding site. If the substrate has multiple binding sites, a bound enzyme can, besides dissociating into the bulk, also hop to another binding site. Calculating transition rate constants between multiple states with forward flux sampling requires a generalized rate expression. We present this expression here and use it to derive explicit expressions for all intrinsic and effective rate constants involving binding to multiple states, including rebinding. We illustrate our approach by computing the intrinsic and effective association, dissociation, and hopping rate constants for a system in which a patchy particle model enzyme binds to a substrate with two binding sites. We find that these rate constants increase as a function of the rotational diffusion constant of the particles. The hopping rate constant decreases as a function of the distance between the binding sites. Finally, we find that blocking one of the binding sites enhances both association and dissociation rate constants. Our approach and results are important for understanding and modeling association reactions in enzyme-substrate systems and other patchy particle systems and open the way for large multiscale simulations of such systems.

Application rate affects the degradation rate and hence emissions of chloropicrin in soil.

PubMed

Ashworth, Daniel J; Yates, Scott R; Stanghellini, Mike; van Wesenbeeck, Ian J

2018-05-01

Increasingly stringent regulations to control soil-air emissions of soil fumigants has led to much research effort aimed at reducing emission potential. Using laboratory soil columns, we aimed to investigate the relationship between chloropicrin (CP) application rate and its emissions from soil across a wide range of CP applications (equivalent to 56-392kgha -1 ). In contrast to the known behavior of other fumigants, total emission percentages were strongly and positively related to application rate (i.e., initial mass), ranging from 4 to 34% across the application rate range. When combined, data from a previous study and the present study showed good overall comparability in terms of CP application rate vs. emission percentage, yielding a second-order polynomial relationship with an R 2 value of 0.93 (n=12). The study revealed that mass losses of CP were strongly disproportional to application rate, also showing a polynomial relationship. Based on degradation studies, we consider that a shorter half-life (faster degradation) at lower application rates limited the amount of CP available for emission. The non-linear relationship between CP application rate and CP emissions (both as % of that applied and as total mass) suggests that low application rates likely lead to disproportionally low emission losses compared with higher application rates; such a relationship could be taken into account when assessing/mitigating risk, e.g., in the setting of buffer zone distances. Copyright © 2017 Elsevier B.V. All rights reserved.

Eigen model with general fitness functions and degradation rates

NASA Astrophysics Data System (ADS)

Hu, Chin-Kun; Saakian, David B.

2006-03-01

We present an exact solution of Eigen's quasispecies model with a general degradation rate and fitness functions, including a square root decrease of fitness with increasing Hamming distance from the wild type. The found behavior of the model with a degradation rate is analogous to a viral quasi-species under attack by the immune system of the host. Our exact solutions also revise the known results of neutral networks in quasispecies theory. To explain the existence of mutants with large Hamming distances from the wild type, we propose three different modifications of the Eigen model: mutation landscape, multiple adjacent mutations, and frequency-dependent fitness in which the steady state solution shows a multi-center behavior.

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.

PCE DNAPL degradation using ferrous iron solid mixture (ISM).

PubMed

Lee, Hong-Kyun; Do, Si-Hyun; Batchelor, Bill; Jo, Young-Hoon; Kong, Sung-Ho

2009-08-01

Ferrous iron solid mixture (ISM) containing Fe(II), Fe(III), and Cl was synthesized for degradation of tetrachloroethene (PCE) as a dense non-aqueous phase liquid (DNAPL), and an extraction procedure was developed to measure concentrations of PCE in both the aqueous and non-aqueous phases. This procedure included adding methanol along with hexane in order to achieve the high extraction efficiency, particularly when solids were present. When PCE was present as DNAPL, dechlorination of PCE was observed to decrease linearly with respect to the total PCE concentration (aqueous and non-aqueous phases) and the concentration of PCE in the aqueous phase was observed to be approximately constant. In the absence of DNAPL, the rate of PCE degradation was observed to be the first-order with respect to the concentration in the aqueous phase. A kinetic model was developed to describe these observations and it was able to fit experimental data well. Increasing the concentration of Fe(II) in ISM increased the values of rate constants, while increasing the concentration of PCE DNAPL did not affect the value of the rate constant. The reactivity of ISM for PCE dechlorination might be close to that of Friedel's salt, and the accumulation of trichloroethylene (TCE) might imply the lower reactivity of ISM for degradation of TCE or the necessity of large amount of Fe(II) in ISM. TCE (the major chlorinated intermediate), ethene (the major non-chlorinated compound), acetylene and ethane were detected, which implied that both hydrogenolysis and beta-elimination were pathways of PCE DNAPL degradation on ISM.

Overview of Field Experience - Degradation Rates & Lifetimes

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

Jordan, Dirk; Kurtz, Sarah

2015-09-14

The way a PV module fails may depend not only on its design and the materials used in its construction, but also on the weather it experiences, the way it is mounted, and the quality control during its manufacture. This presentation gives an overview of Field Experience - what degradation rates and what lifetimes are being observed in various regions.

A simple method relating specific rate constants k(E,J) and Thermally averaged rate constants k(infinity)(T) of unimolecular bond fission and the reverse barrierless association reactions.

PubMed

Troe, J; Ushakov, V G

2006-06-01

This work describes a simple method linking specific rate constants k(E,J) of bond fission reactions AB --> A + B with thermally averaged capture rate constants k(cap)(T) of the reverse barrierless combination reactions A + B --> AB (or the corresponding high-pressure dissociation or recombination rate constants k(infinity)(T)). Practical applications are given for ionic and neutral reaction systems. The method, in the first stage, requires a phase-space theoretical treatment with the most realistic minimum energy path potential available, either from reduced dimensionality ab initio or from model calculations of the potential, providing the centrifugal barriers E(0)(J). The effects of the anisotropy of the potential afterward are expressed in terms of specific and thermal rigidity factors f(rigid)(E,J) and f(rigid)(T), respectively. Simple relationships provide a link between f(rigid)(E,J) and f(rigid)(T) where J is an average value of J related to J(max)(E), i.e., the maximum J value compatible with E > or = E0(J), and f(rigid)(E,J) applies to the transitional modes. Methods for constructing f(rigid)(E,J) from f(rigid)(E,J) are also described. The derived relationships are adaptable and can be used on that level of information which is available either from more detailed theoretical calculations or from limited experimental information on specific or thermally averaged rate constants. The examples used for illustration are the systems C6H6+ <==> C6H5+ + H, C8H10+ --> C7H7+ + CH3, n-C9H12+ <==> C7H7+ + C2H5, n-C10H14+ <==> C7H7+ + C3H7, HO2 <==> H + O2, HO2 <==> HO + O, and H2O2 <==> 2HO.

A direct comparison of U.S. Environmental Protection Agency's method 304B and batch tests for determining activated-sludge biodegradation rate constants for volatile organic compounds

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

Cano, M.L.; Wilcox, M.E.; Compernolle, R. van

Biodegradation rate constants for volatile organic compounds (VOCs) in activated-sludge systems are needed to quantify emissions. One current US environmental Protection Agency method for determining a biodegradation rate constant is Method 304B. In this approach, a specific activated-sludge unit is simulated by a continuous biological treatment system with a sealed headspace. Batch experiments, however, can be alternatives to Method 304B. Two of these batch methods are the batch test that uses oxygen addition (BOX) and the serum bottle test (SBT). In this study, Method 304B was directly compared to BOX and SBT experiments. A pilot-scale laboratory reactor was constructed tomore » serve as the Method 304B unit. Biomass from the unit was also used to conduct BOX and modified SBT experiments (modification involved use of a sealed draft-tube reactor with a headspace recirculation pump instead of a serum bottle) for 1,2-dichloroethane, diisopropyl ether, methyl tertiary butyl ether, and toluene. Three experimental runs--each consisting of one Method 304B experiment, one BOX experiment, and one modified SBT experiment--were completed. The BOX and SBT data for each run were analyzed using a Monod model, and best-fit biodegradation kinetic parameters were determined for each experiment, including a first-order biodegradation rate constant (K{sub 1}). Experimental results suggest that for readily biodegradable VOCs the two batch techniques can provide improved means of determining biodegradation rate constants compared with Method 304B. In particular, these batch techniques avoid the Method 304B problem associated with steady-state effluent concentrations below analytical detection limits. However, experimental results also suggest that the two batch techniques should not be used to determine biodegradation rate constants for slowly degraded VOCs (i.e., K{sub 1} {lt} 0.1 L/g VSS-h).« less

Degradation of PPCPs in activated sludge from different WWTPs in Denmark.

PubMed

Chen, Xijuan; Vollertsen, Jes; Nielsen, Jeppe Lund; Dall, Agnieszka Gieraltowska; Bester, Kai

2015-12-01

Pharmaceuticals and Personal care products (PPCPs) are often found in effluents from wastewater treatment plants (WWTPs) due to insufficient removal during wastewater treatment processes. To understand the factors affecting the removal of PPCPs in classical activated sludge WWTPs, the present study was performed to assess the removal of frequently occurring pharmaceuticals (Naproxen, Fenoprofen, Ketoprofen, Dichlofenac, Carbamazepine) and the biocide Triclosan in activated sludge from four different Danish WWTPs. The respective degradation constants were compared to operational parameters previous shown to be of importance for degradation of micropollutants such as biomass concentration, and sludge retention time (SRT). The most rapid degradation, was observed for NSAID pharmaceuticals (55-90% for Fenoprofen, 77-94% for Ketoprofen and 46-90% for Naproxen), followed by Triclosan (61-91%), while Dichlofenac and Carbamazepine were found to be persistent in the systems. Degradation rate constants were calculated as 0.0026-0.0407 for NSAID pharmaceuticals and 0.0022-0.0065 for triclosan. No relationships were observed between degradation rates and biomass concentrations in the diverse sludges. However, for the investigated PPCPs, the optimal SRT was within 14-20 days (for these values degradation of these PPCPs was the most efficient). Though all of these parameters influence the degradation rate, none of them seems to be overall decisive. These observations indicate that the biological composition of the sludge is more important than the design parameters of the respective treatment plant.

Capacitive Cells for Dielectric Constant Measurement

ERIC Educational Resources Information Center

Aguilar, Horacio Munguía; Maldonado, Rigoberto Franco

2015-01-01

A simple capacitive cell for dielectric constant measurement in liquids is presented. As an illustrative application, the cell is used for measuring the degradation of overheated edible oil through the evaluation of their dielectric constant.

Degradation rates of alachlor, atrazine and bentazone in the profiles of Polish Luvisols

NASA Astrophysics Data System (ADS)

Paszko, Tadeusz; Muszyński, Paweł

2017-07-01

The degradation rates of three herbicides (alachlor, atrazine, and bentazone) were examined according to OECD Guideline 307 in three profiles of grey-brown podzolic soil (Luvisol) in a laboratory experiment. The aim of the experiment was to determine herbicide degradation parameters and their relationships with soil properties. Degradation processes were effectively described by a first-order model. However, in some cases, the best results were produced by bi-phasic kinetics (hockey-stick and bi-exponential model). The degradation rates of the tested herbicides at 25°C and 40% maximum water holding capacity, established based on half-life values in the Ap horizon, increased in the following order: atrazine (32.6-42.8 days) < bentazone (3.4-16.6 days < alachlor (4.4-5.7 days). The correlation analysis and the Principal Component Analysis revealed significant positive correlations between the herbicide degradation rates and the organic matter content of soils. The depth-dependent degradation factors obtained for topsoil and two subsoil horizons (1: 0.42: 0.11 - based on average values, and 1: 0.31: 0.12 - based on median values) reflect the degradation abilities of Polish Luvisols. The values noted are soil-specific; therefore, they can also be applied to other pesticides in Polish Luvisols.

Arrhenius Rate: constant volume burn

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

Menikoff, Ralph

A constant volume burn occurs for an idealized initial state in which a large volume of reactants at rest is suddenly raised to a high temperature and begins to burn. Due to the uniform spatial state, there is no fluid motion and no heat conduction. This reduces the time evolu tion to an ODE for the reaction progress variable. With an Arrhenius reaction rate, two characteristics of thermal ignition are illustrated: induction time and thermal runaway. The Frank-Kamenetskii approximation then leads to a simple expression for the adiabatic induction time. For a first order reaction, the analytic solution is derivedmore » and used to illustrate the effect of varying the activation temperature; in particular, on the induction time. In general, the ODE can be solved numerically. This is used to illustrate the effect of varying the reaction order. We note that for a first order reaction, the time evolution of the reaction progress variable has an exponential tail. In contrast, for a reaction order less than one, the reaction completes in a nite time. The reaction order also affects the induction time.« less

Radiation induced degradation of xanthan gum in aqueous solution

NASA Astrophysics Data System (ADS)

Hayrabolulu, Hande; Demeter, Maria; Cutrubinis, Mihalis; Güven, Olgun; Şen, Murat

2018-03-01

In our previous study, we have investigated the effect of gamma rays on xanthan gum in the solid state and it was determined that dose rate was an important factor effecting the radiation degradation of xanthan gum. In the present study, in order to provide a better understanding of how ionizing radiation effect xanthan gum, we have investigated the effects of ionizing radiation on aqueous solutions of xanthan at various concentrations (0.5-4%). Xanthan solutions were irradiated with gamma rays in air, at ambient temperature, at different dose rates (0.1-3.3-7.0 kGy/h) and doses (2.5-50 kGy). Change in their molecular weights was followed by size exclusion chromatography (SEC). Chain scission yield (G(S)), and degradation rate constants (k) were calculated. It was determined that, solution concentration was a factor effecting the degradation chemical yield and degradation rate of xanthan gum. Chain scission reactions were more effective for lower solution concentrations.

9975 Shipping package component long-term degradation rates

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

Daugherty, W. L.

Special nuclear materials are being stored in the K-Area Complex using 3013 containers that are held within Model 9975 shipping packages. The service life for these packages in storage was recently increased from 15 to 20 years, since some of these packages have been stored for nearly 15 years. A strategy is also being developed whereby such storage might be extended beyond 20 years. This strategy is based on recent calculations that support acceptable 9975 package performance for 20 years with internal heat loads up to 19 watts, and identifies a lower heat load limit for which the package componentsmore » should degrade at half the bounding rate or less, thus doubling the effective storage life for these lower wattage packages. The components of the 9975 package that are sensitive to aging under storage conditions are the fiberboard overpack and the O-ring seals, although some degradation of the lead shield and outer drum are also possible. This report summarizes degradation rates applicable to lower heat load storage conditions. In particular, the O-ring seals should provide leak-tight performance for more than 40 years in packages for which their maximum temperature is ≤135 °F. Similarly, the fiberboard should remain acceptable in performance of its required safety functions for up to 40 years in packages with a maximum fiberboard temperature ≤125 °F.« less

Magnetoelastic galfenol as a stent material for wirelessly controlled degradation rates.

PubMed

DeRouin, Andrew; Guillory, Roger; He, Weilue; Frost, Megan; Goldman, Jeremy; Ong, Keat Ghee

2018-03-23

The gold standard of care for coronary artery disease, a leading cause of death for in the world, is balloon angioplasty in conjunction with stent deployment. However, implantation injuries and long-term presence of foreign material often promotes significant luminal tissue growth, leading to a narrowing of the artery and severely restricted blood flow. A promising method to mitigate this process is the use of biodegradable metallic stents, but thus far they have either degraded too slowly (iron) or disappeared prematurely (magnesium). The present work investigates the use of a unique type of magnetic material, galfenol (iron-gallium), for postoperative wireless control of stent degradation rates. Due to its magnetoelastic property, galfenol experiences longitudinal micron-level elongations when exposed to applied magnetic fields, allowing generation of a microstirring effect that affect its degradation behavior. In vitro indirect cytotoxicity tests on primary rat aortic smooth muscle cells indicated that galfenol byproducts must be concentrated approximately seven times from collected 60 day degradation medium to cause ∼15% of death from all cells. Surface and cross-sectional characterization of the material indicate that galfenol (Fe 80 Ga 20 ) degradation rates (∼0.55% per month) are insufficient for stenting applications. While this material may not be ideal for comprising the entire stent, there is potential for use in combination with other materials. Furthermore, the ability to control degradation rates postimplantation opens new possibilities for biodegradable stents; additional magnetoelastic materials should be investigated for use in stenting applications. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 Wiley Periodicals, Inc.

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.

Degradation of quinolone antibiotic, norfloxacin, in aqueous solution using gamma-ray irradiation.

PubMed

Sayed, Murtaza; Khan, Javed Ali; Shah, Luqman Ali; Shah, Noor S; Khan, Hasan M; Rehman, Faiza; Khan, Abdur Rahman; Khan, Asad M

2016-07-01

This study reports the efficiency of gamma-ray irradiation to degrade quinolone antibiotic, norfloxacin, in aqueous solution. Laboratory batch experiments were conducted to determine the "pseudo-first" order degradation kinetics of norfloxacin in the concentration ranges of 3.4-16.1 mg L(-1) by gamma-ray irradiation. The dose constant was found to be dependent on the initial concentration of norfloxacin and gamma-ray irradiation dose rate (D r). The saturation of norfloxacin sample solutions with N2, air or N2O, and the presence of tert-butanol and 2-propanol showed that (•)OH played more crucial role in the degradation of norfloxacin. The second order rate constants of (•)OH, eaq (-), and (•)H with norfloxacin were calculated to be 8.81 × 10(9), 9.54 × 10(8), and 1.10 × 10(9) M(-1) s(-1), respectively. The effects of various additives including CO3 (2-), HCO3 (-), NO3 (-), NO2 (-), and thiourea and the pH of the medium on the degradation of norfloxacin were also investigated. Norfloxacin degradation was lower in surface water and wastewater than in ultrapure water. Several degradation byproducts of norfloxacin were identified from which the possible degradation pathway was proposed.

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...

Binding Rate Constants Reveal Distinct Features of Disordered Protein Domains.

PubMed

Dogan, Jakob; Jonasson, Josefin; Andersson, Eva; Jemth, Per

2015-08-04

Intrinsically disordered proteins (IDPs) are abundant in the proteome and involved in key cellular functions. However, experimental data about the binding kinetics of IDPs as a function of different environmental conditions are scarce. We have performed an extensive characterization of the ionic strength dependence of the interaction between the molten globular nuclear co-activator binding domain (NCBD) of CREB binding protein and five different protein ligands, including the intrinsically disordered activation domain of p160 transcriptional co-activators (SRC1, TIF2, ACTR), the p53 transactivation domain, and the folded pointed domain (PNT) of transcription factor ETS-2. Direct comparisons of the binding rate constants under identical conditions show that the association rate constant, kon, for interactions between NCBD and disordered protein domains is high at low salt concentrations (90-350 × 10(6) M(-1) s(-1) at 4 °C) but is reduced significantly (10-30-fold) with an increasing ionic strength and reaches a plateau around physiological ionic strength. In contrast, the kon for the interaction between NCBD and the folded PNT domain is only 7 × 10(6) M(-1) s(-1) (4 °C and low salt) and displays weak ionic strength dependence, which could reflect a distinctly different association that relies less on electrostatic interactions. Furthermore, the basal rate constant (in the absence of electrostatic interactions) is high for the NCBD interactions, exceeding those typically observed for folded proteins. One likely interpretation is that disordered proteins have a large number of possible collisions leading to a productive on-pathway encounter complex, while folded proteins are more restricted in terms of orientation. Our results highlight the importance of electrostatic interactions in binding involving IDPs and emphasize the significance of including ionic strength as a factor in studies that compare the binding properties of IDPs to those of ordered proteins.

Role of effluent organic matter in the photochemical degradation of compounds of wastewater origin.

PubMed

Bodhipaksha, Laleen C; Sharpless, Charles M; Chin, Yu-Ping; MacKay, Allison A

2017-03-01

The photoreactivity of treated wastewater effluent organic matter differs from that of natural organic matter, and the indirect phototransformation rates of micropollutants originating in wastewater are expected to depend on the fractional contribution of wastewater to total stream flow. Photodegradation rates of four common compounds of wastewater origin (sulfamethoxazole, sulfadimethoxine, cimetidine and caffeine) were measured in river water, treated municipal wastewater effluent and mixtures of both to simulate various effluent-stream water mixing conditions that could occur in environmental systems. Compounds were chosen for their unique photodegradation pathways with the photochemically produced reactive intermediates, triplet-state excited organic matter ( 3 OM*), singlet oxygen ( 1 O 2 ), and hydroxyl radicals (OH). For all compounds, higher rates of photodegradation were observed in effluent relative to upstream river water. Sulfamethoxazole degraded primarily via direct photolysis, with some contribution from OH and possibly from carbonate radicals and other unidentified reactive intermediates in effluent-containing samples. Sulfadimethoxine also degraded mainly by direct photolysis, and natural organic matter appeared to inhibit this process to a greater extent than predicted by light screening. In the presence of effluent organic matter, sulfadimethoxine showed additional reactions with OH and 1 O 2 . In all water samples, cimetidine degraded by reaction with 1 O 2 (>95%) and caffeine by reaction with OH (>95%). In river water mixtures, photodegradation rate constants for all compounds increased with increasing fractions of effluent. A conservative mixing model was able to predict reaction rate constants in the case of hydroxyl radical reactions, but it overestimated rate constants in the case of 3 OM* and 1 O 2 pathways. Finally, compound degradation rate constants normalized to the rate of light absorption by water correlated with E 2 /E 3 ratios

Degradation of Amino Acids and Structure in Model Proteins and Bacteriophage MS2 by Chlorine, Bromine, and Ozone.

PubMed

Choe, Jong Kwon; Richards, David H; Wilson, Corey J; Mitch, William A

2015-11-17

Proteins are important targets of chemical disinfectants. To improve the understanding of disinfectant-protein reactions, this study characterized the disinfectant:protein molar ratios at which 50% degradation of oxidizable amino acids (i.e., Met, Tyr, Trp, His, Lys) and structure were observed during HOCl, HOBr, and O3 treatment of three well-characterized model proteins and bacteriophage MS2. A critical question is the extent to which the targeting of amino acids is driven by their disinfectant rate constants rather than their geometrical arrangement. Across the model proteins and bacteriophage MS2 (coat protein), differing widely in structure, methionine was preferentially targeted, forming predominantly methionine sulfoxide. This targeting concurs with its high disinfectant rate constants and supports its hypothesized role as a sacrificial antioxidant. Despite higher HOCl and HOBr rate constants with histidine and lysine than for tyrosine, tyrosine generally was degraded in preference to histidine, and to a lesser extent, lysine. These results concur with the prevalence of geometrical motifs featuring histidines or lysines near tyrosines, facilitating histidine and lysine regeneration upon Cl[+1] transfer from their chloramines to tyrosines. Lysine nitrile formation occurred at or above oxidant doses where 3,5-dihalotyrosine products began to degrade. For O3, which lacks a similar oxidant transfer pathway, histidine, tyrosine, and lysine degradation followed their relative O3 rate constants. Except for its low reactivity with lysine, the O3 doses required to degrade amino acids were as low as or lower than for HOCl or HOBr, indicating its oxidative efficiency. Loss of structure did not correlate with loss of particular amino acids, suggesting the need to characterize the oxidation of specific geometric motifs to understand structural degradation.

Likelihood inference of non-constant diversification rates with incomplete taxon sampling.

PubMed

Höhna, Sebastian

2014-01-01

Large-scale phylogenies provide a valuable source to study background diversification rates and investigate if the rates have changed over time. Unfortunately most large-scale, dated phylogenies are sparsely sampled (fewer than 5% of the described species) and taxon sampling is not uniform. Instead, taxa are frequently sampled to obtain at least one representative per subgroup (e.g. family) and thus to maximize diversity (diversified sampling). So far, such complications have been ignored, potentially biasing the conclusions that have been reached. In this study I derive the likelihood of a birth-death process with non-constant (time-dependent) diversification rates and diversified taxon sampling. Using simulations I test if the true parameters and the sampling method can be recovered when the trees are small or medium sized (fewer than 200 taxa). The results show that the diversification rates can be inferred and the estimates are unbiased for large trees but are biased for small trees (fewer than 50 taxa). Furthermore, model selection by means of Akaike's Information Criterion favors the true model if the true rates differ sufficiently from alternative models (e.g. the birth-death model is recovered if the extinction rate is large and compared to a pure-birth model). Finally, I applied six different diversification rate models--ranging from a constant-rate pure birth process to a decreasing speciation rate birth-death process but excluding any rate shift models--on three large-scale empirical phylogenies (ants, mammals and snakes with respectively 149, 164 and 41 sampled species). All three phylogenies were constructed by diversified taxon sampling, as stated by the authors. However only the snake phylogeny supported diversified taxon sampling. Moreover, a parametric bootstrap test revealed that none of the tested models provided a good fit to the observed data. The model assumptions, such as homogeneous rates across species or no rate shifts, appear to be

Photocatalytic degradation of p,p'-DDT under UV and visible light using interstitial N-doped TiO₂.

PubMed

Ananpattarachai, Jirapat; Kajitvichyanukul, Puangrat

2015-01-01

1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (or p,p'-DDT) is one of the most persistent pesticides. It is resistant to breakdown in nature and cause the water contamination problem. In this work, a major objective was to demonstrate the application of N-doped TiO2 in degradation and mineralization of the p,p'-DDT under UV and visible light in aqueous solution. The N-doped TiO2 nanopowders were prepared by a simple modified sol-gel procedure using diethanolamine (DEA) as a nitrogen source. The catalyst characteristics were investigated using XRD, SEM, TEM, and XPS. The adsorption and photocatalytic oxidation of p,p'-DDT using the synthesized N-doped TiO2 under UV and visible light were conducted in a batch photocatalytic experiment. The kinetics and p,p'-DDT degradation performance of the N-doped TiO2 were evaluated. Results show that the N-doped TiO2 can degrade p,p'-DDT effectively under both UV and visible lights. The rate constant of the p,p'-DDT degradation under UV light was only 0.0121 min(-1), whereas the rate constant of the p,p'-DDT degradation under visible light was 0.1282 min(-1). Under visible light, the 100% degradation of p,p'-DDT were obtained from N-doped TiO2 catalyst. The reaction rate of p,p'-DDT degradation using N-doped TiO2 under visible light was sixfold higher than that under UV light. According to Langmuir-Hinshelwood model, the adsorption equilibrium constant (K) for the N-doped TiO2 under visible light was 0.03078 L mg(-1), and the apparent reaction rate constant (k) was 1.3941 mg L(-1)-min. Major intermediates detected during the p,p'-DDT degradation were p,p'-DDE, o,p'-DDE, p,p'-DDD and p,p'-DDD. Results from this work can be applied further for the breakdown of p,p'-DDT molecule in the real contaminated water using this technology.

Degradation of isobutanal at high loading rates in a compost biofilter.

PubMed

Sercu, Bram; Demeestere, Kristof; Baillieul, Hans; Van Langenhove, Herman; Verstraete, Willy

2005-08-01

Biofiltration has been increasingly used for cleaning waste gases, mostly containing low concentrations of odorous compounds. To expand the application area of this technology, the biofiltration of higher pollutant loading rates has to be investigated. This article focuses on the biodegradation of isobutanal (IBAL) in a compost biofilter (BF) at mass loading rates between 211 and 4123 g/m3/day (30-590 ppm(v)). At mass loading rates up to 785 g/m3/day, near 100% removal efficiencies could be obtained. However, after increasing the loading rate to 1500-1900 g/m3/ day, the degradation efficiency decreased to 62-98%. In addition, a pH decrease and production of isobutanol (IBOL) and isobutyric acid (IBAC) were observed. This is the first report showing that an aldehyde can act as electron donor as well as acceptor in a BF. To study the effects of pH, compost moisture content, and electron acceptor availability on the biofiltration of IBAL, IBOL, and IBAC, additional batch and continuous experiments were performed. A pH of 5.2 reduced the IBAL degradation rate and inhibited the IBOL degradation, although adaptation of the microorganisms to low pH was observed in the BFs. IBAC was not degraded in the batch experiments. High moisture content (51%) initially had no effect on the IBOL production, although it negatively affected the IBAL elimination increasingly during a 21-day time-course experiment. In batch experiments, the reduction of IBAL to IBOL did not decrease when the amount of available electron acceptors (oxygen or nitrate) was increased. The IBAL removal efficiency at higher loading rates was limited by a combination of nutrient limitation, pH decrease, and dehydration, and the importance of each limiting factor depended on the influent concentration.

Characterization of naphthalene degradation by Streptomyces sp. QWE-5 isolated from active sludge.

PubMed

Xu, Peng; Ma, Wencheng; Han, Hongjun; Hou, Baolin; Jia, Shengyong

2014-01-01

A bacterial strain, QWE-5, which utilized naphthalene as its sole carbon and energy source, was isolated and identified as Streptomyces sp. It was a Gram-positive, spore-forming bacterium with a flagellum, with whole, smooth, convex and wet colonies. The optimal temperature and pH for QWE-5 were 35 °C and 7.0, respectively. The QWE-5 strain was capable of completely degrading naphthalene at a concentration as high as 100 mg/L. At initial naphthalene concentrations of 10, 20, 50, 80 and 100 mg/L, complete degradation was achieved within 32, 56, 96, 120 and 144 h, respectively. Kinetics of naphthalene degradation was described using the Andrews equation. The kinetic parameters were as follows: qmax (maximum specific degradation rate) = 1.56 h⁻¹, Ks (half-rate constant) = 60.34 mg/L, and KI (substrate-inhibition constant) = 81.76 mg/L. Metabolic intermediates were identified by gas chromatography and mass spectrometry, allowing a new degradation pathway for naphthalene to be proposed. In this pathway, monooxygenation of naphthalene yielded naphthalen-1-ol. Further degradation by Streptomyces sp. QWE-5 produced acetophenone, followed by adipic acid, which was produced as a combination of decarboxylation and hydroxylation processes.

Polymer electrolyte membrane water electrolysis: Restraining degradation in the presence of fluctuating power

NASA Astrophysics Data System (ADS)

Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Kuhri, Susanne; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

2017-02-01

Polymer electrolyte membrane (PEM) water electrolysis generates 'green' hydrogen when conducted with electricity from renewable - but fluctuating - sources like wind or solar photovoltaic. Unfortunately, the long-term stability of the electrolyzer performance is still not fully understood under these input power profiles. In this study, we contrast the degradation behavior of our PEM water electrolysis single cells that occurs under operation with constant and intermittent power and derive preferable operating states. For this purpose, five different current density profiles are used, of which two were constant and three dynamic. Cells operated at 1 A cm-2 show no degradation. However, degradation was observed for the remaining four profiles, all of which underwent periods of high current density (2 A cm-2). Hereby, constant operation at 2 A cm-2 led to the highest degradation rate (194 μV h-1). Degradation can be greatly reduced when the cells are operated with an intermittent profile. Current density switching has a positive effect on durability, as it causes reversible parts of degradation to recover and results in a substantially reduced degradation per mole of hydrogen produced. Two general degradation phenomena were identified, a decreased anode exchange current density and an increased contact resistance at the titanium porous transport layer (Ti-PTL).

Frost heave susceptibility of saturated soil under constant rate of freezing

NASA Astrophysics Data System (ADS)

Ryokai, K.; Iguro, M.; Yoneyama, K.

Introduced are the results of experiments carried out to quantitatively obtain the frost heave pressure and displacement of soil subjected to artificial freezing or freezing around in-ground liquefied natural gas storage tanks. This experiment is conducted to evaluate the frost heave susceptibility of saturated soil under overconsolidation. In other words, this experiment was carried out to obtain the relation of the over-burden pressure and freezing rate to the frost heave ratio by observing the frost heave displacement and freezing time of specimens by freezing the specimens at a constant freezing rate under a constant overburden pressure, while letting water freely flow in and out of the system. Introduced are the procedures for frost heave test required to quantitatively obtain the frost heave displacement and pressure of soil. Furthermore, the relation between the frost heave susceptibility and physical properties of soil obtained by this test is reported.

UV-induced photocatalytic degradation of aqueous acetaminophen: the role of adsorption and reaction kinetics.

PubMed

Basha, Shaik; Keane, David; Nolan, Kieran; Oelgemöller, Michael; Lawler, Jenny; Tobin, John M; Morrissey, Anne

2015-02-01

Nanostructured titania supported on activated carbon (AC), termed as integrated photocatalytic adsorbents (IPCAs), were prepared by ultrasonication and investigated for the photocatalytic degradation of acetaminophen (AMP), a common analgesic and antipyretic drug. The IPCAs showed high affinity towards AMP (in dark adsorption studies), with the amount adsorbed proportional to the TiO2 content; the highest adsorption was at 10 wt% TiO2. Equilibrium isotherm studies showed that the adsorption followed the Langmuir model, indicating the dependence of the reaction on an initial adsorption step, with maximum adsorption capacity of 28.4 mg/g for 10 % TiO2 IPCA. The effects of initial pH, catalyst amount and initial AMP concentration on the photocatalytic degradation rates were studied. Generally, the AMP photodegradation activity of the IPCAs was better than that of bare TiO2. Kinetic studies on the photocatalytic degradation of AMP under UV suggest that the degradation followed Langmuir-Hinshelwood (L-H) kinetics, with an adsorption rate constant (K) that was considerably higher than the photocatalytic rate constant (k r), indicating that the photocatalysis of AMP is the rate-determining step during the adsorption/photocatalysis process.

Constant-load versus heart rate-targeted exercise - Responses of systolic intervals

NASA Technical Reports Server (NTRS)

Lance, V. Q.; Spodick, D. H.

1975-01-01

Various systolic intervals were measured prior to and during heart rate-targeted bicycle ergometer exercise. There were striking similarities within each matched exercise set for Q-Im, isovolumetric contraction time, preejection period (PEP), and PEP/left ventricular ejection time (LVET). LVET was significantly shorter for rate-targeted exercise. It is concluded that either constant-load or rate-targeted bicycle ergometry may be used with the choice of method determined by the purpose of the protocol, and that systolic intervals (except LVET) should not be much altered owing to the method chosen.

Catalase degradation in sunflower cotyledons during peroxisome transition from glyoxysomal to leaf peroxisomal function. [Helianthus annuus

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

Eising, R.; Gerhardt, B.

1987-06-01

First order rate constant for the degradation (degradation constants) of catalase in the cotyledons of sunflower (Helianthus annuus L.) were determined by measuring the loss of catalase containing /sup 14/C-labeled heme. During greening of the cotyledons, a period when peroxisomes change from glyoxysomal to leaf peroxisomal function, the degradation of glyoxysomal catalase is significantly slower than during all other stages of cotyledon development in light or darkness. The degradation constant during the transition stage of peroxisome function amounts to 0.205 day/sup -1/ in contrast to the constants ranging from 0.304 day/sup -1/ to 0.515 day/sup -1/ during the other developmentalmore » stages. Density labeling experiments comprising labeling of catalase with /sup 2/H/sub 2/O and its isopycnic centrifugation on CsCl gradients demonstrated that the determinations of the degradation constants were not substantially affected by reutilization of /sup 14/C-labeled compounds for catalase synthesis. The degradation constants for both glyoxysomal catalase and catalase synthesized during the transition of peroxisome function do not differ. This was shown by labeling the catalases with different isotopes and measuring the isotope ratio during the development of the cotyledons. The results are inconsistent with the concept that an accelerated and selective degradation of glyoxysomes underlies the change in peroxisome function. The data suggest that catalase degradation is at least partially due to an individual turnover of catalase and does not only result from a turnover of the whole peroxisomes.« less

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.

RELATIVE RATE CONSTANTS OF CONTAMINANT CANDIDATE LIST PESTICIDES WITH HYDROXYL RADICALS

EPA Science Inventory

The objective of this study was to establish the rate constants for the reactions of selected pesticides listed on the US EPA Contaminant Candidate List, with UV and hydroxyl radicals (·OH). Batch experiments were conducted in phosphate buffered solution at pH 7. All pestici...

Dose rate effects in radiation degradation of polymer-based cable materials

NASA Astrophysics Data System (ADS)

Plaček, V.; Bartoníček, B.; Hnát, V.; Otáhal, B.

2003-08-01

Cable ageing under the nuclear power plant (NPP) conditions must be effectively managed to ensure that the required plant safety and reliability are maintained throughout the plant service life. Ionizing radiation is one of the main stressors causing age-related degradation of polymer-based cable materials in air. For a given absorbed dose, radiation-induced damage to a polymer in air environment usually depends on the dose rate of the exposure. In this work, the effect of dose rate on the degradation rate has been studied. Three types of NPP cables (with jacket/insulation combinations PVC/PVC, PVC/PE, XPE/XPE) were irradiated at room temperature using 60Co gamma ray source at average dose rates of 7, 30 and 100 Gy/h with the doses up to 590 kGy. The irradiated samples have been tested for their mechanical properties, thermo-oxidative stability (using differential scanning calorimetry, DSC), and density. In the case of PVC and PE samples, the tested properties have shown evident dose rate effects, while the XPE material has shown no noticeable ones. The values of elongation at break and the thermo-oxidative stability decrease with the advanced degradation, density tends to increase with the absorbed dose. For XPE samples this effect can be partially explained by the increase of crystallinity. It was tested by the DSC determination of the crystalline phase amount.

Bacterial methylmercury degradation in Florida Everglades peat sediment

USGS Publications Warehouse

Marvin-DiPasquale, M. C.; Oremland, R.S.

1998-01-01

Methylmercury (MeHg) degradation was investigated along an eutrophication gradient in the Florida Everglades by quantifying 14CH4 and 14CO2 production after incubation of anaerobic sediments with [14C]MeHg. Degradation rate constants (k) were consistently ???0.1 d-1 and decreased with sediment depth. Higher k values were observed when shorter incubation times and lower MeHg amendment levels were used, and k increased 2-fold as in-situ MeHg concentrations were approached. The average floc layer k was 0.046 ?? 0.023 d-1 (n = 17) for 1-2 day incubations. In-situ degradation rates were estimated to be 0.02-0.5 ng of MeHg (g of dry sediment)-1 d-1, increasing from eutrophied to pristine areas. Nitrate-respiring bacteria did not demethylate MeHg, and NO3- addition partially inhibited degradation in some cases. MeHg degradation rates were not affected by PO43- addition. 14CO2 production in all samples indicated that oxidative demethylation (OD) was an important degradation mechanism. OD occurred over 5 orders of magnitude of applied MeHg concentration, with lowest limits [1-18 ng of MeHg (g of dry sediment)-1] in the range of in-situ MeHg levels. Sulfate reducers and methanogens were the primary agents of anaerobic OD, although it is suggested that methanogens dominate degradation at in-situ MeHg concentrations. Specific pathways of OD by these two microbial groups are proposed.Methylmercury (MeHg) degradation was investigated along an eutrophication gradient in the Florida Everglades by quantifying 14CH4 and 14CO2 production after incubation of anaerobic sediments with [14C]MeHg. Degradation rate constants (k) were consistently ???0.1 d-1 and decreased with sediment depth. Higher k values were observed when shorter incubation times and lower MeHg amendment levels were used, and k increased 2-fold as in-situ MeHg concentrations were approached. The average floc layer k was 0.046??0.023 d-1 (n = 17) for 1-2 day incubations. In-situ degradation rates were estimated to be 0

Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis.

PubMed

Yang, Liming; Yu, Liya E; Ray, Madhumita B

2008-07-01

In this study, photo/photocatalytic oxidation of common analgesic and antipyretic drug, paracetamol (acetaminophen), was investigated to determine the optimal operating conditions for degradation in water. UVA (365 nm) radiation alone degraded negligible amount of paracetamol, whereas paracetamol concentration decreased substantially under an irradiation of UVC (254 nm) with marginal changes in total organic carbon (TOC). In the presence of TiO2, much faster photodegradation of paracetamol and effective mineralization occurred; more than 95% of 2.0mM paracetamol was degraded within 80 min. The degradation rate constant decreased with an increase in the initial concentration of paracetamol, while it increased with light intensity and oxygen concentration. The degradation rate also increased with TiO2 loading until a concentration of 0.8 g L(-1). The degradation rate slowly increased between pH 3.5 and 9.5, but significantly decreased with increasing pH between 9.5 and 11.0. Based on the experimental data, a kinetic equation describing paracetamol photocatalytic degradation with various process parameters is obtained.

Degradation of caffeic acid in subcritical water and online HPLC-DPPH assay of degradation products.

PubMed

Khuwijitjaru, Pramote; Suaylam, Boonyanuch; Adachi, Shuji

2014-02-26

Caffeic acid was subjected to degradation under subcritical water conditions within 160-240 °C and at a constant pressure of 5 MPa in a continuous tubular reactor. Caffeic acid degraded quickly at these temperatures; the main products identified by liquid chromatography-diode array detection/mass spectrometry were hydroxytyrosol, protocatechuic aldehyde, and 4-vinylcatechol. The reaction rates for the degradation of caffeic acid and the formation of products were evaluated. Online high-performance liquid chromatography/2,2-diphenyl-1-picryhydrazyl assay was used to determine the antioxidant activity of each product in the solution. It was found that the overall antioxidant activity of the treated solution did not change during the degradation process. This study showed a potential of formation of antioxidants from natural phenolic compounds under these subcritical water conditions, and this may lead to a discovering of novel antioxidants compounds during the extraction by this technique.

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.

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.

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.

Micro-mechanical model for the tension-stabilized enzymatic degradation of collagen tissues

NASA Astrophysics Data System (ADS)

Nguyen, Thao; Ruberti, Jeffery

We present a study of how the collagen fiber structure influences the enzymatic degradation of collagen tissues. Experiments of collagen fibrils and tissues show that mechanical tension can slow and halt enzymatic degradation. Tissue-level experiments also show that degradation rate is minimum at a stretch level coincident with the onset of strain-stiffening in the stress response. To understand these phenomena, we developed a micro-mechanical model of a fibrous collagen tissue undergoing enzymatic degradation. Collagen fibers are described as sinusoidal elastica beams, and the tissue is described as a distribution of fibers. We assumed that the degradation reaction is inhibited by the axial strain energy of the crimped collagen fibers. The degradation rate law was calibrated to experiments on isolated single fibrils from bovine sclera. The fiber crimp and properties were fit to uniaxial tension tests of tissue strips. The fibril-level kinetic and tissue-level structural parameters were used to predict tissue-level degradation-induced creep rate under a constant applied force. We showed that we could accurately predict the degradation-induce creep rate of the pericardium and cornea once we accounted for differences in the fiber crimp structure and properties.

Benzene degradation in a denitrifying biofilm reactor: activity and microbial community composition.

PubMed

van der Waals, Marcelle J; Atashgahi, Siavash; da Rocha, Ulisses Nunes; van der Zaan, Bas M; Smidt, Hauke; Gerritse, Jan

2017-06-01

Benzene is an aromatic compound and harmful for the environment. Biodegradation of benzene can reduce the toxicological risk after accidental or controlled release of this chemical in the environment. In this study, we further characterized an anaerobic continuous biofilm culture grown for more than 14 years on benzene with nitrate as electron acceptor. We determined steady state degradation rates, microbial community composition dynamics in the biofilm, and the initial anaerobic benzene degradation reactions. Benzene was degraded at a rate of 0.15 μmol/mg protein/day and a first-order rate constant of 3.04/day which was fourfold higher than rates reported previously. Bacteria belonging to the Peptococcaceae were found to play an important role in this anaerobic benzene-degrading biofilm culture, but also members of the Anaerolineaceae were predicted to be involved in benzene degradation or benzene metabolite degradation based on Illumina MiSeq analysis of 16S ribosomal RNA genes. Biomass retention in the reactor using a filtration finger resulted in reduction of benzene degradation capacity. Detection of the benzene carboxylase encoding gene, abcA, and benzoic acid in the culture vessel indicated that benzene degradation proceeds through an initial carboxylation step.

Dependence of pesticide degradation on sorption: nonequilibrium model and application to soil reactors

NASA Astrophysics Data System (ADS)

Guo, Lei; Jury, William A.; Wagenet, Robert J.; Flury, Markus

2000-04-01

The effect of sorption on degradation of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in a soil amended with various amounts of activated carbon (AC). The relationship between sorption and decay of 2,4-D was analyzed using analytical solutions for equilibrium sorption and to a two-site nonequilibrium adsorption model coupled with two first-order degradation terms for the dissolved and sorbed pesticide, respectively. The sorption parameters in the latter model were determined based on data obtained from batch sorption experiments, while those for degradation were obtained from incubation experiments. The adsorption coefficients, ranging from 0.811 to >315 ml g -1, increased at higher AC, and were negatively related to degradation as measured by the first-order rate constant, implying that degradation is faster from the liquid phase than from the sorbed phase. A nonlinear fit of the decay curves to the nonequilibrium model revealed that degradation rate constants were 0.157 and 0.00243 day -1 for the liquid and sorbed phases, respectively, differing by a factor of 65. Similar results were also obtained using the equilibrium model. A parameter sensitivity analysis of the nonequilibrium model indicates that nonequilibrium sorption will initially favor degradation; however, over the long term, will decrease degradation when desorption kinetics becomes the limiting factor in the degradation process. In the presence of a lag phase that allows appreciable amounts of chemical to diffuse into kinetic sorption sites, nonequilibrium sorption will only impede degradation.

Chloride effect on TNT degradation by zerovalent iron or zinc during water treatment.

PubMed

Hernandez, Rafael; Zappi, Mark; Kuo, Chiang-Hai

2004-10-01

Addition of corrosion promoters, such as sodium and potassium chloride, accelerated TNT degradation during water treatment using zerovalent zinc and iron. It was theorized that corrosion promoters could be used to accelerate electron generation from metallic species, create new reactive sites on the surface of metals during contaminated water treatment, and minimize passivating effects. The surface area normalized pseudo-first-order rate constant for the reaction of zerovalent zinc with TNT in the absence of KCl was 1.364 L x m(-2) x h(-1). In the presence of 0.3 mM and 3 mM KCI, the rate constant increased to 10.5 L x m(-2) x h(-1) and 51.0 L x m(-2) x h(-1), respectively. For the reaction with zerovalent iron and TNT, the rate constant increased from 6.5 (L/m2 x h) in the absence of KCl to 37 L x m(-2) x h(-1) using 3 mM KCl. The results demonstrate that chloride based corrosion promoters enhance the rate of TNT degradation. The in-situ breakage of the oxide layer using corrosion promoters was applied as a treatment to maintain the long-term activity of the metallic species. Zinc maintained a high reactivity toward TNT, and the reactivity of iron increased after 5 treatment cycles using 3 mM KCI. Zinc and iron scanning electron micrographs indicate that TNT degradation rate enhancement is caused by the pitting corrosion mechanism.

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.

Degradation of florfenicol in water by UV/Na2S 2O 8 process.

PubMed

Gao, Yu-Qiong; Gao, Nai-Yun; Deng, Yang; Yin, Da-Qiang; Zhang, Yan-Sen

2015-06-01

UV irradiation-activated sodium persulfate (UV/PS) was studied to degrade florfenicol (FLO), a phenicol antibiotic commonly used in aquaculture, in water. Compared with UV/H2O2 process, UV/PS process achieves a higher FLO degradation efficiency, greater mineralization, and less cost. The quantum yield for direct photolysis of FLO and the second-order rate constant of FLO with sulfate radicals were determined. The effects of various factors, namely PS concentration, anions (NO3 (-), Cl(-), and HCO3 (-)), ferrous ion, and humic acid (HA), on FLO degradation were investigated. The results showed that the pseudo-first-order rate constant increased linearly with increased PS concentration. The tested anions all adversely affected FLO degradation performance with the order of HCO3 (-) > Cl(-) > NO3 (-). Coexisting ferrous ions enhanced FLO degradation at a Fe(2+)/PS molar ratio under 1:1. HA significantly inhibited FLO degradation due to radical scavenging and light-screening effect. Toxicity assessment showed that it is capable of controlling the toxicity for FLO degradation. These findings indicated that UV/PS is a promising technology for water polluted by antibiotics, and the treatment is optimized only after the impacts of water characteristics are carefully considered.

Legume-Cereal Intercropping Improves Forage Yield, Quality and Degradability.

PubMed

Zhang, Jie; Yin, Binjie; Xie, Yuhuai; Li, Jing; Yang, Zaibin; Zhang, Guiguo

2015-01-01

Intercropping legume with cereal is an extensively applied planting pattern in crop cultivation. However, forage potential and the degradability of harvested mixtures from intercropping system remain unclear. To investigate the feasibility of applying an intercropping system as a forage supply source to ruminants, two consecutive experiments (experiments 1 and 2) involving a field cultivation trial and a subsequent in vivo degradable experiment were conducted to determine the forage production performance and the ruminally degradable characteristics of a harvested mixture from an alfalfa/corn-rye intercropping system. In experiment 1, the intercropping system was established by alternating alfalfa and corn or rye with a row ratio of 5:2. Dry matter (DM) and nutrient yields were determined. In experiment 2, forages harvested from the different treatments were used as feedstuff to identify nutrient degradation kinetics and distribution of components between the rapidly degradable (a), potentially degradable (b) and the degradation rate constant (c) of 'b' fraction by in sacco method in Small-Tail Han wether Sheep. The intercropping system of alfalfa and corn-rye provided higher forage production performance with net increases of 9.52% and 34.81% in DM yield, 42.13% and 16.74% in crude protein (CP) yield, 25.94% and 69.99% in degradable DM yield, and 16.96% and 5.50% in degradable CP yield than rotation and alfalfa sole cropping systems, respectively. In addition, the harvest mixture from intercropping system also had greater 'a' fraction, 'b' fraction, 'c' values, and effective degradability (E value) of DM and CP than corn or rye hay harvested from rotation system. After 48-h exposure to rumen microbes, intercropping harvest materials were degraded to a higher extent than separately degraded crop stems from the sole system as indicated by visual microscopic examination with more tissues disappeared. Thus, the intercropping of alfalfa and corn-rye exhibited a greater

Quantifying the degradation of organic matter in marine sediments: A review and synthesis

NASA Astrophysics Data System (ADS)

Arndt, Sandra; Jørgensen, B. B.; LaRowe, D. E.; Middelburg, J. J.; Pancost, R. D.; Regnier, P.

2013-08-01

Quantifying the rates of biogeochemical processes in marine sediments is essential for understanding global element cycles and climate change. Because organic matter degradation is the engine behind benthic dynamics, deciphering the impact that various forces have on this process is central to determining the evolution of the Earth system. Therefore, recent developments in the quantitative modeling of organic matter degradation in marine sediments are critically reviewed. The first part of the review synthesizes the main chemical, biological and physical factors that control organic matter degradation in sediments while the second part provides a general review of the mathematical formulations used to model these processes and the third part evaluates their application over different spatial and temporal scales. Key transport mechanisms in sedimentary environments are summarized and the mathematical formulation of the organic matter degradation rate law is described in detail. The roles of enzyme kinetics, bioenergetics, temperature and biomass growth in particular are highlighted. Alternative model approaches that quantify the degradation rate constant are also critically compared. In the third part of the review, the capability of different model approaches to extrapolate organic matter degradation rates over a broad range of temporal and spatial scales is assessed. In addition, the structure, functions and parameterization of more than 250 published models of organic matter degradation in marine sediments are analyzed. The large range of published model parameters illustrates the complex nature of organic matter dynamics, and, thus, the limited transferability of these parameters from one site to another. Compiled model parameters do not reveal a statistically significant correlation with single environmental characteristics such as water depth, deposition rate or organic matter flux. The lack of a generic framework that allows for model parameters to be

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.

[Degradation Kinetics and Formation of Disinfection By-products During Linuron Chlorination in Drinking Water].

PubMed

Ling, Xiao; Hu, Chen-yan; Cheng, Ming; Gu, Jian

2015-05-01

Chlorination degradation of linuron was studied using the common disinfectant sodium hypochlorite, the effects of chlorine dosage, pH value, bromine ion concentrationand temperature were systematically investigated, and the formation characteristics of disinfection by-products (DBPs) during the chlorination reaction was analyzed. The results showed that the chlorination degradation kinetics of linuron by sodium hypochlorite could be well described by the second-order kinetic model. Moreover, pH values had a great impact on the degradation reaction, and the rate constant reached the maximum level at pH 7, and the base elementary reaction rate constants of HOCl and OCl- with linuron were 4.84 x 10(2) L · (mol · h)(-1) and 3.80 x 10(2) L · (mol · h)(-1), respectively. The reaction rate decreased with the addition of bromide ion and increased with increasing temperature. Furthermore, many kinds of disinfection by- products were produced during the chlorination degradation of linuron, including CF, DCAN, TCNM and halogen acetone. Under conditions of different solution pH and different bromide ion concentrations, there would be significant difference in the types and concentrations of disinfection by-products.

Degradation rates of phorbol esters in Jatropha curcas L. oil and pressed seeds under different storage conditions.

PubMed

Phasukarratchai, Naphatsarnan; Damrongsiri, Seelawut; Tongcumpou, Chantra

2017-03-01

Phorbol esters (PEs), found in Jatropha curcas crude oil (JCO) and J. curcas pressed seeds (JPS), are known as bioactive compounds in agricultural and pharmaceutical applications. The degradation rates of PEs in JCO and JPS under various conditions is important for the utilisation of PEs. Thus the objective of this study was to determine the PE degradation rates in JCO and JPS under different storage conditions. PE degradation rates were found to be first-order reactions. The slowest degradation rate was at 0.9 × 10 -3 d -1 for both JCO and JPS unexposed to light at 4 °C. Light intensity (1097 lx and 4690 lx, representing diffused sunlight and fluorescent lighting, respectively) and temperature (25 to 35 °C) were the significant degradation factors. Light exposure led to 280% to 380% higher degradation rates in JCO than in JPS due to light penetration through the transparent oil. Dried and sterilised JPS showed an 80% to 90% lower PE degradation rate than untreated JPS under all storage conditions since biodegradation was assembly limited. The PEs were unstable under the studied conditions, especially when exposed to light and room temperature. To protect against PE degradation, a material should be stored in a light-protected container and below 4 °C. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

PubMed

Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

2014-05-22

Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

Modeling crystal growth from solution with molecular dynamics simulations: approaches to transition rate constants.

PubMed

Reilly, Anthony M; Briesen, Heiko

2012-01-21

The feasibility of using the molecular dynamics (MD) simulation technique to study crystal growth from solution quantitatively, as well as to obtain transition rate constants, has been studied. The dynamics of an interface between a solution of Lennard-Jones particles and the (100) face of an fcc lattice comprised of solute particles have been studied using MD simulations, showing that MD is, in principle, capable of following growth behavior over large supersaturation and temperature ranges. Using transition state theory, and a nearest-neighbor approximation growth and dissolution rate constants have been extracted from equilibrium MD simulations at a variety of temperatures. The temperature dependence of the rates agrees well with the expected transition state theory behavior. © 2012 American Institute of Physics

Influence of UV dose on the UV/H2O2 process for the degradation of carbamazepine in wastewater.

PubMed

Somathilake, Purnima; Dominic, John Albino; Achari, Gopal; Langford, Cooper H; Tay, Joo-Hwa

2018-05-02

This study evaluates the influence of UV dose on degradation of carbamazepine (CBZ) in wastewater under UV-C (λ = 254 nm) photolysis with and without H 2 O 2 . The rate of degradation of CBZ exhibited a direct dependence on the intensity of incident UV irradiation as the rate of degradation was observed to increase linearly (R 2  = 0.98) with UV intensity between 1.67 and 8.95 × 10 17 photons/s. More than 95% of the CBZ that spiked in wastewater rapidly degraded within 4 min with a first-order rate constant of 1.2 min -1 for an optimum H 2 O 2 dose of 100 mg/L. Bench-scale continuous flow reactor experiments also showed that CBZ degraded with first-order kinetics at a rate constant of 1.02 min -1 . The kinetic parameters obtained for a continuous bench-scale reactor were in good agreement with the relationships developed through batch experiments with only a marginal deviation of ± 6.5%. The relationship between UV intensity and CBZ degradation rate obtained in this study was extrapolated to the UV disinfection unit of a wastewater treatment plant to predict possible degradation of CBZ during UV disinfection. The addition of 100 mg/L of H 2 O 2 to the secondary-treated effluent entering the UV disinfection unit is predicted to achieve over 60% degradation of CBZ.

Factors controlling the abiotic photo-degradation of monomethylmercury in surface waters

NASA Astrophysics Data System (ADS)

Black, Frank J.; Poulin, Brett A.; Flegal, A. Russell

2012-05-01

Photo-decomposition is among the most important mechanisms responsible for degrading monomethylmercury (MMHg) in aquatic systems, but this process is not fully understood. We investigated the relative importance of different factors in controlling the rate of MMHg photo-decomposition in surface waters in experiments using DOM isolated from natural waters. We found no evidence of net abiotic production of MMHg in any dark or light exposed treatments. The average (mean ± s.d.) MMHg photo-decomposition rate constant for all light exposed samples using DOM concentrated from three coastal wetlands was 0.0099 ± 0.0020 E-1m2 (range of 0.006-0.015 E-1m2) when expressed in photon flux from 330-700 nm. This was roughly 3-fold higher than the average MMHg photo-decomposition rate constant in coastal seawater of 0.0032 ± 0.0010 E-1m2. MMHg photo-degradation was highly wavelength dependent. The ratio of MMHg photo-decomposition rate constants, with respect to photon flux, was 400:37:1 for UVB:UVA:PAR. However, when integrated across the entire water column over which MMHg photo-demethylation occurs, PAR was responsible for photo-degrading more MMHg than UVB and UVA combined in the three wetland sites because of the more rapid attenuation of UV light with depth. MMHg half-lives in the wetlands were calculated for the upper 250 cm where photo-degradation occurred, and ranged from 7.6 to 20 days under typical summer sunlight conditions at 37°N. Rates of MMHg photo-decomposition decreased with increasing salinity, and were 27% higher at a salinity of 5 than those at a salinity of 25. This difference could not be accounted for by changes in the complexation of MMHg by DOM and chloride. Differences in MMHg photo-degradation rate constants of up to 18% were measured between treatments using DOM concentrated from three different wetlands. Surprisingly, increasing DOM concentration from 1.5 to 11.3 mg OC L-1 had only a small (6%) effect on MMHg photo-decomposition, which was much

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 ...

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang (David)

2015-01-01

Insulation resistance (IR) degradation in Ni-BaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure and direct-current (DC) leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current-time dependence data fit well to an exponential form, and a characteristic growth time ?SD can be determined. A greater value of tau(sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in Ni-BaTiO3 capacitors. The reduction of barrier height as a function of time follows an exponential relation of phi (??)=phi (0)e(exp -2?t), where the degradation rate constant ??=??o??(????/????) is inversely proportional to the mean time to failure (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi(0) will favor a slow IR degradation process, but a lower phi(0) will also promote electronic carrier conduction across the barrier and decrease the insulation resistance. As a result, a moderate barrier height phi(0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant ??) will result in a minimized IR degradation process and the most improved reliability in Ni-BaTiO3 multilayer ceramic capacitors.

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang David

2015-01-01

Insulation resistance (IR) degradation in NiBaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure (TTF) and direct current leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current time dependence data fit well to an exponential form, and a characteristic growth time tau (sub SD) can be determined. A greater value of tau (sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in NiBaTiO3 capacitors. The reduction of barrier height as a function oftime follows an exponential relation of phi (t ) = phi (0) e (exp -2Kt), where 13 the degradation rate constant K Koe (Ek/kT) is inversely proportional to the mean TTF (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi (0) will favor a slow IR degradation process, but a lower phi (0) will also promote electronic carrier conduction across the barrier and decrease the IR. As a result, a moderate barrier height phi (0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant K) will result in a minimized IR degradation process and the most improved reliability in NiBaTiO3 multilayer ceramic capacitors.

Laser Measurements of the H Atom + Ozone Rate Constant at Atmospheric Temperatures

NASA Astrophysics Data System (ADS)

Liu, Y.; Smith, G. P.; Peng, J.; Reppert, K. J.; Callahan, S. L.

2015-12-01

The exothermic H + O3 reaction produces OH(v) Meinel band emissions, used to derive mesospheric H concentrations and chemical heating rates. We have remeasured its rate constant to reduce resulting uncertainties and the measurement extend to lower mesospheric temperatures using modern laser techniques. H atoms are produced by pulsed ultraviolet laser trace photolysis of O3, followed by reaction of O(D) with added H2. A second, delayed, frequency-mixed dye laser measures the reaction decay rate with the remaining ozone by laser induced fluorescence. We monitor either the H atom decay by 2 photon excitation at 205 nm and detection of red fluorescence, or the OH(v=9) product time evolution with excitation of the B-X (0,9) band at 237 nm and emission in blue B-A bands. By cooling the enclosed low pressure flow cell we obtained measurements from 146-305 K. Small kinetic modeling corrections are made for secondary regeneration of H atoms. The results fully confirm the current NASA JPL recommendation for this rate constant, and establish its extrapolation down to the lower temperatures of the mesosphere. This work was supported by the NSF Aeronomy Program and an NSF Physics summer REU student grant.

Unsteady flow past an airfoil pitched at constant rate

NASA Technical Reports Server (NTRS)

Lourenco, L.; Vandommelen, L.; Shib, C.; Krothapalli, A.

1992-01-01

The unsteady flow past a NACA 0012 airfoil that is undertaking a constant-rate pitching up motion is investigated experimentally by the PIDV technique in a water towing tank. The Reynolds number is 5000, based upon the airfoil's chord and the free-stream velocity. The airfoil is pitching impulsively from 0 to 30 deg. with a dimensionless pitch rate alpha of 0.131. Instantaneous velocity and associated vorticity data have been acquired over the entire flow field. The primary vortex dominates the flow behavior after it separates from the leading edge of the airfoil. Complete stall emerges after this vortex detaches from the airfoil and triggers the shedding of a counter-rotating vortex near the trailing edge. A parallel computational study using the discrete vortex, random walk approximation has also been conducted. In general, the computational results agree very well with the experiment.

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.

Constant growth rate can be supported by decreasing energy flux and increasing aerobic glycolysis.

PubMed

Slavov, Nikolai; Budnik, Bogdan A; Schwab, David; Airoldi, Edoardo M; van Oudenaarden, Alexander

2014-05-08

Fermenting glucose in the presence of enough oxygen to support respiration, known as aerobic glycolysis, is believed to maximize growth rate. We observed increasing aerobic glycolysis during exponential growth, suggesting additional physiological roles for aerobic glycolysis. We investigated such roles in yeast batch cultures by quantifying O2 consumption, CO2 production, amino acids, mRNAs, proteins, posttranslational modifications, and stress sensitivity in the course of nine doublings at constant rate. During this course, the cells support a constant biomass-production rate with decreasing rates of respiration and ATP production but also decrease their stress resistance. As the respiration rate decreases, so do the levels of enzymes catalyzing rate-determining reactions of the tricarboxylic-acid cycle (providing NADH for respiration) and of mitochondrial folate-mediated NADPH production (required for oxidative defense). The findings demonstrate that exponential growth can represent not a single metabolic/physiological state but a continuum of changing states and that aerobic glycolysis can reduce the energy demands associated with respiratory metabolism and stress survival. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Degradation characteristics of 2,4-dichlorophenoxyacetic acid in electro-biological system.

PubMed

Zhang, Jingli; Cao, Zhanping; Zhang, Hongwei; Zhao, Lianmei; Sun, Xudong; Mei, Feng

2013-11-15

The reductive degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in an electro-biological system, a biological system and an electric catalytic system, respectively. Electrochemical characteristics were monitored by cyclic voltammetry and the intermediate products of 2,4-D degradation were determined by high speed liquid chromatography (HPLC). The results showed that all 2,4-D degradations in the three systems conformed to the kinetics characteristics of one-order reaction, and the degradation kinetics constants were 28.74 × 10(-2) h(-1), 19.73 × 10(-2) h(-1) and 3.54 × 10(-2) h(-1), respectively. The kinetics constant in the electro-biological system was higher than the sum in the other two systems by 19%. The electrochemical assistance provided the electrons and accelerated the electron transfer rate in the microbial degradation of 2,4-D. The degradation resulted from the microbial reduction strengthened by the electrochemical assistance. The electron transfer existed between the electrode, cytochrome, NAD and the pollutants. A long-range electron transfer process could be achieved on the multi-phase interfaces between the electrode, bacteria and the pollutants. Copyright © 2013 Elsevier B.V. All rights reserved.

Photo degradation of methyl orange an azo dye by advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism.

PubMed

Gomathi Devi, L; Girish Kumar, S; Mohan Reddy, K; Munikrishnappa, C

2009-05-30

Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The

Microfabricated microengine with constant rotation rate

DOEpatents

Romero, Louis A.; Dickey, Fred M.

1999-01-01

A microengine uses two synchronized linear actuators as a power source and converts oscillatory motion from the actuators into constant rotational motion via direct linkage connection to an output gear or wheel. The microengine provides output in the form of a continuously rotating output gear that is capable of delivering drive torque at a constant rotation to a micromechanism. The output gear can have gear teeth on its outer perimeter for directly contacting a micromechanism requiring mechanical power. The gear is retained by a retaining means which allows said gear to rotate freely. The microengine is microfabricated of polysilicon on one wafer using surface micromachining batch fabrication.

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.

Elucidating PID Degradation Mechanisms and In Situ Dark I–V Monitoring for Modeling Degradation Rate in CdTe Thin-Film Modules

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

Hacke, Peter; Spataru, Sergiu; Johnston, Steve

A progression of potential-induced degradation (PID) mechanisms are observed in CdTe modules, including shunting/junction degradation and two different manifestations of series resistance depending on the stress level and water ingress. The dark I-V method for in-situ characterization of Pmax based on superposition was adapted for the thin-film modules undergoing PID in view of the degradation mechanisms observed. An exponential model based on module temperature and relative humidity was fit to the PID rate for multiple stress levels in chamber tests and validated by predicting the observed degradation of the module type in the field.

Degradation of acrylamide by the UV/chlorine advanced oxidation process.

PubMed

Gao, Ze-Chen; Lin, Yi-Li; Xu, Bin; Pan, Yang; Xia, Sheng-Ji; Gao, Nai-Yun; Zhang, Tian-Yang; Chen, Ming

2017-11-01

The degradation of acrylamide (AA) during UV/chlorine advanced oxidation process (AOP) was investigated in this study. The degradation of AA was negligible during UV irradiation alone. However, AA could be effectively degraded and mineralized during UV/chlorination due to the generation of hydroxyl radicals (OH). The degradation kinetics of AA during UV/chlorination fitted the pseudo-first order kinetics with the rate constant between AA and OH radicals being determined as 2.11 × 10 9  M -1  s -1 . The degradation rate and mineralization of AA during UV/chlorination were significantly promoted at acidic conditions as well as increasing chlorine dosage. The volatile degradation products of AA during UV/chlorination were identified using gas chromatography-mass spectrometry and the degradation pathways were then proposed accordingly. The formation of disinfection by-products (DBPs) in Milli-Q water and tap water during UV/chlorination of AA was also investigated. The DBPs included chloroform, dichloroacetonitrile, trichloroacetonitrile, 2,2-dichloroacetamide and 2,2,2-trichloroacetamide. Furthermore, the variations of AA degradation during UV/chlorination in different real water samples were evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Degradation of diclofenac by UV-activated persulfate process: Kinetic studies, degradation pathways and toxicity assessments.

PubMed

Lu, Xian; Shao, Yisheng; Gao, Naiyun; Chen, Juxiang; Zhang, Yansen; Xiang, Huiming; Guo, Youluo

2017-07-01

Diclofenac (DCF) is the frequently detected non-steroidal pharmaceuticals in the aquatic environment. In this study, the degradation of DCF was evaluated by UV-254nm activated persulfate (UV/PS). The degradation of DCF followed the pseudo first-order kinetics pattern. The degradation rate constant (k obs ) was accelerated by UV/PS compared to UV alone and PS alone. Increasing the initial PS dosage or solution pH significantly enhanced the degradation efficiency. Presence of various natural water constituents had different effects on DCF degradation, with an enhancement or inhibition in the presence of inorganic anions (HCO 3 - or Cl - ) and a significant inhibition in the presence of NOM. In addition, preliminary degradation mechanisms and major products were elucidated using LC-MS/MS. Hydroxylation, decarbonylation, ring-opening and cyclation reaction involving the attack of SO 4 • - or other substances, were the main degradation mechanism. TOC analyzer and Microtox bioassay were employed to evaluate the mineralization and cytotoxicity of solutions treated by UV/PS at different times, respectively. Limited elimination of TOC (32%) was observed during the mineralization of DCF. More toxic degradation products and their related intermediate species were formed, and the UV/PS process was suitable for removing the toxicity. Of note, longer degradation time may be considered for the final toxicity removal. Copyright © 2017. Published by Elsevier Inc.

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors.

PubMed

González, Antonia Sandoval; Martínez, Susana Silva

2008-09-01

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.

Absolute rate constant for the O plus NO chemiluminescence in the near infrared

NASA Technical Reports Server (NTRS)

Golde, M. F.; Roche, A. E.; Kaufman, F.

1973-01-01

Infrared chemiluminescence from the process O + NO (+M) NO2 + hv (+M) has been studied between 1.3 and 4.1 micrometer. The wavelength dependence of the continuum between 1.3 and 3.3 micrometer is in fair agreement with previous studies and the measured radiative rate constant at 1.51 micrometer establishes the NO-O glow in this spectral range as a secondary emission standard. Comparison with previous studies of the visible region of the glow implies that the overall radiative rate constant lies in the range (9.4 to 11.2) x 10 to the minus 17 power cu cm sec/1. In the region 3.3 to 4.1 micrometer, the previously observed broad band, peaking at 3.7 micrometer, shows a complex kinetic dependence on O and M.

Kinetics and Quantitative Structure—Activity Relationship Study on the Degradation Reaction from Perfluorooctanoic Acid to Trifluoroacetic Acid

PubMed Central

Gong, Chen; Sun, Xiaomin; Zhang, Chenxi; Zhang, Xue; Niu, Junfeng

2014-01-01

Investigation of the degradation kinetics of perfluorooctanoic acid (PFOA) has been carried out to calculate rate constants of the main elementary reactions using the multichannel Rice-Ramsperger-Kassel-Marcus theory and canonical variational transition state theory with small-curvature tunneling correction over a temperature range of 200~500 K. The Arrhenius equations of rate constants of elementary reactions are fitted. The decarboxylation is role step in the degradation mechanism of PFOA. For the perfluorinated carboxylic acids from perfluorooctanoic acid to trifluoroacetic acid, the quantitative structure–activity relationship of the decarboxylation was analyzed with the genetic function approximation method and the structure–activity model was constructed. The main parameters governing rate constants of the decarboxylation reaction from the eight-carbon chain to the two-carbon chain were obtained. As the structure–activity model shows, the bond length and energy of C1–C2 (RC1–C2 and EC1–C2) are positively correlated to rate constants, while the volume (V), the energy difference between EHOMO and ELUMO (ΔE), and the net atomic charges on atom C2 (QC2) are negatively correlated. PMID:25196516

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

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.

Thermal degradation kinetics of all-trans and cis-carotenoids in a light-induced model system.

PubMed

Xiao, Ya-Dong; Huang, Wu-Yang; Li, Da-Jing; Song, Jiang-Feng; Liu, Chun-Quan; Wei, Qiu-Yu; Zhang, Min; Yang, Qiu-Ming

2018-01-15

Thermal degradation kinetics of lutein, zeaxanthin, β-cryptoxanthin, β-carotene was studied at 25, 35, and 45°C in a model system. Qualitative and quantitative analyses of all-trans- and cis-carotenoids were conducted using HPLC-DAD-MS technologies. Kinetic and thermodynamic parameters were calculated by non-linear regression. A total of 29 geometrical isomers and four oxidation products were detected, including all-trans-, keto compounds, mono-cis- and di-cis-isomers. Degradations of all-trans-lutein, zeaxanthin, β-cryptoxanthin, and β-carotene were described by a first-order kinetic model, with the order of rate constants as k β -carotene >k β -cryptoxanthin >k lutein >k zeaxanthin . Activation energies of zeaxanthin, lutein, β-cryptoxanthin, and β-carotene were 65.6, 38.9, 33.9, and 8.6kJ/moL, respectively. cis-carotenoids also followed with the first-order kinetic model, but they did not show a defined sequence of degradation rate constants and activation energies at different temperatures. A possible degradation pathway of four carotenoids was identified to better understand the mechanism of carotenoid degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Degradation rates of glycerol polyesters at acidic and basic conditions

USDA-ARS?s Scientific Manuscript database

Polyesters prepared from glycerol with mixtures of adipic and citric acids were evaluated in the laboratory to estimate degradation rates over a range of pH conditions. These renewable polymers provide a market for glycerol that is generated during biodiesel production. The polyesters were prepared...

Load-bearing capacity and biological allowable limit of biodegradable metal based on degradation rate in vivo.

PubMed

Cho, Sung Youn; Chae, Soo-Won; Choi, Kui Won; Seok, Hyun Kwang; Han, Hyung Seop; Yang, Seok Jo; Kim, Young Yul; Kim, Jong Tac; Jung, Jae Young; Assad, Michel

2012-08-01

In this study, a newly developed Mg-Ca-Zn alloy for low degradation rate and surface erosion properties was evaluated. The compressive, tensile, and fatigue strength were measured before implantation. The degradation behavior was evaluated by analyzing the microstructure and local hardness of the explanted specimen. Mean and maximum degradation rates were measured using micro CT equipment from 4-, 8-, and 16- week explants, and the alloy was shown to display surface erosion properties. Based on these characteristics, the average and minimum load bearing capacities in tension, compression, and bending modes were calculated. According to the degradation rate and references of recommended dietary intakes (RDI), the Mg-Ca-Zn alloy appears to be safe for human use. Copyright © 2012 Wiley Periodicals, Inc.

Simulation of substrate degradation in composting of sewage sludge

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

Zhang Jun; Gao Ding, E-mail: gaod@igsnrr.ac.c; Chen Tongbin

2010-10-15

To simulate the substrate degradation kinetics of the composting process, this paper develops a mathematical model with a first-order reaction assumption and heat/mass balance equations. A pilot-scale composting test with a mixture of sewage sludge and wheat straw was conducted in an insulated reactor. The BVS (biodegradable volatile solids) degradation process, matrix mass, MC (moisture content), DM (dry matter) and VS (volatile solid) were simulated numerically by the model and experimental data. The numerical simulation offered a method for simulating k (the first-order rate constant) and estimating k{sub 20} (the first-order rate constant at 20 {sup o}C). After comparison withmore » experimental values, the relative error of the simulation value of the mass of the compost at maturity was 0.22%, MC 2.9%, DM 4.9% and VS 5.2%, which mean that the simulation is a good fit. The k of sewage sludge was simulated, and k{sub 20}, k{sub 20s} (first-order rate coefficient of slow fraction of BVS at 20 {sup o}C) of the sewage sludge were estimated as 0.082 and 0.015 d{sup -1}, respectively.« less

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

NASA Technical Reports Server (NTRS)

Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

2004-01-01

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Degradation of n-butylparaben and 4- tert-octylphenol in H 2O 2/UV system

NASA Astrophysics Data System (ADS)

BŁędzka, Dorota; Gryglik, Dorota; Olak, Magdalena; Gębicki, Jerzy L.; Miller, Jacek S.

2010-04-01

The degradation of two endocrine disrupting compounds: n-butylparaben (BP) and 4- tert-octylphenol (OP) in the H 2O 2/UV system was studied. The effect of operating variables: initial hydrogen peroxide concentration, initial substrate concentration, pH of the reaction solution and photon fluency rate of radiation at 254 nm on reaction rate was investigated. The influence of hydroxyl radical scavengers, humic acid and nitrate anion on reaction course was also studied. A very weak scavenging effect during BP degradation was observed indicating reactions different from hydroxyl radical oxidation. The second-order rate constants of BP and OP with OH radicals were estimated to be 4.8×10 9 and 4.2×10 9 M -1 s -1, respectively. For BP the rate constant equal to 2.0×10 10 M -1 s -1was also determined using water radiolysis as a source of hydroxyl radicals.

Prediction of Rate Constant for Supramolecular Systems with Multiconfigurations.

PubMed

Guo, Tao; Li, Haiyan; Wu, Li; Guo, Zhen; Yin, Xianzhen; Wang, Caifen; Sun, Lixin; Shao, Qun; Gu, Jingkai; York, Peter; Zhang, Jiwen

2016-02-25

The control of supramolecular systems requires a thorough understanding of their dynamics, especially on a molecular level. It is extremely difficult to determine the thermokinetic parameters of supramolecular systems, such as drug-cyclodextrin complexes with fast association/dissociation processes by experimental techniques. In this paper, molecular modeling combined with novel mathematical relationships integrating the thermodynamic/thermokinetic parameters of a series of isomeric multiconfigurations to predict the overall parameters in a range of pH values have been employed to study supramolecular dynamics at the molecular level. A suitable form of Eyring's equation was derived and a two-stage model was introduced. The new approach enabled accurate prediction of the apparent dissociation/association (k(off)/k(on)) and unbinding/binding (k-r/kr) rate constants of the ubiquitous multiconfiguration complexes of the supramolecular system. The pyronine Y (PY) was used as a model system for the validation of the presented method. Interestingly, the predicted k(off) value ((40 ± 1) × 10(5) s(-1), 298 K) of PY is largely in agreement with that previously determined by fluorescence correlation spectroscopy ((5 ± 3) × 10(5) s(-1), 298 K). Moreover, the k(off)/k(on) and k-r/kr for flurbiprofen-β-cylcodextrin and ibuprofen-β-cyclodextrin systems were also predicted and suggested that the association processes are diffusion-controlled. The methodology is considered to be especially useful in the design and selection of excipients for a supramolecular system with preferred association and dissociation rate constants and understanding their mechanisms. It is believed that this new approach could be applicable to a wide range of ligand-receptor supramolecular systems and will surely help in understanding their complex mechanism.

[Kinetic Characteristics of Degradation of Geosmin and 2-Methylisoborneol by Bacillus subtilis].

PubMed

Ma, Nian-nian; Luo, Guo-zhi; Tan, Hong-xin; Yao, Miao-lan; Wang, Xiao-yong

2015-04-01

The earthy and musty odor problem in aquaculture systems has been a worldwide problem, especially in freshwater aquaculture systems. Geosmin (GSM) and 2-methylisoborneol (2-MIB), the most common causative agents of the off-flavor in fish, are lipophilic secondary metabolites of cyanobacteria, actinomycetes, and other microorganisms. The odor threshold concentrations for 2-MIB and GSM are approximately 9-42 ng x L(-1) and 4-10 ng x L(-1), and 600 ng x kg(-1) and 900 ng x kg(-1) in the aquaculture water and fish, respectively. With such a low odor threshold concentration, the off-flavor compounds greatly reduce the quality and economic value of aquatic products. This renders the fish, especially some valuable fish produced in recirculating aquaculture systems (RAS), unmarketable. The study reported the kinetic characteristics of degradation of GSM and 2-MIB by Bacillus subtilis and discussed the impacts of the initial concentration of GSM and 2-MIB (T1, T2) and inoculation amount (T1, T3 ) on the biodegradation rate. The result demonstrated that these two compounds could be degraded by B. subtilis effectively and the biodegradation rate reached more than 90% in T1, T2 and T3 treatments. The biodegradation of these two compounds behaved as a pseudo-first-order kinetics with rate constants (K) in the range of 0.14-0.41. K values indicated that the degradation rate was dependent on the inoculation amount but the start concentration of GSM and MIB. The degradation kinetics showed the maximum specific rate value (u(max)) and the Monod constant (K(s)) were 0.311 and 1.73, however, 2-MIB degradation process did not meet the Monod microbial growth equation (R2 = 0.781).

Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides.

PubMed

Jia, Lijuan; Shen, Zhemin; Su, Pingru

2016-05-01

Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants (k) were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity, all of the investigated organic compounds were divided into two groups (Group A and Group B). The percentage adsorption of organic compounds in Group A was less than 15% (wt./wt.) and that in the Group B was higher than 15% (wt./wt.). For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation (as a synergistic process) took place. Results showed that the relationship between the rate constants (k values) and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process, EHOMO and Fukui indices (f(0)x, f(-)x, f(+)x) were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process. Copyright © 2015. Published by Elsevier B.V.

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

NASA Technical Reports Server (NTRS)

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

1995-01-01

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Accurate acceleration of kinetic Monte Carlo simulations through the modification of rate constants.

PubMed

Chatterjee, Abhijit; Voter, Arthur F

2010-05-21

We present a novel computational algorithm called the accelerated superbasin kinetic Monte Carlo (AS-KMC) method that enables a more efficient study of rare-event dynamics than the standard KMC method while maintaining control over the error. In AS-KMC, the rate constants for processes that are observed many times are lowered during the course of a simulation. As a result, rare processes are observed more frequently than in KMC and the time progresses faster. We first derive error estimates for AS-KMC when the rate constants are modified. These error estimates are next employed to develop a procedure for lowering process rates with control over the maximum error. Finally, numerical calculations are performed to demonstrate that the AS-KMC method captures the correct dynamics, while providing significant CPU savings over KMC in most cases. We show that the AS-KMC method can be employed with any KMC model, even when no time scale separation is present (although in such cases no computational speed-up is observed), without requiring the knowledge of various time scales present in the system.

Acoustic emission of rock mass under the constant-rate fluid injection

NASA Astrophysics Data System (ADS)

Shadrin Klishin, AV, VI

2018-03-01

The authors study acoustic emission in coal bed and difficult-to-cave roof under injection of fluid by pumps at a constant rate. The functional connection between the roof hydrofracture length and the total number of AE pulses is validated, it is also found that the coal bed hydroloosening time, injection rate and time behavior of acoustic emission activity depend on the fluid injection volume required until the fluid breakout in a roadway through growing fractures. In the formulas offered for the practical application, integral parameters that characterize permeability and porosity of rock mass and process parameters of the technology are found during test injection.

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.

Rate of hydrolysis and degradation of the cyanogenic glycoside - dhurrin - in soil.

PubMed

Johansen, Henrik; Rasmussen, Lars Holm; Olsen, Carl Erik; Bruun Hansen, Hans Christian

2007-02-01

Cyanogenic glycosides are common plant toxins. Toxic hydrogen cyanide originating from cyanogenic glycosides may affect soil processes and water quality. In this study, hydrolysis, degradation and sorption of dhurrin (4-hydroxymandelonitrile-beta-d-glucoside) produced by sorghum has been studied in order to assess its fate in soil. The log K(ow) of dhurrin was -1.18+/-0.08 (22 degrees C). Hydrolysis was a first-order reaction with respect to dhurrin and hydroxyl ion concentrations. Half lives ranged from 1.2h (pH 8.6; 25 degrees C) to 530d (pH 4; 25 degrees C). The activation energy of hydrolysis was 112+9kJ. At pH 5.8 and room temperature, addition of humic acids (50gl(-1)) increased the rate of hydrolysis tenfold, while addition of kaolinite or goethite (100-250gl(-1)) both decreased the rate considerably. No significant sorption to soil components could be observed. The degradation rates of dhurrin in top and subsoils of Oxisols, Ultisols, Alfisols and Mollisols were studied at 22 degrees C (25mgl(-1), soil:liquid 1:1 (w:V), pH 3.8-8.1). Half-lives were 0.25-2h for topsoils, and 5-288h in subsoils. Hydrolysis in solution explained up to 45% of the degradation in subsoils whereas the contribution in topsoils was less than 14%, indicating the importance of enzymatic degradation processes. The highest risk of dhurrin leaching will take place when the soil is a low activity acid shallow soil with low content of clay minerals, iron oxides and humic acids.

Current rates and mechanisms of subsea permafrost degradation in the East Siberian Arctic Shelf

NASA Astrophysics Data System (ADS)

Shakhova, Natalia; Semiletov, Igor; Gustafsson, Orjan; Sergienko, Valentin; Lobkovsky, Leopold; Dudarev, Oleg; Tumskoy, Vladimir; Grigoriev, Michael; Mazurov, Alexey; Salyuk, Anatoly; Ananiev, Roman; Koshurnikov, Andrey; Kosmach, Denis; Charkin, Alexander; Dmitrevsky, Nicolay; Karnaukh, Victor; Gunar, Alexey; Meluzov, Alexander; Chernykh, Denis

2017-06-01

The rates of subsea permafrost degradation and occurrence of gas-migration pathways are key factors controlling the East Siberian Arctic Shelf (ESAS) methane (CH4) emissions, yet these factors still require assessment. It is thought that after inundation, permafrost-degradation rates would decrease over time and submerged thaw-lake taliks would freeze; therefore, no CH4 release would occur for millennia. Here we present results of the first comprehensive scientific re-drilling to show that subsea permafrost in the near-shore zone of the ESAS has a downward movement of the ice-bonded permafrost table of ~14 cm year-1 over the past 31-32 years. Our data reveal polygonal thermokarst patterns on the seafloor and gas-migration associated with submerged taliks, ice scouring and pockmarks. Knowing the rate and mechanisms of subsea permafrost degradation is a prerequisite to meaningful predictions of near-future CH4 release in the Arctic.

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments

NASA Astrophysics Data System (ADS)

Sun, Ming-Y. i.; Aller, Robert C.; Lee, Cindy; Wakeham, Stuart G.

2002-06-01

Degradation patterns of sedimentary algal lipids were tracked with time under variable redox treatments designed to mimic conditions in organic-rich, bioturbated deposits. Uniformly 13C-labeled algae were mixed with Long Island Sound surface muddy sediments and exposed to different redox regimes, including continuously oxic and anoxic, and oscillated oxic: anoxic conditions. Concentrations of several 13C-labeled algal fatty acids (16:1, 16:0 and 18:1), phytol and an alkene were measured serially. Results showed a large difference (∼10×) in first-order degradation rate constants of cell-associated lipids between continuously oxic and anoxic conditions. Exposure to oxic conditions increased the degradation of cell-associated lipids, and degradation rate constants were positive functions (linear or nonlinear) of the fraction of time sediments were oxic. Production of two new 13C-labeled compounds (iso-15:0 fatty acid and hexadecanol) further indicated that redox conditions and oxic: anoxic oscillations strongly affect microbial degradation of algal lipids and net synthesis of bacterial biomass. Production of 13C-labeled iso-15:0 fatty acid (a bacterial biomarker) was inversely proportional to the fraction of time sediments were oxic, rapidly decreasing after 10 days of incubation under oxic and frequently oscillated conditions. Turnover of bacterial biomass was faster under continuously or occasionally oxic conditions than under continuously anoxic conditions. 13C-labeled hexadecanol, an intermediate degradation product, accumulated under anoxic conditions but not under oxic or periodically oxic conditions. The frequency of oxic: anoxic oscillation clearly alters both the rate and pathways of lipid degradation in surficial sediments. Terminal degradation efficiency and lipid products from degradation of algal material depend on specific patterns of redox fluctuations.

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 and mechanism for the sonochemical degradation of a nonionic surfactant.

PubMed

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

The sonolytic degradation of the nonionic surfactant, octaethylene glycol monododecyl ether (C(12)E(8)), has been studied at various initial concentrations below and above its critical micelle concentration (CMC). It has been observed that the degradation rate increases with an increase in the initial concentration of the surfactant until the CMC is reached. Above the CMC an almost constant degradation rate is observed, suggesting that the surfactant in its monomer form is involved in the degradation process. The degradation process of C(12)E(8) involves two distinct primary processes occurring at the bubble/solution interface: (a) hydroxylation/oxidation of the surfactant and (b) pyrolytic fragmentation of the surfactant. The oxidative cleavage of ethylene oxide units provides evidence for OH radical attack. Hydroxylation of the ethoxy chain gives rise to various short-chain carboxyalkyl-polyethylene glycol intermediates. The polyethylene glycol chain formed, due to the scission of the C(12)E(8) molecule, undergoes rapid hydroxylation/oxidation to yield simple compounds that have the potential to undergo further degradation. The detection of multiple intermediates indicates that several processes affect the complete degradation pathways of the surfactant molecule. TOC analysis, however, indicates that the sonolytic mineralization of the surfactant is difficult to achieve at reasonable rates due to the relatively low surface activity of the degradation products formed during sonolysis.

Modeling the effect of adsorption on the degradation rate of propiconazole in profiles of Polish Luvisols.

PubMed

Paszko, Tadeusz; Jankowska, Monika

2018-06-18

Laboratory adsorption and degradation studies were carried out to determine the effect of time-dependent adsorption on propiconazole degradation rates in samples from three Polish Luvisols. Strong propiconazole adsorption (organic carbon normalized adsorption coefficients K oc in the range of 1217-7777 mL/g) was observed in batch experiments, with a typical biphasic mechanism with a fast initial step followed by the time-dependent step, which finished within 48 h in the majority of soils. The time-dependent step observed in incubation experiments was longer (duration from 5 to 23 d), and its contribution to total adsorption was from 20% to 34%. The half-lives obtained at 25 °C and 40% maximum water holding capacity of soil, were in the range of 34.7-112.9 d in the Ap horizon and in the range of 42.3-448.8 d for subsoils. The very strong correlations, between degradation rates in pore water and soil organic carbon and soil microbial activity, indicated that microbial degradation of propiconazole was most likely the only significant process responsible for the decay of this compound under aerobic conditions for the whole of the examined soil profiles. Modeling of the processes showed that only models coupling adsorption and degradation were able to correctly describe the experimental data. The analysis of the bioavailability factor values showed that degradation was not limited by the rate of propiconazole desorption from soil, but sorption affected the degradation rate by decreasing its availability for microorganisms. Copyright © 2018. Published by Elsevier Inc.

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Degradation of polyvinyl alcohol (PVA) by UV/chlorine oxidation: Radical roles, influencing factors, and degradation pathway.

PubMed

Ye, Bei; Li, Yue; Chen, Zhuo; Wu, Qian-Yuan; Wang, Wen-Long; Wang, Ting; Hu, Hong-Ying

2017-11-01

Polyvinyl alcohol (PVA) is widely used in industry but is difficult to degrade. In this study, the synergistic effect of UV irradiation and chlorination on degradation of PVA was investigated. UV irradiation or chlorination alone did not degrade PVA. By contrast, UV/chlorine oxidation showed good efficiency for PVA degradation via generation of active free radicals, such as OH and Cl. The relative importance of these two free radicals in the oxidation process was evaluated, and it was shown that OH contributed more to PVA degradation than Cl did. The degradation of PVA followed pseudo first order kinetics. The rate constant k increased linearly from 0 min -1 to 0.3 min -1 with increasing chlorine dosage in range of 0 mg/L to 20 mg/L. However, when the chlorine dosage was increased above 20 mg/L, scavenging effect of free radicals occurred, and the degradation efficiency of PVA did not increase much more. Acidic media increased the degradation efficiency of PVA by UV/chlorine oxidation more than basic or neutral media because of the higher ratio of [HOCl]/[OCl - ], higher free radical quantum yields, and the lower free radical quenching effect under acidic conditions. Results of Fourier Transform Infrared Spectroscopy showed that carbonyl groups in degradation products were formed during UV/chlorine oxidation, and a possible degradation pathway via alcohol to carbonyl was proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Thermal Degradation Kinetics Modeling of Benzophenones and Xanthones during High-Temperature Oxidation of Cyclopia genistoides (L.) Vent. Plant Material.

PubMed

Beelders, Theresa; de Beer, Dalene; Joubert, Elizabeth

2015-06-10

Degradation of the major benzophenones, iriflophenone-3-C-glucoside-4-O-glucoside and iriflophenone-3-C-glucoside, and the major xanthones, mangiferin and isomangiferin, of Cyclopia genistoides followed first-order reaction kinetics during high-temperature oxidation of the plant material at 80 and 90 °C. Iriflophenone-3-C-glucoside-4-O-glucoside was shown to be the most thermally stable compound. Isomangiferin was the second most stable compound at 80 °C, while its degradation rate constant was influenced the most by increased temperature. Mangiferin and iriflophenone-3-C-glucoside had comparable degradation rate constants at 80 °C. The thermal degradation kinetic model was subsequently evaluated by subjecting different batches of plant material to oxidative conditions (90 °C/16 h). The model accurately predicted the individual contents of three of the compounds in aqueous extracts prepared from oxidized plant material. The impact of benzophenone and xanthone degradation was reflected in the decreased total antioxidant capacity of the aqueous extracts, as determined using the oxygen radical absorbance capacity and DPPH(•) scavenging assays.

Pseudo-extravasation rate constant of dynamic susceptibility contrast-MRI determined from pharmacokinetic first principles.

PubMed

Li, Xin; Varallyay, Csanad G; Gahramanov, Seymur; Fu, Rongwei; Rooney, William D; Neuwelt, Edward A

2017-11-01

Dynamic susceptibility contrast-magnetic resonance imaging (DSC-MRI) is widely used to obtain informative perfusion imaging biomarkers, such as the relative cerebral blood volume (rCBV). The related post-processing software packages for DSC-MRI are available from major MRI instrument manufacturers and third-party vendors. One unique aspect of DSC-MRI with low-molecular-weight gadolinium (Gd)-based contrast reagent (CR) is that CR molecules leak into the interstitium space and therefore confound the DSC signal detected. Several approaches to correct this leakage effect have been proposed throughout the years. Amongst the most popular is the Boxerman-Schmainda-Weisskoff (BSW) K 2 leakage correction approach, in which the K 2 pseudo-first-order rate constant quantifies the leakage. In this work, we propose a new method for the BSW leakage correction approach. Based on the pharmacokinetic interpretation of the data, the commonly adopted R 2 * expression accounting for contributions from both intravascular and extravasating CR components is transformed using a method mathematically similar to Gjedde-Patlak linearization. Then, the leakage rate constant (K L ) can be determined as the slope of the linear portion of a plot of the transformed data. Using the DSC data of high-molecular-weight (~750 kDa), iron-based, intravascular Ferumoxytol (FeO), the pharmacokinetic interpretation of the new paradigm is empirically validated. The primary objective of this work is to empirically demonstrate that a linear portion often exists in the graph of the transformed data. This linear portion provides a clear definition of the Gd CR pseudo-leakage rate constant, which equals the slope derived from the linear segment. A secondary objective is to demonstrate that transformed points from the initial transient period during the CR wash-in often deviate from the linear trend of the linearized graph. The inclusion of these points will have a negative impact on the accuracy of the leakage

Denitrification synergized with ANAMMOX for the anaerobic degradation of benzene: performance and microbial community structure.

PubMed

Peng, Shuchan; Zhang, Lilan; Zhang, DaiJun; Lu, Peili; Zhang, Xiaoting; He, Qiang

2017-05-01

To evaluate the effect of anaerobic ammonium oxidation (ANAMMOX) on benzene degradation under denitrification, a sequencing batch reactor (SBR) under denitrification synergized with ANAMMOX (SBR-DenAna) for benzene degradation was established by inoculating anaerobic ammonium-oxidizing bacteria (AnAOB) into a SBR under denitrification reactor (SBR-Den) for benzene degradation. The average rate of benzene degradation and the maximum first-order kinetic constant in SBR-DenAna were 2.34- and 1.41-fold those in SBR-Den, respectively, indicating that ANAMMOX improved the degradation of benzene under denitrification synergized with ANAMMOX. However, the average rate of benzene degradation decreased by 35% in the denitrification-ANAMMOX synergistic reactor when 10 mg N L -1 NO 2 - was added; the rate recovered once NO 2 - was depleted, indicating that ANAMMOX might detoxify NO 2 - . Results from high-throughput sequencing analysis revealed that Azoarcus within the family Rhodocyclaceae might be associated with benzene degradation in the two SBRs. AnAOB affiliated with the family Candidatus Brocadiaceae were just detected in SBR-DenAna.

Current rates and mechanisms of subsea permafrost degradation in the East Siberian Arctic Shelf

PubMed Central

Shakhova, Natalia; Semiletov, Igor; Gustafsson, Orjan; Sergienko, Valentin; Lobkovsky, Leopold; Dudarev, Oleg; Tumskoy, Vladimir; Grigoriev, Michael; Mazurov, Alexey; Salyuk, Anatoly; Ananiev, Roman; Koshurnikov, Andrey; Kosmach, Denis; Charkin, Alexander; Dmitrevsky, Nicolay; Karnaukh, Victor; Gunar, Alexey; Meluzov, Alexander; Chernykh, Denis

2017-01-01

The rates of subsea permafrost degradation and occurrence of gas-migration pathways are key factors controlling the East Siberian Arctic Shelf (ESAS) methane (CH4) emissions, yet these factors still require assessment. It is thought that after inundation, permafrost-degradation rates would decrease over time and submerged thaw-lake taliks would freeze; therefore, no CH4 release would occur for millennia. Here we present results of the first comprehensive scientific re-drilling to show that subsea permafrost in the near-shore zone of the ESAS has a downward movement of the ice-bonded permafrost table of ∼14 cm year−1 over the past 31–32 years. Our data reveal polygonal thermokarst patterns on the seafloor and gas-migration associated with submerged taliks, ice scouring and pockmarks. Knowing the rate and mechanisms of subsea permafrost degradation is a prerequisite to meaningful predictions of near-future CH4 release in the Arctic. PMID:28639616

Effect of Moisture Content of Chitin-Calcium Silicate on Rate of Degradation of Cefotaxime Sodium.

PubMed

Al-Nimry, Suhair S; Alkhamis, Khouloud A

2018-04-01

Assessment of incompatibilities between active pharmaceutical ingredient and pharmaceutical excipients is an important part of preformulation studies. The objective of the work was to assess the effect of moisture content of chitin calcium silicate of two size ranges (two specific surface areas) on the rate of degradation of cefotaxime sodium. The surface area of the excipient was determined using adsorption method. The effect of moisture content of a given size range on the stability of the drug was determined at 40°C in the solid state. The moisture content was determined at the beginning and the end of the kinetic study using TGA. The degradation in solution was studied for comparison. Increasing the moisture content of the excipient of size range 63-180 μm (surface area 7.2 m 2 /g) from 3.88 to 8.06% increased the rate of degradation of the drug more than two times (from 0.0317 to 0.0718 h -1 ). While an opposite trend was observed for the excipient of size range < 63 μm (surface area 55.4 m 2 /g). The rate of degradation at moisture content < 3% was 0.4547 h -1 , almost two times higher than that (0.2594 h -1 ) at moisture content of 8.54%, and the degradation in solid state at both moisture contents was higher than that in solution (0.0871 h -1 ). In conclusion, the rate of degradation in solid should be studied taking into consideration the specific surface area and moisture content of the excipient at the storage condition and it may be higher than that in solution.

Thermal degradation kinetics of phycocyanin encapsulation as an antioxidant agent

NASA Astrophysics Data System (ADS)

Nilamsari, A. M.; Yunanda, A.; Hadiyanto, H.

2018-01-01

Phycocyanin is a blue-light pigment that found in Cyanobacteria and two Eukaryotics algae such as Rhodophyta and Crytophyta. Phycocyanin is soluble in water and has a strong fluorescent properties as an antioxidant and normally used in food industry, cosmetic, biotechnology, and drug. However, Phycocyanin is easily damaged by a heating process. The aim of this study is to obtain the optimal condition of phycocyanin encapsulation with different coating materials, Chitosan and Carrageenan, by the calculation of heat resistance of antioxidant activity (D), range of temperature that increase the rate of degradation (Z), rate constant of degradation (k), and activation energy (Ea). The ratio of phycocyanin and the coating material are 2% (w/v) and 2 % (w/v).

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.

Rate constant for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

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

Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The presentmore » work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants.« less

Predicting chemical degradation during storage from two successive concentration ratios: Theoretical investigation.

PubMed

Peleg, Micha; Normand, Mark D

2015-09-01

When a vitamin's, pigment's or other food component's chemical degradation follows a known fixed order kinetics, and its rate constant's temperature-dependence follows a two parameter model, then, at least theoretically, it is possible to extract these two parameters from two successive experimental concentration ratios determined during the food's non-isothermal storage. This requires numerical solution of two simultaneous equations, themselves the numerical solutions of two differential rate equations, with a program especially developed for the purpose. Once calculated, these parameters can be used to reconstruct the entire degradation curve for the particular temperature history and predict the degradation curves for other temperature histories. The concept and computation method were tested with simulated degradation under rising and/or falling oscillating temperature conditions, employing the exponential model to characterize the rate constant's temperature-dependence. In computer simulations, the method's predictions were robust against minor errors in the two concentration ratios. The program to do the calculations was posted as freeware on the Internet. The temperature profile can be entered as an algebraic expression that can include 'If' statements, or as an imported digitized time-temperature data file, to be converted into an Interpolating Function by the program. The numerical solution of the two simultaneous equations requires close initial guesses of the exponential model's parameters. Programs were devised to obtain these initial values by matching the two experimental concentration ratios with a generated degradation curve whose parameters can be varied manually with sliders on the screen. These programs too were made available as freeware on the Internet and were tested with published data on vitamin A. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Estimate Of The Decay Rate Constant of Hydrogen Sulfide Generation From Landfilled Drywall

EPA Science Inventory

Research was conducted to investigate the impact of particle size on H2S gas emissions and estimate a decay rate constant for H2S gas generation from the anaerobic decomposition of drywall. Three different particle sizes of regular drywall and one particle size of paperless drywa...

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh.

PubMed

Horneman, A; Stute, M; Schlosser, P; Smethie, W; Santella, N; Ho, D T; Mailloux, B; Gorman, E; Zheng, Y; van Geen, A

2008-04-04

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

PubMed

Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

2012-11-20

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

Tannin content and rate of ruminal protein degradation of legume hays

USDA-ARS?s Scientific Manuscript database

This work evaluated ruminal protein degradation rates of legume hays that varied in tannin content. Two cuttings of 5 varieties of birdsfoot trefoil, (Lotus corniculatus), selected for different tannin contents but similar NDF and CP contents, and Spredor 4 alfalfa (control) were conserved as hay. S...

Effect of application rate on fumigant degradation in five agricultural soils

USDA-ARS?s Scientific Manuscript database

Fumigants continue to be used in soil disinfestation for many high value crops. There is a significant knowledge gap on how fumigant concentration in soil impacts fumigant dissipation and determination of the most efficient rate. The aim of this study was to determine the degradation characteristics...

Estimation of hydrolysis rate constants for carbamates

EPA Science Inventory

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...

Efficient degradation of TCE in groundwater using Pd and electro-generated H2 and O2: a shift in pathway from hydrodechlorination to oxidation in the presence of ferrous ions.

PubMed

Yuan, Songhu; Mao, Xuhui; Alshawabkeh, Akram N

2012-03-20

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.

Efficient Degradation of TCE in Groundwater Using Pd and Electro-generated H2 and O2: A Shift in Pathway from Hydrodechlorination to Oxidation in the Presence of Ferrous Ions

PubMed Central

Yuan, Songhu; Mao, Xuhui; Alshawabkeh, Akram N.

2012-01-01

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H2 and O2 is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H2O2 up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radical are detected due to decomposition of H2O2, slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na2SO4, NaCl, NaNO3, NaHCO3, K2SO4, CaSO4 and MgSO4 does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppresses degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation. PMID:22315993

Degradation rate of praziquantel and fenbendazole in rainbow trout following oral administration.

PubMed

Soukupova-Markova, Zdenka; Doubkova, Veronika; Marsalek, Petr; Svobodova, Zdenka; Papezikova, Ivana; Lang, Stepan; Navratil, Stanislav; Palikova, Miroslava

2015-01-01

The aim of this study was to evaluate and compare the rate of degradation and elimination of praziquantel and fenbendazole antiparasitics following oral administration to salmonids. In addition, we determine whether the length of the legal withdrawal period is sufficient for complete elimination of antiparasitic residue from the body. The use of these drugs in fish is currently considered off-label and data on degradation are not available for rainbow trout. The model species for this experiment was the rainbow trout (Oncorhynchus mykiss) and praziquantel and fenbendazole were chosen for experimental therapy. Both drugs were administered into the gastrointestinal tract using a stomach tube. Concentrations of fenbendazole and praziquantel were established through high performance liquid chromatography-tandem mass spectrometry. Our results show that concentrations of praziquantel and fenbendazole reach their maximum in the body within 24 hours of administration, with concentrations dropping sharply over the following 24 hours. With one exception, when trace amounts of both substances were found in blood plasma, the drugs were completely degraded and eliminated from the body by the end of the experiment (corresponding to 497.6 degree days). Praziquantel and fenbendazole both show a high rate of degradation and elimination from fish. As both substances were eliminated from the body within the required withdrawal period (i.e. within 500 degree days) they can be safely used based on current knowledge of their therapeutic effect for treating helminth infections.

Extension of the master sintering curve for constant heating rate modeling

NASA Astrophysics Data System (ADS)

McCoy, Tammy Michelle

The purpose of this work is to extend the functionality of the Master Sintering Curve (MSC) such that it can be used as a practical tool for predicting sintering schemes that combine both a constant heating rate and an isothermal hold. Rather than just being able to predict a final density for the object of interest, the extension to the MSC will actually be able to model a sintering run from start to finish. Because the Johnson model does not incorporate this capability, the work presented is an extension of what has already been shown in literature to be a valuable resource in many sintering situations. A predicted sintering curve that incorporates a combination of constant heating rate and an isothermal hold is more indicative of what is found in real-life sintering operations. This research offers the possibility of predicting the sintering schedule for a material, thereby having advanced information about the extent of sintering, the time schedule for sintering, and the sintering temperature with a high degree of accuracy and repeatability. The research conducted in this thesis focuses on the development of a working model for predicting the sintering schedules of several stabilized zirconia powders having the compositions YSZ (HSY8), 10Sc1CeSZ, 10Sc1YSZ, and 11ScSZ1A. The compositions of the four powders are first verified using x-ray diffraction (XRD) and the particle size and surface area are verified using a particle size analyzer and BET analysis, respectively. The sintering studies were conducted on powder compacts using a double pushrod dilatometer. Density measurements are obtained both geometrically and using the Archimedes method. Each of the four powders is pressed into ¼" diameter pellets using a manual press with no additives, such as a binder or lubricant. Using a double push-rod dilatometer, shrinkage data for the pellets is obtained over several different heating rates. The shrinkage data is then converted to reflect the change in relative

Nonadiabatic effects on the charge transfer rate constant: A numerical study of a simple model system

NASA Astrophysics Data System (ADS)

Shin, Seokmin; Metiu, Horia

1995-06-01

We use a minimal model to study the effects of the upper electronic states on the rate of a charge transfer reaction. The model consists of three ions and an electron, all strung on a line. The two ions at the ends of the structure are held fixed, but the middle ion and the electron are allowed to move in one dimension, along the line joining them. The system has two bound states, one in which the electron ties the movable ion to the fixed ion at the left, and the other in which the binding takes place to the fixed ion at the right. The transition between these bound states is a charge transfer reaction. We use the flux-flux correlation function theory to perform two calculations of the rate constant for this reaction. In one we obtain numerically the exact rate constant. In the other we calculate the exact rate constant for the case when the reaction proceeds exclusively on the ground adiabatic state. The difference between these calculations gives the magnitude of the nonadiabatic effects. We find that the nonadiabatic effects are fairly large even when the gap between the ground and the excited adiabatic state substantially exceeds the thermal energy. The rate in the nonadiabatic theory is always smaller than that of the adiabatic one. Both rate constants satisfy the Arrhenius formula. Their activation energies are very close but the nonadiabatic one is always higher. The nonadiabatic preexponential is smaller, due to the fact that the upper electronic state causes an early recrossing of the reactive flux. The description of this reaction in terms of two diabatic states, one for reactants and one for products, is not always adequate. In the limit when nonadiabaticity is small, we need to use a third diabatic state, in which the electron binds to the moving ion as the latter passes through the transition state; this is an atom transfer process. The reaction changes from an atom transfer to an electron transfer, as nonadiabaticity is increased.

Rate constants for chemical reactions in high-temperature nonequilibrium air

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1986-01-01

In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

DISSOCIATION OF ARSENITE-PEPTIDE COMPLEXES: TRIPHASIC NATURE, RATE CONSTANTS, HALF LIVES AND BIOLOGICAL IMPORTANCE

EPA Science Inventory

We determined the number and the dissociation rate constants of different complexes formed from arsenite and two peptides containing either one (RV AVGNDYASGYHYGV for peptide 20) or three cysteines (LE AWQGK VEGTEHLYSMK K for peptide 10) via radioactive 73As labeled arsenite and ...

Applying constraints on model-based methods: Estimation of rate constants in a second order consecutive reaction

NASA Astrophysics Data System (ADS)

Kompany-Zareh, Mohsen; Khoshkam, Maryam

2013-02-01

This paper describes estimation of reaction rate constants and pure ultraviolet/visible (UV-vis) spectra of the component involved in a second order consecutive reaction between Ortho-Amino benzoeic acid (o-ABA) and Diazoniom ions (DIAZO), with one intermediate. In the described system, o-ABA was not absorbing in the visible region of interest and thus, closure rank deficiency problem did not exist. Concentration profiles were determined by solving differential equations of the corresponding kinetic model. In that sense, three types of model-based procedures were applied to estimate the rate constants of the kinetic system, according to Levenberg/Marquardt (NGL/M) algorithm. Original data-based, Score-based and concentration-based objective functions were included in these nonlinear fitting procedures. Results showed that when there is error in initial concentrations, accuracy of estimated rate constants strongly depends on the type of applied objective function in fitting procedure. Moreover, flexibility in application of different constraints and optimization of the initial concentrations estimation during the fitting procedure were investigated. Results showed a considerable decrease in ambiguity of obtained parameters by applying appropriate constraints and adjustable initial concentrations of reagents.

Evaluation of Fuel Cell Operation and Degradation

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

Williams, Mark; Gemmen, Randall; Richards, George

The concepts of area specific resistance (ASR) and degradation are developed for different fuel cell operating modes. The concepts of exergetic efficiency and entropy production were applied to ASR and degradation. It is shown that exergetic efficiency is a time-dependent function useful describing the thermal efficiency of a fuel cell and the change in thermal efficiency of a degrading fuel cell. Entropy production was evaluated for the cases of constant voltage operation and constant current operation of the fuel cell for a fuel cell undergoing ohmic degradation. It was discovered that the Gaussian hypergeometric function describes the cumulative entropy andmore » electrical work produced by fuel cells operating at constant voltage. The Gaussian hypergeometric function is found in many applications in modern physics. This paper builds from and is an extension of several papers recently published by the authors in the Journal of The Electrochemical Society (ECS), ECS Transactions, Journal of Power Sources, and the Journal of Fuel Cell Science and Technology.« less

Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

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

Erben-Russ, M.; Michel, C.; Bors, W.

1987-04-23

The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA)more » was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.« less

Degradation of sulfamethazine in sewage sludge mixture by gamma irradiation

NASA Astrophysics Data System (ADS)

Chu, Libing; Wang, Jianlong; Liu, Yuankun

2015-03-01

The gamma-irradiation-induced degradation of antibiotics sulfamethazine (SMT) in sludge mixture was investigated. The results showed that gamma irradiation was effective in removing SMT from contaminated sludge mixture. With an initial SMT concentration of 10 mg/L, the SMT removal efficiency reached 65% at 1.0 kGy and increased to 98% at 2.5 kGy. The SMT degradation rate was lower in the sludge mixture than that in pure water. The pseudo first-order kinetic constant of SMT degradation in pure water was 2.3 times higher than that in the sludge mixture. Analysis of the SMT concentrations in the supernatant and sludge residue revealed that 93-97% of SMT was observed in the supernatant and the detected SMT in the sludge residue was 168±29, 147±4, and 87±9 μg/g dry weight following irradiation at doses of 0, 1.0 and 2.5 kGy, respectively. The sludge solubilization slowly increased from 1.5% to 3.5% with increasing dose from 1.0 to 5.0 kGy, while the sludge activity decreased by 85-98%. Addition of H2O2 exhibited a synergetic effect on the degradation of SMT, with the pseudo first-order kinetic constant k increasing by around 25%.

Influencing factors and kinetic studies of imidacloprid degradation by ozonation.

PubMed

Chen, Shi; Deng, Jing; Deng, Yang; Gao, Naiyun

2018-03-02

Batch kinetic tests in ozonation of imidacloprid from water were performed in this study. The pseudo-first-order rate constant of imidacloprid degradation was increased from 0.079 to 0.326 min -1 with the increasing pH from 6.02 to 8.64 at an average ozone dose of 1.149 mg L -1 . When the alkalinity was increased from 0 to 250 mg L -1 NaHCO 3 , the pseudo-first-order rate constants decreased from 0.121 to 0.034 min -1 . These results suggested that the predominant oxidant gradually switched from ozone to hydroxyl radicals ([Formula: see text]) with the increase in solution pH. The secondary rate constant [Formula: see text] (10.92 ± 0.12 M -1 s -1 ) for the reaction of imidacloprid and molecular ozone was determined at pH 2.0 and in the presence of 50 mM ter-butyl alcohol (p-chlorobenzoic acid, pCBA), respectively. An indirect competition method was used to determine the secondary rate constant for [Formula: see text] oxidation of imidacloprid in the presence of pCBA as the reference compound. The rate constants [Formula: see text] were estimated to range 2.65-3.79 M -1 s -1 at pH 6.02-8.64. Results obtained from this study demonstrate that ozonation appears to be an effective method to remove imidacloprid from water.

Accelerated Testing Methodology in Constant Stress-Rate Testing for Advanced Structural Ceramics: A Preloading Technique

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.; Huebert, Dean; Bartlett, Allen; Choi, Han-Ho

2001-01-01

Preloading technique was used as a means of an accelerated testing methodology in constant stress-rate ('dynamic fatigue') testing for two different brittle materials. The theory developed previously for fatigue strength as a function of preload was further verified through extensive constant stress-rate testing for glass-ceramic and CRT glass in room temperature distilled water. The preloading technique was also used in this study to identify the prevailing failure mechanisms at elevated temperatures, particularly at lower test rate in which a series of mechanisms would be associated simultaneously with material failure, resulting in significant strength increase or decrease. Two different advanced ceramics including SiC whisker-reinforced composite silicon nitride and 96 wt% alumina were used at elevated temperatures. It was found that the preloading technique can be used as an additional tool to pinpoint the dominant failure mechanism that is associated with such a phenomenon of considerable strength increase or decrease.

Accelerated Testing Methodology in Constant Stress-Rate Testing for Advanced Structural Ceramics: A Preloading Technique

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.; Huebert, Dean; Bartlett, Allen; Choi, Han-Ho

2001-01-01

Preloading technique was used as a means of an accelerated testing methodology in constant stress-rate (dynamic fatigue) testing for two different brittle materials. The theory developed previously for fatigue strength as a function of preload was further verified through extensive constant stress-rate testing for glass-ceramic and CRT glass in room temperature distilled water. The preloading technique was also used in this study to identify the prevailing failure mechanisms at elevated temperatures, particularly at lower test rates in which a series of mechanisms would be associated simultaneously with material failure, resulting in significant strength increase or decrease. Two different advanced ceramics including SiC whisker-reinforced composite silicon nitride and 96 wt% alumina were used at elevated temperatures. It was found that the preloading technique can be used as an additional tool to pinpoint the dominant failure mechanism that is associated with such a phenomenon of considerable strength increase or decrease.

Kinetic models and pathways of ronidazole degradation by chlorination, UV irradiation and UV/chlorine processes.

PubMed

Qin, Lang; Lin, Yi-Li; Xu, Bin; Hu, Chen-Yan; Tian, Fu-Xiang; Zhang, Tian-Yang; Zhu, Wen-Qian; Huang, He; Gao, Nai-Yun

2014-11-15

Degradation kinetics and pathways of ronidazole (RNZ) by chlorination (Cl2), UV irradiation and combined UV/chlorine processes were investigated in this paper. The degradation kinetics of RNZ chlorination followed a second-order behavior with the rate constants calculated as (2.13 ± 0.15) × 10(2) M(-2) s(-1), (0.82 ± 0.52) × 10(-2) M(-1) s(-1) and (2.06 ± 0.09) × 10(-1) M(-1) s(-1) for the acid-catalyzed reaction, as well as the reactions of RNZ with HOCl and OCl(-), respectively. Although UV irradiation degraded RNZ more effectively than chlorination did, very low quantum yield of RNZ at 254 nm was obtained as 1.02 × 10(-3) mol E(-1). RNZ could be efficiently degraded and mineralized in the UV/chlorine process due to the generation of hydroxyl radicals. The second-order rate constant between RNZ and hydroxyl radical was determined as (2.92 ± 0.05) × 10(9) M(-1) s(-1). The degradation intermediates of RNZ during the three processes were identified with Ultra Performance Liquid Chromatography - Electrospray Ionization - mass spectrometry and the degradation pathways were then proposed. Moreover, the variation of chloropicrin (TCNM) and chloroform (CF) formation after the three processes were further evaluated. Enhanced formation of CF and TCNM precursors during UV/chlorine process deserves extensive attention in drinking water treatment. Copyright © 2014 Elsevier Ltd. 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

Growth rate and trapping efficacy of nematode-trapping fungi under constant and fluctuating temperatures.

PubMed

Fernández, A S; Larsen, M; Wolstrup, J; Grønvold, J; Nansen, P; Bjørn, H

1999-08-01

The effect of temperature on radial growth and predatory activity of different isolates of nematode-trapping fungi was assessed. Four isolates of Duddingtonia flagrans and one isolate of Arthrobotrys oligospora were inoculated on petri dishes containing either cornmeal agar (CMA) or faecal agar and then incubated for 14 days under three different constant and fluctuating temperature regimes. The radial growth was similar on the two substrates at each temperature regime. All fungal isolates showed a higher growth rate at a constant 20 degrees C. At 10 degrees and 15 degrees C, all D. flagrans isolates showed very similar patterns of radial growth at both constant and fluctuating temperatures. At 20 degrees C, they grew significantly faster at constant than at fluctuating temperatures. A. oligospora grew significantly faster than all D. flagrans isolates except when incubated at a fluctuating 20 degrees C. Spores of each fungal isolate were added to faecal cultures containing eggs of Cooperia oncophora at a concentration of 6250 spores/g faeces. The cultures were incubated for 14 days at the same temperature regimes described above. Control faeces (without fungal material) were also cultured. More larvae were recovered from the fungus-treated cultures incubated at a constant 10 degrees or 15 degrees C than from those incubated at the respective fluctuating temperatures, except for one D. flagrans isolate. Incubation at 20 degrees C showed the opposite effect. The general reduction observed in the number of nematode larvae due to fungal trapping was 18-25% and 48-80% for a constant and fluctuating 10 degrees C, 70-96% and 93-95% for a constant and fluctuating 15 degrees C, and 63-98% and 0-25% for a constant and fluctuating 20 degrees C, respectively.

Promoting degradation of 2,4-dichlorophenoxyacetic acid with fermentative effluents from hydrogen-producing reactor.

PubMed

Yang, Zhiman; Shi, Xiaoshuang; Dai, Meng; Wang, Lin; Xu, Xiaohui; Guo, Rongbo

2018-06-01

This research aims to identifying the potential effect of using a hydrogen-producing reactor's effluent as an enrichment amendment for enhancing the degradation rates of 2,4-dichlorophenoxyacetic acid (2,4-D) during the bioremediation of contaminated paddy soils. The results showed that addition of the effluents to 2,4-D- degrading enrichment culture enhanced (up to 1.3-fold) the degradation rate constant of 2,4-D. The enhancement effect most probably resulted from the co-metabolic degradation of 2,4-D facilitated by volatile fatty acids (e.g., acetate, propionate, and butyrate) in the effluents which served as the beneficial substrates. Results from DNA sequencing analysis showed that the effluent additions shifted the bacterial community composition in the enrichment culture. Dechloromonas and Clostridium were two dominant bacterial genera involved in 2,4-D degradation. The findings will make a substantial contribution to remediation of soils contaminated with 2,4-D. Copyright © 2018 Elsevier Ltd. All rights reserved.

Radical Chemistry and Structural Relationships of PPCP Degradation by UV/Chlorine Treatment in Simulated Drinking Water.

PubMed

Guo, Kaiheng; Wu, Zihao; Shang, Chii; Yao, Bo; Hou, Shaodong; Yang, Xin; Song, Weihua; Fang, Jingyun

2017-09-19

The UV/chlorine process is an emerging advanced oxidation process (AOP) used for the degradation of micropollutants. However, the radical chemistry of this AOP is largely unknown for the degradation of numerous structurally diverse micropollutants in water matrices of varying quality. These issues were addressed by grouping 34 pharmaceuticals and personal care products (PPCPs) according to the radical chemistry of their degradation in the UV/chlorine process at practical PPCP concentrations (1 μg L -1 ) and in different water matrices. The contributions of HO • and reactive chlorine species (RCS), including Cl • , Cl 2 •- , and ClO • , to the degradation of different PPCPs were compound specific. RCS showed considerable reactivity with olefins and benzene derivatives, such as phenols, anilines, and alkyl-/alkoxybenzenes. A good linear relationship was found between the RCS reactivity and negative values of the Hammett ∑σ p + constant for aromatic PPCPs, indicating that electron-donating groups promote the attack of benzene derivatives by RCS. The contribution of HO • , but not necessarily RCS, to PPCP removal decreased with increasing pH. ClO • showed high reactivity with some PPCPs, such as carbamazepine, caffeine, and gemfibrozil, with second-order rate constants of 9.2 × 10 7 , 1.03 × 10 8 , and 4.16 × 10 8 M -1 s -1 , respectively, which contributed to their degradation. Natural organic matter (NOM) induced significant scavenging of ClO • and greatly decreased the degradation of PPCPs that was attributable to ClO • , with a second-order rate constant of 4.5 × 10 4 (mg L -1 ) -1 s -1 . Alkalinity inhibited the degradation of PPCPs that was primarily attacked by HO • and Cl • but had negligible effects on the degradation of PPCPs by ClO • . This is the first study on the reactivity of RCS, particularly ClO • , with structurally diverse PPCPs under simulated drinking water condition.

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 V.; Hammes-Schiffer, Sharon

2015-11-21

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 proton donor-acceptor vibrational modes. 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 in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. 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. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to

Effect of ultrasonic frequency on degradation of methylene blue in the presence of particle

NASA Astrophysics Data System (ADS)

Kobayashi, Daisuke; Suzuki, Atsushi; Takahashi, Tomoki; Matsumoto, Hideyuki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

2012-05-01

Techniques for the degradation of hazardous organic compounds have been investigated such as solvent extraction, incineration, chemical dehalogenation and biodegradation, etc. Ultrasound has been found to be an attractive advanced technology for the degradation of hazardous organic compounds in water. In addition, the sonochemical reaction is enhanced by particle addition. However, the enhancement mechanism of particle addition has not been investigated well, because ultrasound enhances not only chemical reaction but also mass transfer. In this study, the degradation process of methylene blue as the model hazardous organic compound by ultrasonic irradiation was investigated. The effects of ultrasonic irradiation condition on degradation rate were investigated. The effect of ultrasonic frequency on improvement of degradation reaction by particle addition was also investigated. In addition, the effects of ultrasonic frequency on ultrasonic power and chemical efficiency were investigated by calorimetry and SE value. The degradation rate constants were estimated from the results of temporal change of the concentration of methylene blue assuming first order kinetics for the decomposition. There was a linear relation in the degradation rate and the ultrasonic power. In addition, the degradation rates at 127 kHz and 490 kHz were much larger than that at 22.8 kHz. The effect of ultrasonic frequency on sonochemical efficiency has been investigated, and the sonochemical effects in the range of frequency of 200 - 500 kHz are 10 times larger than those in the lower or higher frequency regions. Therefore, the degradation rate of methylene blue was considered to estimate using sonochemical efficiency. The degradation process of methylene blue was intensified by particle addition, and the degradation rate increased with increasing amount of particle. On the other hand, the enhancement of degradation rate by particle addition was influenced by both ultrasonic frequency and species

Estimation of Anaerobic Debromination Rate Constants of PBDE Pathways Using an Anaerobic Dehalogenation Model.

PubMed

Karakas, Filiz; Imamoglu, Ipek

2017-04-01

This study aims to estimate anaerobic debromination rate constants (k m ) of PBDE pathways using previously reported laboratory soil data. k m values of pathways are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model. Debromination activities published in the literature in terms of bromine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The range of estimated k m values is between 0.0003 and 0.0241 d -1 . The median and maximum of k m values are found to be comparable to the few available biologically confirmed rate constants published in the literature. The estimated k m values can be used as input to numerical fate and transport models for a better and more detailed investigation of the fate of individual PBDEs in contaminated sediments. Various remediation scenarios such as monitored natural attenuation or bioremediation with bioaugmentation can be handled in a more quantitative manner with the help of k m estimated in this study.

Degradation of chloroacetanilide herbicides by anodic fenton treatment.

PubMed

Friedman, Carey L; Lemley, Ann T; Hay, Anthony

2006-04-05

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.

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

Modeling steady-state methanogenic degradation of phenols in groundwater

USGS Publications Warehouse

Bekins, Barbara A.; Godsy, E. Michael; Goerlitz, Donald F.

1993-01-01

Field and microcosm observations of methanogenic phenolic compound degradation indicate that Monod kinetics governs the substrate disappearance but overestimates the observed biomass. In this paper we present modeling results from an ongoing multidisciplinary study of methanogenic biodegradation of phenolic compounds in a sand and gravel aquifer contaminated by chemicals and wastes used in wood treatment. Field disappearance rates of four phenols match those determined in batch microcosm studies previously performed by E.M. Godsy and coworkers. The degradation process appears to be at steady-state because even after a sustained influx over several decades, the contaminants still are disappearing in transport downgradient. The existence of a steady-state degradation profile of each substrate together with a low biomass density in the aquifer indicate that the bacteria population is exhibiting no net growth. This may be due to the oligotrophic nature of the biomass population in which utilization and growth are approximately independent of concentration for most of the concentration range. Thus a constant growth rate should exist over much of the contaminated area which may in turn be balanced by an unusually high decay or maintenance rate due to hostile conditions or predation.

Mangroves in peril: unprecedented degradation rates of peri-urban mangroves in Kenya

NASA Astrophysics Data System (ADS)

Bosire, J. O.; Kaino, J. J.; Olagoke, A. O.; Mwihaki, L. M.; Ogendi, G. M.; Kairo, J. G.; Berger, U.; Macharia, D.

2013-10-01

Marine ecosystems are experiencing unprecedentedly high degradation rates than any other ecosystem on the planet, which in some instances are up to four times that of rainforests. Mangrove ecosystems have especially been impacted by compounded anthropogenic pressures leading to significant cover reductions of between 35 and 50% (equivalent to 1-2% loss pa) for the last half century. The main objective of this study was to test the hypothesis that peri-urban mangroves suffering from compounded and intense pressures may be experiencing higher degradation rates than the global mean (and/or national mean for Kenya) using Mombasa mangroves (comprising of Tudor and Mwache creeks) as a case study. Stratified sampling was used to sample along 22 and 10 belt transects in Mwache and Tudor respectively, set to capture stand heterogeneity in terms of species composition and structure in addition to perceived human pressure gradients using proximity to human habitations as a proxy. We acquired SPOT (HRV/ HRVIR/ HRS) imageries of April 1994, May 2000 and January 2009 and a vector mangrove map of 1992 at a scale of 1 : 50 000 for cover change and species composition analysis. Results from image classification of the 2009 image had 80.23% overall accuracy and Cohen's Kappa of 0.77, thus proving satisfactory for use in this context. Structural data indicate that complexity index (CI) which captures stand structural development was higher in Mwache at 1.80 compared to Tudor at 1.71. From cover change data, Tudor had lost 86.9% of the forest between 1992 and 2009, compared to Mwache at 45.4% representing very high hitherto undocumented degradation rates of 5.1 and 2.7% pa, respectively. These unprecedentedly high degradation rates, which far exceed not only the national mean (for Kenya of 0.7% pa) but the global mean as well, strongly suggest that these mangroves are highly threatened due to compounded pressures. Strengthening of governance regimes through enforcement and compliance

Mangroves in peril: unprecedented degradation rates of peri-urban mangroves in Kenya

NASA Astrophysics Data System (ADS)

Bosire, J. O.; Kaino, J. J.; Olagoke, A. O.; Mwihaki, L. M.; Ogendi, G. M.; Kairo, J. G.; Berger, U.; Macharia, D.

2014-05-01

Marine ecosystems are experiencing unprecedented degradation rates higher than any other ecosystem on the planet, which in some instances are up to 4 times those of rainforests. Mangrove ecosystems have especially been impacted by compounded anthropogenic pressures leading to significant cover reductions of between 35 and 50% (equivalent to 1-2% loss pa) for the last half century. The main objective of this study was to test the hypothesis that peri-urban mangroves suffering from compounded and intense pressures may be experiencing higher degradation rates than the global mean (and/or national mean for Kenya) using Mombasa mangroves (comprising Tudor and Mwache creeks) as a case study. Stratified sampling was used to sample along 22 and 10 belt transects in Mwache and Tudor respectively, set to capture stand heterogeneity in terms of species composition and structure in addition to perceived human pressure gradients using proximity to human habitations as a proxy. We acquired SPOT (HRV/ HRVIR/ HRS) images of April 1994, May 2000 and January 2009 and a vector mangrove map of 1992 at a scale of 1:50 000 for cover change and species composition analysis. Results from image classification of the 2009 image had 80.23% overall accuracy and Cohen's kappa of 0.77, thus proving satisfactory for use in this context. Structural data indicate that complexity index (CI) which captures stand structural development was higher in Mwache at 1.80 compared to Tudor at 1.71. From cover change data, Tudor lost 86.9% of the forest between 1992 and 2009, compared to Mwache at 45.4%, representing very high hitherto undocumented degradation rates of 5.1 and 2.7% pa, respectively. These unprecedentedly high degradation rates, which far exceed not only the national mean (for Kenya of 0.7% pa) but the global mean as well, strongly suggest that these mangroves are highly threatened due to compounded pressures. Strengthening of governance regimes through enforcement and compliance to halt

Study on the aerobic biodegradability and degradation kinetics of 3-NP; 2,4-DNP and 2,6-DNP.

PubMed

She, Zonglian; Xie, Tian; Zhu, Yingjie; Li, Leilei; Tang, Gaifeng; Huang, Jian

2012-11-30

Four biodegradability tests (BOD(5)/COD ratio, production of carbon dioxide, relative oxygen uptake rate and relative enzymatic activity) were used to determine the aerobic biodegradability of 3-nitrophenol (3-NP), 2,4-dinitrophenol (2,4-DNP) and 2,6-dinitrophenol (2,6-DNP). Furthermore, biodegradation kinetics of the compounds was investigated in sequencing batch reactors both in the presence of glucose (co-substrate) and with nitrophenol as the sole carbon source. Among the three tested compounds, 3-NP showed the best biodegradability while 2,6-DNP was the most difficult to be biodegraded. The Haldane equation was applied to the kinetic test data of the nitrophenols. The kinetic constants are as follows: the maximum specific degradation rate (K(max)), the saturation constants (K(S)) and the inhibition constants (K(I)) were in the range of 0.005-2.98 mg(mgSS d)(-1), 1.5-51.9 mg L(-1) and 1.8-95.8 mg L(-1), respectively. The presence of glucose enhanced the degradation of the nitrophenols at low glucose concentrations. The degradation of 3-NP was found to be accelerated with the increasing of glucose concentrations from 0 to 660 mg L(-1). At high (1320-2000 mg L(-1)) glucose concentrations, the degradation rate of 3-NP was reduced and the K(max) of 3-NP was even lower than the value obtained in the absence of glucose, suggesting that high concentrations of co-substrate could inhibit 3-NP biodegradation. At 2,4-DNP concentration of 30 mg L(-1), the K(max) of 2,4-DNP with glucose as co-substrate was about 30 times the value with 2,4-DNP as sole substrate. 2,6-DNP preformed high toxicity in the case of sole carbon source degradation and the kinetic data was hardly obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Degradation kinetics of gamma-oryzanol in antioxidant-stripped rice bran oil during thermal oxidation.

PubMed

Khuwijitjaru, Pramote; Yuenyong, Thippawan; Pongsawatmanit, Rungnaphar; Adachi, Shuji

2009-01-01

Gamma-oryzanol, a group of phytosterol ferulates found in rice bran, possesses antioxidative activity and other bioactivities. The kinetics of thermal degradation of gamma-oryzanol in stripped rice bran oil (SRBO) were investigated under heating at 132, 160, 192 and 222 degrees C for 480, 140, 60 and 50 h, respectively. Losses of the overall gamma-oryzanol and its components (cycloartenyl ferulate, 24-methylene cycloartanyl ferulate, campesteryl ferulate and beta-sitosteryl ferulate) could be expressed by the first-order kinetics model. The rate constant of thermal degradation of gamma-oryzanol increased with increasing heating temperatures. The temperature dependence of the obtained rate constants was found to obey the Arrhenius equation. Campesteryl ferulate showed slightly more thermally resistant than other components at temperature lower than 160 degrees C. However, the change in the absorbance from 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay as a function of heating time exhibited the same pattern for the SRBO with and without gamma-oryzanol for all studied heating temperatures.

New Solar PV Tool Accurately Calculates Degradation Rates, Saving Money and

Science.gov Websites

Guiding Business Decisions | News | NREL New Solar PV Tool Accurately Calculates Degradation Rates, Saving Money and Guiding Business Decisions News Release: New Solar PV Tool Accurately Calculates ; said Dirk Jordan, engineer and solar PV researcher at NREL. "We spent years building consensus in

Chromatographic determination of itopride hydrochloride in the presence of its degradation products.

PubMed

Kaul, Neeraj; Agrawal, Himani; Maske, Pravin; Rao, Janhavi Ramchandra; Mahadik, Kakasaheb Ramoo; Kadam, Shivajirao S

2005-08-01

Two sensitive and reproducible methods are described for the quantitative determination of itopride hydrochloride (IH) in the presence of its degradation products. The first method is based on HPLC separation on a reversed phase Kromasil column [C18 (5-microm, 25 cm x 4.6 mm, ID)] at ambient temperature using a mobile phase consisting of methanol and water (70:30, v/v) adjusted to pH 4.0 with orthophosphoric acid with UV detection at 258 nm. The flow rate was 1.0 mL per min with an average operating pressure of 180 kg/cm2. The second method is based on HPTLC separation on silica gel 60 F254 using toluene:methanol:chloroform:10% ammonia (5.0:3.0:6.0:0.1, v/v/v/v) as mobile phase at 270 nm. The analysis of variance (ANOVA) and Student's t-test were applied to correlate the results of IH determination in dosage form by means of HPLC and HPTLC methods. The drug was subjected to acid and alkali hydrolysis, oxidation, dry heat, wet heat treatment, UV, and photodegradation. The proposed HPLC method was utilized to investigate the kinetics of the acidic, alkaline, and oxidative degradation processes at different temperatures and the apparent pseudo-first-order rate constant, half-life, and activation energy were calculated. In addition the pH-rate profile of degradation of IH in constant ionic strength buffer solutions in the pH range 2-11 was studied.

Theoretical Discussion of Electron Transport Rate Constant at TCNQ / Ge and TiO2 System

NASA Astrophysics Data System (ADS)

Al-agealy, Hadi J. M.; Alshafaay, B.; Hassooni, Mohsin A.; Ashwiekh, Ahmed M.; Sadoon, Abbas K.; Majeed, Raad H.; Ghadhban, Rawnaq Q.; Mahdi, Shatha H.

2018-05-01

We have been studying and estimation the electronic transport constant at TCNQ / Ge and Tio2 interface by means of tunneling potential (TP), transport energy reorientation (TER), driving transition energy DTE and coupling coefficient constant. A simple quantum model for the transition processes was adapted to estimation and analysis depending on the quantum state for donor state |α D > and acceptor stated |α A > and assuming continuum levels of the system. Evaluation results were performed for the surfaces of Ge and Tio2 as best as for multilayer TCNQ. The results show an electronic transfer feature for electronic TCNQ density of states and a semiconductor behavior. The electronic rate constant result for both systems shows a good tool to election system in applied devices. All these results indicate the

Comparative Thermal Degradation Patterns of Natural Yellow Colorants Used in Foods.

PubMed

Giménez, Pedro J; Fernández-López, José A; Angosto, José M; Obón, José M

2015-12-01

There is a great interest in natural yellow colorants due to warnings issued about certain yellow food colorings of synthetic origin. However, no comparative studies have been reported of their thermal stability. For this reason, the thermal stabilities of six natural yellow colorants used in foods--lutein, riboflavin, curcumin, ß-carotene, gardenia yellow and Opuntia betaxanthins--were studied in simple solutions over a temperature range 30-90 °C. Spectral properties and visual color were investigated during 6 h of heat treatment. Visual color was monitored from the CIEL*a*b* parameters. The remaining absorbance at maximum wavelength and the total color difference were used to quantify color degradation. The rate of color degradation increased as the temperature rose. The results showed that the thermal degradation of the colorants followed a first-order reaction kinetics. The reaction rate constants and half-life periods were determined as being central to understanding the color degradation kinetics. The temperature-dependent degradation was adequately modeled on the Arrhenius equation. Activation energies ranged from 3.2 kJmol(-1) (lutein) to 43.7 kJmol(-1) (Opuntia betaxanthins). ß-carotene and lutein exhibited high thermal stability, while betaxanthins and riboflavin degraded rapidly as temperature increased. Gardenia yellow and curcumin were in an intermediate position.

Dose rate effects on array CCDs exposed by Co-60 γ rays induce saturation output degradation and annealing tests

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

Wang, Zujun, E-mail: wangzujun@nint.ac.cn; Chen, Wei; He, Baoping

The experimental tests of dose rate and annealing effects on array charge-coupled devices (CCDs) are presented. The saturation output voltage (V{sub S}) versus the total dose at the dose rates of 0.01, 0.1, 1.0, 10.0 and 50 rad(Si)/s are compared. Annealing tests are performed to eliminate the time-dependent effects. The V{sub S} degradation levels depend on the dose rates. The V{sub S} degradation mechanism induced by dose rate and annealing effects is analyzed. The V{sub S} at 20 krad(Si) with the dose rate of 0.03 rad(Si)/s are supplemented to assure the degradation curves between the dose rates of 0.1 andmore » 0.01 rad(Si)/s. The CCDs are divided into two groups, with one group biased and the other unbiased during {sup 60}Co γ radiation. The V{sub S} degradation levels of the biased CCDs during radiation are more severe than that of the unbiased CCDs.« less

Reaction rate constants and mean population percentage for nitrifiers in an alternating oxidation ditch system.

PubMed

Mantziaras, I D; Katsiri, A

2011-01-01

This paper presents a methodology for the determination of reaction rate constants for nitrifying bacteria and their mean population percentage in biomass in an alternating oxidation ditch system. The method used is based on the growth rate equations of the ASM1 model (IWA) (Henze et al. in Activated sludge models ASM1, ASM2, ASM2d, and ASM3. IWA Scientific and Technical Report no. 9, IWA Publishing, London, UK, 2000) and the application of mass balance equations for nitrifiers and ammonium nitrogen in an operational cycle of the ditch system. The system consists of two ditches operating in four phases. Data from a large-scale oxidation ditch pilot plant with a total volume of 120 m(3) within an experimental period of 8 months was used. Maximum specific growth rate for autotrophs (μ(A)) and the half-saturation constant for ammonium nitrogen (K(NH)) were found to be 0.36 day(-1) and 0.65 mgNH(4)-N/l, respectively. Additionally, the average population percentage of the nitrifiers in the biomass was estimated to be around 3%.

Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment.

PubMed

Liu, Chao; Qiang, Zhimin; Adams, Craig; Tian, Fang; Zhang, Tao

2009-08-01

The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ x mol(-1). At pH 7.0 and 25 degrees C, the rate constant was 25.2+/-0.4M(-1)s(-1). Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for <5% and >or=95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 microg L(-1)), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 microg L(-1)). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.

Impact of humic acid on the degradation of levofloxacin by aqueous permanganate: Kinetics and mechanism.

PubMed

Xu, Ke; Ben, Weiwei; Ling, Wencui; Zhang, Yu; Qu, Jiuhui; Qiang, Zhimin

2017-10-15

Levofloxacin (LF) is a frequently detected fluoroquinolone in surface water, and permanganate (MnO 4 - ) is a commonly used oxidant in drinking water treatment. This study investigated the impact of humic acid (HA) on LF degradation by aqueous MnO 4 - from both kinetic and mechanistic aspects. In the absence of HA, the second-order rate constant (k) of LF degradation by MnO 4 - was determined to be 3.9 M -1  s -1 at pH 7.5, which increased with decreasing pH. In the presence of HA, the pseudo-first-order rate constant (k obs ) of LF degradation at pH 7.5 was significantly increased by 3.8- and 2.8-fold at [HA] o :[KMnO 4 ] o (mass ratio) = 0.5 and 1, respectively. Secondary oxidant scavenging and electron paramagnetic resonance tests indicated that HA could form a complex with Mn(III), a strongly oxidative intermediate produced in the reaction of MnO 4 - with HA, to induce the successive formation of superoxide radicals (O 2 - ) and hydroxyl radicals (OH). The resulting OH primarily contributed to the accelerated LF degradation, and the complex [HA-Mn(III)] could account for the rest of acceleration. The degradation of LF and its byproducts during MnO 4 - oxidation was mainly through hydroxylation, dehydrogenation and carboxylation, and the presence of HA led to a stronger destruction of LF. This study helps better understand the degradation of organic micropollutants by MnO 4 - in drinking water treatment. Copyright © 2017 Elsevier Ltd. 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.

Theory for rates, equilibrium constants, and Brønsted slopes in F1-ATPase single molecule imaging experiments

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2015-01-01

A theoretical model of elastically coupled reactions is proposed for single molecule imaging and rotor manipulation experiments on F1-ATPase. Stalling experiments are considered in which rates of individual ligand binding, ligand release, and chemical reaction steps have an exponential dependence on rotor angle. These data are treated in terms of the effect of thermodynamic driving forces on reaction rates, and lead to equations relating rate constants and free energies to the stalling angle. These relations, in turn, are modeled using a formalism originally developed to treat electron and other transfer reactions. During stalling the free energy profile of the enzymatic steps is altered by a work term due to elastic structural twisting. Using biochemical and single molecule data, the dependence of the rate constant and equilibrium constant on the stall angle, as well as the Børnsted slope are predicted and compared with experiment. Reasonable agreement is found with stalling experiments for ATP and GTP binding. The model can be applied to other torque-generating steps of reversible ligand binding, such as ADP and Pi release, when sufficient data become available. PMID:26483483

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

The use of microcalorimetry and HPLC for the determination of degradation kinetics and thermodynamic parameters of Perindopril Erbumine in aqueous solutions.

PubMed

Simoncic, Z; Roskar, R; Gartner, A; Kogej, K; Kmetec, V

2008-05-22

Perindopril Erbumine (PER) is one of the newly used angiotensin-converting enzyme inhibitors (ACE inhibitors) and is used for the treatment of patients with hypertension and symptomatic heart failure. It has two main degradation pathways, i.e. the degradation by hydrolysis and the degradation by cyclization. An isothermal heat conduction microcalorimetry (MC) and high pressure liquid chromatography (HPLC) were used for the characterization of aqueous solutions of PER and its stability properties. The rates of heat evolved during degradation of perindopril were measured by MC as a function of temperature and pH and from these data rate constant and change in enthalpy of the reactions were determined. With the HPLC method the concentration of perindopril and its degradation products were measured as a function of time in aqueous solutions of different pH that were stored at different temperatures. We demonstrated that reactions of degradation of perindopril at observed conditions follow the first order kinetics. The Arrhenius equation for each pH was determined. At pH 6.8 only one degradation pathway is present, i.e. the degradation by hydrolysis. Degradation constants for this pathway calculated from MC data are in good agreement with those obtained from HPLC. MC as a non-specific technique was shown to be useful in studies of PER when one reaction was present in the sample and also when more chemical and physical processes were simultaneously running.

Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

PubMed

Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

2016-02-01

The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

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…

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.

Modeling of thermal degradation kinetics of the C-glucosyl xanthone mangiferin in an aqueous model solution as a function of pH and temperature and protective effect of honeybush extract matrix.

PubMed

Beelders, Theresa; de Beer, Dalene; Kidd, Martin; Joubert, Elizabeth

2018-01-01

Mangiferin, a C-glucosyl xanthone, abundant in mango and honeybush, is increasingly targeted for its bioactive properties and thus to enhance functional properties of food. The thermal degradation kinetics of mangiferin at pH3, 4, 5, 6 and 7 were each modeled at five temperatures ranging between 60 and 140°C. First-order reaction models were fitted to the data using non-linear regression to determine the reaction rate constant at each pH-temperature combination. The reaction rate constant increased with increasing temperature and pH. Comparison of the reaction rate constants at 100°C revealed an exponential relationship between the reaction rate constant and pH. The data for each pH were also modeled with the Arrhenius equation using non-linear and linear regression to determine the activation energy and pre-exponential factor. Activation energies decreased slightly with increasing pH. Finally, a multi-linear model taking into account both temperature and pH was developed for mangiferin degradation. Sterilization (121°C for 4min) of honeybush extracts dissolved at pH4, 5 and 7 did not cause noticeable degradation of mangiferin, although the multi-linear model predicted 34% degradation at pH7. The extract matrix is postulated to exert a protective effect as changes in potential precursor content could not fully explain the stability of mangiferin. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spatial Moment Equations for a Groundwater Plume with Degradation and Rate-Limited Sorption

EPA Science Inventory

In this note, we analytically derive the solution for the spatial moments of groundwater solute concentration distributions simulated by a one-dimensional model that assumes advective-dispersive transport with first-order degradation and rate-limited sorption. Sorption kinetics...

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

PubMed

Zhai, Zihan; Yang, Ting; Zhang, Boya; Zhang, Jianbo

2015-07-01

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment. Copyright © 2015. Published by Elsevier B.V.

DNA Profiling Success Rates from Degraded Skeletal Remains in Guatemala.

PubMed

Johnston, Emma; Stephenson, Mishel

2016-07-01

No data are available regarding the success of DNA Short Tandem Repeat (STR) profiling from degraded skeletal remains in Guatemala. Therefore, DNA profiling success rates relating to 2595 skeletons from eleven cases at the Forensic Anthropology Foundation of Guatemala (FAFG) are presented. The typical postmortem interval was 30 years. DNA was extracted from bone powder and amplified using Identifiler and Minifler. DNA profiling success rates differed between cases, ranging from 50.8% to 7.0%, the overall success rate for samples was 36.3%. The best DNA profiling success rates were obtained from femur (36.2%) and tooth (33.7%) samples. DNA profiles were significantly better from lower body bones than upper body bones (p = <0.0001). Bone samples from males gave significantly better profiles than samples from females (p = <0.0001). These results are believed to be related to bone density. The findings are important for designing forensic DNA sampling strategies in future victim recovery investigations. © 2016 American Academy of Forensic Sciences.

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 and Reaction Coordinate of Trp-Cage Folding in Explicit Water

PubMed Central

Juraszek, Jarek; Bolhuis, Peter G.

2008-01-01

We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the protein maintains its compact configuration, while a (de)increase of secondary structure is observed. The calculated folding rate agrees reasonably with experiment, while the unfolding rate is 10 times higher. We discuss possible origins for this mismatch. We recomputed the rates with the forward flux sampling method, and found a discrepancy of four orders of magnitude, probably caused by the method's higher sensitivity to the choice of order parameter with respect to transition interface sampling. Finally, we used the previously computed transition path-sampling ensemble to screen combinations of many order parameters for the best model of the reaction coordinate by employing likelihood maximization. We found that a combination of the root mean-square deviation of the helix and of the entire protein was, of the set of tried order parameters, the one that best describes the reaction coordination. PMID:18676648

Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene

DOE PAGES

Lane, J. Matthew; Moore, Nathan W.

2018-02-01

Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less

Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene

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

Lane, J. Matthew; Moore, Nathan W.

Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less

Derivative spectrophotometry for the determination of faropenem in the presence of degradation products: an application for kinetic studies.

PubMed

Cielecka-Piontek, Judyta

2013-07-01

A simple and selective derivative spectrophotometric method was developed for the quantitative determination of faropenem in pure form and in pharmaceutical dosage. The method is based on the zero-crossing effect of first-derivative spectrophotometry (λ = 324 nm), which eliminates the overlapping effect caused by the excipients present in the pharmaceutical preparation, as well as degradation products, formed during hydrolysis, oxidation, photolysis, and thermolysis. The method was linear in the concentration range 2.5-300 μg/mL (r = 0.9989) at λ = 341 nm; the limits of detection and quantitation were 0.16 and 0.46 μg/mL, respectively. The method had good precision (relative standard deviation from 0.68 to 2.13%). Recovery of faropenem ranged from 97.9 to 101.3%. The first-order rate constants of the degradation of faropenem in pure form and in pharmaceutical dosage were determined by using first-derivative spectrophotometry. A statistical comparison of the validation results and the observed rate constants for faropenem degradation with these obtained with the high-performance liquid chromatography method demonstrated that both were compatible.

Encapsulation of alpha-amylase into starch-based biomaterials: an enzymatic approach to tailor their degradation rate.

PubMed

Azevedo, Helena S; Reis, Rui L

2009-10-01

This paper reports the effect of alpha-amylase encapsulation on the degradation rate of a starch-based biomaterial. The encapsulation method consisted in mixing a thermostable alpha-amylase with a blend of corn starch and polycaprolactone (SPCL), which were processed by compression moulding to produce circular disks. The presence of water was avoided to keep the water activity low and consequently to minimize the enzyme activity during the encapsulation process. No degradation of the starch matrix occurred during processing and storage (the encapsulated enzyme remained inactive due to the absence of water), since no significant amount of reducing sugars was detected in solution. After the encapsulation process, the released enzyme activity from the SPCL disks after 28days was found to be 40% comparatively to the free enzyme (unprocessed). Degradation studies on SPCL disks, with alpha-amylase encapsulated or free in solution, showed no significant differences on the degradation behaviour between both conditions. This indicates that alpha-amylase enzyme was successfully encapsulated with almost full retention of its enzymatic activity and the encapsulation of alpha-amylase clearly accelerates the degradation rate of the SPCL disks, when compared with the enzyme-free disks. The results obtained in this work show that degradation kinetics of the starch polymer can be controlled by the amount of encapsulated alpha-amylase into the matrix.

Degradation of anionic surfactants during drying of UASBR sludges on sand drying beds.

PubMed

Mungray, Arvind Kumar; Kumar, Pradeep

2008-09-01

Anionic surfactant (AS) concentrations in wet up-flow anaerobic sludge blanket reactor (UASBR) sludges from five sewage treatment plants (STPs) were found to range from 4480 to 9,233 mg kg(-1)dry wt. (average 7,347 mg kg(-1)dry wt.) over a period of 18 months. After drying on sand drying beds (SDBs), AS in dried-stabilized sludges averaged 1,452 mg kg(-1)dry wt., a reduction of around 80%. The kinetics of drying followed simple first-order reduction of moisture with value of drying constant (k(d))=0.051 d(-1). Reduction of AS also followed first-order kinetics. AS degradation rate constant (k(AS)) was found to be 0.034 d(-1) and half-life of AS as 20 days. The order of rates of removal observed was k(d)>k(AS)>k(COD)>k(OM) (drying >AS degradation>COD reduction>organic matter reduction). For the three applications of dried-stabilized sludges (soil, agricultural soil, grassland), values of risk quotient (RQ) were found to be <1, indicating no risk.

Scaling of Polymer Degradation Rate within a High-Reynolds-Number Turbulent Boundary Layer

NASA Astrophysics Data System (ADS)

Elbing, Brian; Solomon, Michael; Perlin, Marc; Dowling, David; Ceccio, Steven

2009-11-01

An experiment conducted at the U.S. Navy's Large Cavitation Channel on a 12.9 m long flat-plate test model produced the first quantitative measurements of polymer molecular weight within a turbulent boundary layer. Testing was conducted at speeds to 20 m/s and downstream distance based Reynolds numbers to 220 million. These results showed that the rate of polymer degradation by scission of the polymer chains increases with increased speed, downstream distance and surface roughness. With the surface fully rough at 20 m/s there was no measureable level of drag reduction at the first measurement location (0.56 m downstream of injection). These results are scaled with the assumption that the rate of degradation is dependent on the polymer residence time in the flow and the local shear rate. A successful collapse of the data within the measurement uncertainty was achieved over a range of flow speed (6.6 to 20 m/s), surface roughness (smooth and fully rough) and downstream distance from injection (0.56 to 9.28 m).

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

PubMed

Karakas, Filiz; Imamoglu, Ipek

2017-02-15

This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

An optimal policy for deteriorating items with time-proportional deterioration rate and constant and time-dependent linear demand rate

NASA Astrophysics Data System (ADS)

Singh, Trailokyanath; Mishra, Pandit Jagatananda; Pattanayak, Hadibandhu

2017-12-01

In this paper, an economic order quantity (EOQ) inventory model for a deteriorating item is developed with the following characteristics: (i) The demand rate is deterministic and two-staged, i.e., it is constant in first part of the cycle and linear function of time in the second part. (ii) Deterioration rate is time-proportional. (iii) Shortages are not allowed to occur. The optimal cycle time and the optimal order quantity have been derived by minimizing the total average cost. A simple solution procedure is provided to illustrate the proposed model. The article concludes with a numerical example and sensitivity analysis of various parameters as illustrations of the theoretical results.

(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

Effect of dairy manure rate and the stabilization time of amended soils on atrazine degradation.

PubMed

Aguilera, Paula; Briceño, Gabriela; Candia, Maribel; Mora, Maria de la Luz; Demanet, Rolando; Palma, Graciela

2009-10-01

The application rate of liquid cow manure (LCM) in the field and the stabilization time of amended soils before application of pre-plant herbicides are factors that determine their efficiency. This study includes evaluation of residual atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) in soil and amended soils with equivalent rate of 100,000; 200,000; and 300,000 L ha(-1) of LCM and the effect of pre-incubation time of amended soils on atrazine degradation. The study was carried out under controlled conditions using an Andisol with previous historical application of atrazine. The respiratory activity and fluorescein diacetate (FDA) studies indicated that the time necessary for stabilization of amended soils is over 20-30 d. During the measurement of respiratory and FDA activity, no significant differences were observed when atrazine was applied. The half-life of atrazine ranged from 5 to 8d and the relative distribution of degradation products seem to be affected by the application of LCM. The pre-incubation time of amended soil and LCM dose would not affect atrazine degradation rate, when the soil has a history of herbicide application. However, repeated applications of LCM in a long period of time could change the soil pH and increase the content of dissolved organic carbon (DOC) which could further contribute to a faster degradation of atrazine. Both effects would reduce the effectiveness of atrazine in weed control.

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.

Inverse method to estimate kinetic degradation parameters of grape anthocyanins in wheat flour under simultaneously changing temperature and moisture.

PubMed

Lai, K P K; Dolan, K D; Ng, P K W

2009-06-01

Thermal and moisture effects on grape anthocyanin degradation were investigated using solid media to simulate processing at temperatures above 100 degrees C. Grape pomace (anthocyanin source) mixed with wheat pastry flour (1: 3, w/w dry basis) was used in both isothermal and nonisothermal experiments by heating the same mixture at 43% (db) initial moisture in steel cells in an oil bath at 80, 105, and 145 degrees C. To determine the effect of moisture on anthocyanin degradation, the grape pomace-wheat flour mixture was heated isothermally at 80 degrees C at constant moisture contents of 10%, 20%, and 43% (db). Anthocyanin degradation followed a pseudo first-order reaction with moisture. Anthocyanins degraded more rapidly with increasing temperature and moisture. The effects of temperature and moisture on the rate constant were modeled according to the Arrhenius and an exponential relationship, respectively. The nonisothermal reaction rate constant and activation energy (mean +/- standard error) were k(80 degrees C, 43% (db) moisture) = 2.81 x 10(-4)+/- 1.1 x 10(-6) s(-1) and DeltaE = 75273 +/- 197 J/g mol, respectively. The moisture parameter for the exponential model was 4.28 (dry basis moisture content)(-1). One possible application of this study is as a tool to predict the loss of anthocyanins in nutraceutical products containing grape pomace. For example, if the process temperature history and moisture history in an extruded snack fortified with grape pomace is known, the percentage anthocyanin loss can be predicted.

Effect of geochemical properties on degradation of trichloroethylene by stabilized zerovalent iron nanoparticle with Na-acrylic copolymer.

PubMed

Chen, Meng-yi; Su, Yuh-fan; Shih, Yang-hsin

2014-11-01

Stable nanoscale zero-valent iron (NZVI) particles have been developed to remediate chlorinated compounds. The degradation kinetics and efficiency of trichloroethylene (TCE) by a commercial stabilized NZVI with Na-acrylic copolymer (acNZVI) were investigated and compared with those by laboratory-synthesized NZVI and carboxymethyl cellulose (CMC)-stabilized NZVI particles. Results show that the degradation of TCE by acNZVI was faster than that by NZVI and CMC-NZVI. Increase in temperature enhanced the degradation rate and efficiency of TCE with acNZVI. The activation energy of TCE degradation by acNZVI was estimated to be 23 kJ/mol. The degradation rate constants of TCE decreased from 0.064 to 0.026 min(-1) with decrease in initial pH from 9.03 to 4.23. Common groundwater anions including NO3(-), Cl(-), HCO3(-), and SO4(2-) inhibited slightly the degradation efficiencies of TCE by acNZVI. The Na-acrylic copolymer-stabilized NZVI, which exhibited high degradation kinetics and efficiency, could be a good remediation agent for chlorinated organic compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Investigation into adsorption and photocatalytic degradation of gaseous benzene in an annular fluidized bed photocatalytic reactor.

PubMed

Geng, Qijin; Tang, Shankang; Wang, Lintong; Zhang, Yunchen

2015-01-01

The adsorption and photocatalytic degradation of gaseous benzene were investigated considering the operating variables and kinetic mechanism using nano-titania agglomerates in an annular fluidized bed photocatalytic reactor (AFBPR) designed. The special adsorption equilibrium constant, adsorption active sites, and apparent reaction rate coefficient of benzene were determined by linear regression analysis at various gas velocities and relative humidities (RH). Based on a series of photocatalytic degradation kinetic equations, the influences of operating variables on degradation efficiency, apparent reaction rate coefficient and half-life were explored. The findings indicated that the operating variables have obviously influenced the adsorption/photocatalytic degradation and corresponding kinetic parameters. In the photocatalytic degradation process, the relationship between photocatalytic degradation efficiency and RH indicated that water molecules have a dual-function which was related to the structure characteristics of benzene. The optimal operating conditions for photocatalytic degradation of gaseous benzene in AFBPR were determined as the fluidization number at 1.9 and RH required related to benzene concentration. This investigation highlights the importance of controlling RH and benzene concentration in order to obtain the desired synergy effect in photocatalytic degradation processes.

USE OF ROUGH SETS AND SPECTRAL DATA FOR BUILDING PREDICTIVE MODELS OF REACTION RATE CONSTANTS

EPA Science Inventory

A model for predicting the log of the rate constants for alkaline hydrolysis of organic esters has been developed with the use of gas-phase min-infrared library spectra and a rule-building software system based on the mathematical theory of rough sets. A diverse set of 41 esters ...

Evaluation and comparison of diffusion MR methods for measuring apparent transcytolemmal water exchange rate constant

NASA Astrophysics Data System (ADS)

Tian, Xin; Li, Hua; Jiang, Xiaoyu; Xie, Jingping; Gore, John C.; Xu, Junzhong

2017-02-01

Two diffusion-based approaches, CG (constant gradient) and FEXI (filtered exchange imaging) methods, have been previously proposed for measuring transcytolemmal water exchange rate constant kin, but their accuracy and feasibility have not been comprehensively evaluated and compared. In this work, both computer simulations and cell experiments in vitro were performed to evaluate these two methods. Simulations were done with different cell diameters (5, 10, 20 μm), a broad range of kin values (0.02-30 s-1) and different SNR's, and simulated kin's were directly compared with the ground truth values. Human leukemia K562 cells were cultured and treated with saponin to selectively change cell transmembrane permeability. The agreement between measured kin's of both methods was also evaluated. The results suggest that, without noise, the CG method provides reasonably accurate estimation of kin especially when it is smaller than 10 s-1, which is in the typical physiological range of many biological tissues. However, although the FEXI method overestimates kin even with corrections for the effects of extracellular water fraction, it provides reasonable estimates with practical SNR's and more importantly, the fitted apparent exchange rate AXR showed approximately linear dependence on the ground truth kin. In conclusion, either CG or FEXI method provides a sensitive means to characterize the variations in transcytolemmal water exchange rate constant kin, although the accuracy and specificity is usually compromised. The non-imaging CG method provides more accurate estimation of kin, but limited to large volume-of-interest. Although the accuracy of FEXI is compromised with extracellular volume fraction, it is capable of spatially mapping kin in practice.

Slow Crack Growth Analysis of Brittle Materials with Finite Thickness Subjected to Constant Stress-Rate Flexural Loading

NASA Technical Reports Server (NTRS)

Chio, S. R.; Gyekenyesi, J. P.

1999-01-01

A two-dimensional, numerical analysis of slow crack growth (SCG) was performed for brittle materials with finite thickness subjected to constant stress-rate ("dynamic fatigue") loading in flexure. The numerical solution showed that the conventional, simple, one-dimensional analytical solution can be used with a maximum error of about 5% in determining the SCG parameters of a brittle material with the conditions of a normalized thickness (a ratio of specimen thickness to initial crack size) T > 3.3 and of a SCG parameter n > 10. The change in crack shape from semicircular to elliptical configurations was significant particularly at both low stress rate and low T, attributed to predominant difference in stress intensity factor along the crack front. The numerical solution of SCG parameters was supported within the experimental range by the data obtained from constant stress-rate flexural testing for soda-lime glass microslides at ambient temperature.

Research of Isolation and Degradation Conditions of Petroleum Degrading Marine

NASA Astrophysics Data System (ADS)

Fangrui, Guo

2017-01-01

A novel petroleum-degrading microbial strain was isolated from sediment samples in estuary of Bohai Sea estuary beaches. The strain was primarily identified as Alcanivorax sp. and named Alcanivorax sp. H34. Effect of PH values, temperature, nitrogen and phosphorus concentrations on degradation of H34 were investigated. The paraffinic components average degradation rate of H34 ungrowth cells under optimized conditions was studied. The results showed that the optimal growth conditions of H34 are were temperature of 30°C, initial PH of 7.0, nitrogen concentration of 3g/L, phosphorus concentration of 3g/L, and paraffinic components average degradation rates of H34 ungrowth cells was 41.6%, while total degradation rate was 45.5%.

Bacterial secondary production on vascular plant detritus: relationships to detritus composition and degradation rate.

PubMed Central

Moran, M A; Hodson, R E

1989-01-01

Bacterial production at the expense of vascular plant detritus was measured for three emergent plant species (Juncus effusus, Panicum hemitomon, and Typha latifolia) degrading in the littoral zone of a thermally impacted lake. Bacterial secondary production, measured as tritiated thymidine incorporation into DNA, ranged from 0.01 to 0.81 microgram of bacterial C mg of detritus-1 day-1. The three plant species differed with respect to the amount of bacterial productivity they supported per milligram of detritus, in accordance with the predicted biodegradability of the plant material based on initial nitrogen content, lignin content, and C/N ratio. Bacterial production also varied throughout the 22 weeks of in situ decomposition and was positively related to the nitrogen content and lignin content of the remaining detritus, as well as to the temperature of the lake water. Over time, production was negatively related to the C/N ratio and cellulose content of the degrading plant material. Bacterial production on degrading plant material was also calculated on the basis of plant surface area and ranged from 0.17 to 1.98 micrograms of bacterial C cm-2 day-1. Surface area-based calculations did not correlate well with either initial plant composition or changing composition of the remaining detritus during decomposition. The rate of bacterial detritus degradation, calculated from measured production of surface-attached bacteria, was much lower than the actual rate of weight loss of plant material. This discrepancy may be attributable to the importance of nonbacterial organisms in the degradation and loss of plant material from litterbags or to the microbially mediated solubilization of particulate material prior to bacterial utilization, or both. PMID:2802603

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

Degradation of alkylphenol ethoxylate surfactants in water with ultrasonic irradiation

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

Destaillats, H.; Hung, H.M.; Hoffmann, M.R.

2000-01-15

During the last years, many efforts have been devoted to the elimination of alkylphenol ethoxylate surfactants from aqueous systems. In this paper, the sonochemical degradation of aqueous solutions of Triton X-100 was performed at an ultrasonic frequency of 358 kHz and an applied power of 50 W. Analysis of the reaction products by HPLC-ES-MS suggests that the hydrophobic alkyl chain is the preferential site for oxidation. Alkylphenol, or short-chain ethoxylated phenols, were not generated as byproducts. To verify this hypothesis, the sonochemical degradation of the corresponding alkylphenols (e.g., tertoctylphenol) was performed under the same conditions; in these cases, similar ratemore » constants and products were observed. These results differ from those reported for the biodegradation of alkylphenol ethoxylates. A substantial increase in the rate constant was observed for the degradation of Triton X-100 below its critical micelle concentration. This observation indicates that micelle formation serves to effectively isolate the free surfactant monomers from the water-air interface of the oscillating cavitation bubbles, thus decreasing the overall efficiency of the sonochemical process. The hydrophobic tail of the molecule is no longer exposed directly to the bubble hot spot when it is pointed into the core of the micelles.« less

Batch growth kinetic studies of locally isolated cyanide-degrading Serratia marcescens strain AQ07.

PubMed

Karamba, Kabiru Ibrahim; Ahmad, Siti Aqlima; Zulkharnain, Azham; Yasid, Nur Adeela; Ibrahim, Salihu; Shukor, Mohd Yunus

2018-01-01

The evaluation of degradation and growth kinetics of Serratia marcescens strain AQ07 was carried out using three half-order models at all the initial concentrations of cyanide with the values of regression exceeding 0.97. The presence of varying cyanide concentrations reveals that the growth and degradation of bacteria were affected by the increase in cyanide concentration with a total halt at 700 ppm KCN after 72 h incubation. In this study, specific growth and degradation rates were found to trail the substrate inhibition kinetics. These two rates fitted well to the kinetic models of Teissier, Luong, Aiba and Heldane, while the performance of Monod model was found to be unsatisfactory. These models were used to clarify the substrate inhibition on the bacteria growth. The analyses of these models have shown that Luong model has fitted the experimental data with the highest coefficient of determination ( R 2 ) value of 0.9794 and 0.9582 with the lowest root mean square error (RMSE) value of 0.000204 and 0.001, respectively, for the specific rate of degradation and growth. It is the only model that illustrates the maximum substrate concentration ( S m ) of 713.4 and empirical constant ( n ) of 1.516. Tessier and Aiba fitted the experimental data with a R 2 value of 0.8002 and 0.7661 with low RMSE of 0.0006, respectively, for specific biodegradation rate, while having a R 2 value of 0.9 and RMSE of 0.001, respectively, for specific growth rate. Haldane has the lowest R 2 value of 0.67 and 0.78 for specific biodegradation and growth rate with RMSE of 0.0006 and 0.002, respectively. This indicates the level of the bacteria stability in varying concentrations of cyanide and the maximum cyanide concentration it can tolerate within a specific time period. The biokinetic constant predicted from this model demonstrates a good ability of the locally isolated bacteria in cyanide remediation in industrial effluents.

Rate constants for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

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

Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The presentmore » work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants. The experimental results can be expressed in Arrhenius form in units of cm{sup 3} molecule{sup -1} s{sup -1} as follows: K{sub OH+n-heptane} = (2.48 {+-} 0.17) x 10{sup -10} exp[(-1927 {+-} 69 K)/T] (838-1287 K); k{sub OH+2,2,3,3-TMB} = (8.26 {+-} 0.89) x 10{sup -11} exp[(-1337 {+-} 94 K)/T] (789-1061 K); K{sub OH+n-pentane} = (1.60 {+-} 0.25) x 10{sup -10} exp[(-1903 {+-} 146 K)/T] (823-1308 K); K{sub OH+n-hexane} = (2.79 {+-} 0.39) x 10{sup -10} exp[(-2301 {+-} 134 K)/T] (798-1299 K); and k{sub OH+2,3-DMB} = (1.27 {+-} 0.16) x 10{sup -10} exp[(-1617 {+-} 118 K)/T] (843-1292 K). The available experimental data, along with lower-T determinations, were used to obtain evaluations of the experimental rate constants over the temperature range from {approx}230 to 1300 K for most of the title reactions. These extended-temperature-range evaluations, given as three-parameter fits, are as follows: k{sub OH+n-heptane} = 2.059 x 10{sup -5}T{sup 1.401} exp(33 K

The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

PubMed

Chen, Q; Song, J M; Pan, F; Xia, F L; Yuan, J Y

2009-10-01

Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

NASA Astrophysics Data System (ADS)

Cannon, William R.; Baker, Scott E.

2017-10-01

Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

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.

High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

DOE PAGES

Nguyen, Thanh Lam; Stanton, John F.

2017-06-02

Hydrogen abstraction from NH 3 by OH to produce H 2O 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 to 20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Here, quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

Degradation of environment pollutant dyes using phytosynthesized metal nanocatalysts

NASA Astrophysics Data System (ADS)

MeenaKumari, M.; Philip, Daizy

2015-01-01

We present for the first time biogenic reduction and stabilization of gold and silver ions at room temperature using fruit juice of Punica granatum. The formation, morphology and crystalline structure of the synthesized nanoparticles are determined using UV-Visible, XRD and TEM. An attempt to reveal the partial role of phenolic hydroxyls in the reduction of Au3+ and Ag+ is done through FTIR analysis. The synthesized nanoparticles are used as potential catalysts in the degradation of a cationic phenothiazine dye, an anionic mono azo dye and a cationic fluorescent dye. The calculated values of percentage removal of dyes and the rate constants from pseudo first order kinetic data fit give a comparative study on degradation of organic dyes in presence of prepared gold and silver nanoparticles.

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water.

PubMed

Hao, Xiao Long; Zhou, Ming Hua; Lei, Le Cheng

2007-03-22

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.

Poly(amido-amine)-based hydrogels with tailored mechanical properties and degradation rates for tissue engineering.

PubMed

Martello, Federico; Tocchio, Alessandro; Tamplenizza, Margherita; Gerges, Irini; Pistis, Valentina; Recenti, Rossella; Bortolin, Monica; Del Fabbro, Massimo; Argentiere, Simona; Milani, Paolo; Lenardi, Cristina

2014-03-01

Poly(amido-amine) (PAA) hydrogels containing the 2,2-bisacrylamidoacetic acid-4-amminobutyl guanidine monomeric unit have a known ability to enhance cellular adhesion by interacting with the arginin-glycin-aspartic acid (RGD)-binding αVβ3 integrin, expressed by a wide number of cell types. Scientific interest in this class of materials has traditionally been hampered by their poor mechanical properties and restricted range of degradation rate. Here we present the design of novel biocompatible, RGD-mimic PAA-based hydrogels with wide and tunable degradation rates as well as improved mechanical and biological properties for biomedical applications. This is achieved by radical polymerization of acrylamide-terminated PAA oligomers in both the presence and absence of 2-hydroxyethylmethacrylate. The degradation rate is found to be precisely tunable by adjusting the PAA oligomer molecular weight and acrylic co-monomer concentration in the starting reaction mixture. Cell adhesion and proliferation tests on Madin-Darby canine kidney epithelial cells show that PAA-based hydrogels have the capacity to promote cell adhesion up to 200% compared to the control. Mechanical tests show higher compressive strength of acrylic chain containing hydrogels compared to traditional PAA hydrogels. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process.

PubMed

Xiang, Yingying; Fang, Jingyun; Shang, Chii

2016-03-01

The UV/chlorine advanced oxidation process (AOP), which forms reactive species such as hydroxyl radicals (HO) and reactive chlorine species (RCS) such as chlorine atoms (Cl) and Cl2(-), is being considered as an alternative to the UV/H2O2 AOP for the degradation of emerging contaminants. This study investigated the kinetics and pathways of the degradation of a recalcitrant pharmaceutical and personal care product (PPCP)-ibuprofen (IBP)-by the UV/chlorine AOP. The degradation of IBP followed the pseudo first-order kinetics. The first-order rate constant was 3.3 times higher in the UV/chlorine AOP than in the UV/H2O2 AOP for a given chemical molar dosage at pH 6. The first-order rate constant decreased from 3.1 × 10(-3) s(-1) to 5.5 × 10(-4) s(-1) with increasing pH from 6 to 9. Both HO and RCS contributed to the degradation, and the contribution of RCS increased from 22% to 30% with increasing pH from 6 to 9. The degradation was initiated by HO-induced hydroxylation and Cl-induced chlorine substitution, and sustained through decarboxylation, demethylation, chlorination and ring cleavage to form more stable products. Significant amounts of chlorinated intermediates/byproducts were formed from the UV/chlorine AOP, and four chlorinated products were newly identified. The yield of total organic chlorine (TOCl) was 31.6 μM after 90% degradation of 50 μM IBP under the experimental conditions. The known disinfection by-products (DBPs) comprised 17.4% of the TOCl. The effects of water matrix in filtered drinking water on the degradation were not significant, demonstrating the practicality of the UV/chlorine AOP for the control of some refractory PPCPs. However, the toxicity of the chlorinated products should be further assessed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of various advanced oxidation processes for the degradation of 4-chloro-2 nitrophenol.

PubMed

Saritha, P; Aparna, C; Himabindu, V; Anjaneyulu, Y

2007-11-19

In the present study an attempt is made efficiently to degrade USEPA listed 4-chloro-2-nitrophenol (4C-2-NP), widely available in bulk drug and pesticide wastes using various advanced oxidation processes (AOPs). A comparative assessment using various AOPs (UV, H(2)O(2,) UV/H(2)O(2), Fenton, UV/Fenton and UV/TiO(2)) was attempted after initial optimization studies, viz., varying pH, peroxide concentration, iron concentration, and TiO(2) loading. The degradation of the study compound was estimated using chemical oxygen demand (COD) reduction and compound reduction using spectrophotometric methods and further validated with high performance liquid chromatography (HPLC). The degradation trends followed the order: UV/Fenton > UV/TiO(2) > UV/H(2)O(2) > Fenton > H(2)O(2) > UV(.) It can be inferred from the studies that UV/Fenton was the most effective in partial mineralization of 4C-2-NP. However, lower costs were obtained with H(2)O(2). Kinetic constants were evaluated using first order equations to determine the rate constant K.

Photochemical parameters of atmospheric source gases: accurate determination of OH reaction rate constants over atmospheric temperatures, UV and IR absorption spectra

NASA Astrophysics Data System (ADS)

Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.

2012-12-01

The emissions of halogenated (Cl, Br containing) organics of both natural and anthropogenic origin contribute to the balance of and changes in the stratospheric ozone concentration. The associated chemical cycles are initiated by the photochemical decomposition of the portion of source gases that reaches the stratosphere. Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound lifetime in the troposphere and release of active halogen in the stratosphere for a majority of halogen source gases. Therefore, the accuracy of photochemical data is of primary importance for the purpose of comprehensive atmospheric modeling and for simplified kinetic estimations of global impacts on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP). The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still may constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the presentation is to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. A detailed inventory of accountable sources of

Thermal degradation kinetics of anthocyanins from blood orange, blackberry, and roselle using the arrhenius, eyring, and ball models.

PubMed

Cisse, Mady; Vaillant, Fabrice; Acosta, Oscar; Dhuique-Mayer, Claudie; Dornier, Manuel

2009-07-22

Anthocyanin stability was assessed over temperatures ranging from 30 to 90 degrees C for seven products: blood orange juice [Citrus sinensis (L.) Osbeck]; two tropical highland blackberry juices (Rubus adenotrichus Schlech.), one with high content and the other with low content of suspended insoluble solids (SIS); and four roselle extracts (Hibiscus sabdariffa L.). The blackberry juice showed the highest content of anthocyanins with 1.2 g/L (two times less in the roselle extracts and 12 times less in the blood orange juice). The rate constant for anthocyanin degradation and isothermal kinetic parameters were calculated according to three models: Arrhenius, Eyring, and Ball. Anthocyanins in blood orange juice presented the highest rate constant for degradation, followed by the blackberry juices and roselle extracts. Values of activation energies were 66 and 37 kJ/mol, respectively, for blood orange and blackberry and 47-61 kJ/mol for roselle extracts. For the blackberry juices, a high SIS content provided only slight protection for the anthocyanins. The increasing content of dissolved oxygen, from 0.5 to 8.5 g/L, did not significantly increase the rate constant. For both isothermal and nonisothermal treatments, all three models accurately predicted anthocyanin losses from different food matrices.

Absolute rate constants for the reaction of OH with cyclopentane and cycloheptane from 233 to 351 K.

PubMed

Gennaco, Michael A; Huang, Yi-wen; Hannun, Reem A; Dransfield, Timothy J

2012-12-27

Absolute rate constant measurements for the reactions of OH with cyclopentane and cycloheptane in the gas phase in 6-8 Torr of nitrogen from 233 to 351 K in the Harvard University High-Pressure Flow System (HPFS) are reported. Hydroxyl concentrations were measured using laser-induced fluorescence, and alkane concentrations were measured using Fourier transform infrared spectroscopy. Results were fit to a modified Arrhenius equation based on transition state theory (ignoring tunneling): k(T) = B e(-E(a)/T)/T(1 - e(-1.44ν(1)/T))(2)(1 - e(-1.44ν(2)/T)), with ν(1) and ν(2) bending frequencies set to 280 and 500 cm(-1) . Results were as follows for E(a) (K) and k (298) (10(-12) cm(3) s(-1)): cyclopentane, 460 ± 32, 4.85; cycloheptane, 319 ± 36, 9.84. This work represents the second absolute temperature-dependent rate constant measurement reported for cycloheptane, and the third absolute temperature-dependent rate constant measurement reported near room temperature for the reaction of OH and cyclopentane. For the title reactions, the reaction barriers reported here are in agreement with the reaction barrier previously reported for cyclohexane and considerably higher than the barrier previously reported for cyclo-octane, a result that is not predicted by our current understanding of hydrocarbon reactivity.

First-principles calculation of photo-induced electron transfer rate constants in phthalocyanine-C60 organic photovoltaic materials: Beyond Marcus theory

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

Classical Marcus theory is commonly adopted in solvent-mediated charge transfer (CT) process to obtain the CT rate constant, but it can become questionable when the intramolecular vibrational modes dominate the CT process as in OPV devices because Marcus theory treats these modes classically and therefore nuclear tunneling is not accounted for. We present a computational scheme to obtain the electron transfer rate constant beyond classical Marcus theory. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided. Ab initio calculations are used to obtain the basic parameters needed for calculating the electron transfer rate constant. We apply our methodology to phthalocyanine(H2PC)-C60 organic photovoltaic system where one C60 acceptor and one or two H2PC donors are included to model the donor-acceptor interface configuration. We obtain the electron transfer and recombination rate constants for all accessible charge transfer (CT) states, from which the CT exciton dynamics is determined by employing a master equation. The role of higher lying excited states in CT exciton dynamics is discussed. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

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.

Geraniol (2,6-dimethyl-2,6-octadien-8-ol) reactions with ozone and OH radical: Rate constants and gas-phase products

NASA Astrophysics Data System (ADS)

Forester, Crystal D.; Ham, Jason E.; Wells, J. R.

The bimolecular rate constants, kOH+geraniol, (231±58)×10 -12 cm 3 molecule -1 s -1 and k+geraniol, (9.3±2.3)×10 -16 cm 3 molecule -1 s -1, were measured using the relative rate technique for the reaction of the hydroxyl radical (OH) and ozone (O 3) with 2,6-dimethyl-2,6-octadien-8-ol (geraniol) at (297±3) K and 1 atmosphere total pressure. To more clearly define part of geraniol's indoor environment degradation mechanism, the products of the geraniol+OH and geraniol+O 3 reactions were also investigated. The identified geraniol+OH and geraniol+O 3 reaction products were: acetone, hydroxyacetaldehyde (glycolaldehyde, HC( dbnd O)CH 2OH), ethanedial (glyoxal, HC( dbnd O)C( dbnd O)H), and 2-oxopropanal (methylglyoxal, CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 4-oxopentanal as the other major geraniol+OH and geraniol+O 3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible geraniol+OH and geraniol+O 3 reaction mechanisms based on previously published volatile organic compound+OH and volatile organic compound+O 3 gas-phase reaction mechanisms.

Nuclear Radiation Degradation Study on HD Camera Based on CMOS Image Sensor at Different Dose Rates.

PubMed

Wang, Congzheng; Hu, Song; Gao, Chunming; Feng, Chang

2018-02-08

In this work, we irradiated a high-definition (HD) industrial camera based on a commercial-off-the-shelf (COTS) CMOS image sensor (CIS) with Cobalt-60 gamma-rays. All components of the camera under test were fabricated without radiation hardening, except for the lens. The irradiation experiments of the HD camera under biased conditions were carried out at 1.0, 10.0, 20.0, 50.0 and 100.0 Gy/h. During the experiment, we found that the tested camera showed a remarkable degradation after irradiation and differed in the dose rates. With the increase of dose rate, the same target images become brighter. Under the same dose rate, the radiation effect in bright area is lower than that in dark area. Under different dose rates, the higher the dose rate is, the worse the radiation effect will be in both bright and dark areas. And the standard deviations of bright and dark areas become greater. Furthermore, through the progressive degradation analysis of the captured image, experimental results demonstrate that the attenuation of signal to noise ratio (SNR) versus radiation time is not obvious at the same dose rate, and the degradation is more and more serious with increasing dose rate. Additionally, the decrease rate of SNR at 20.0, 50.0 and 100.0 Gy/h is far greater than that at 1.0 and 10.0 Gy/h. Even so, we confirm that the HD industrial camera is still working at 10.0 Gy/h during the 8 h of measurements, with a moderate decrease of the SNR (5 dB). The work is valuable and can provide suggestion for camera users in the radiation field.

Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

DOE PAGES

Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; ...

2015-06-17

In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constantmore » voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.« less

Modeling the degradation kinetics of ascorbic acid.

PubMed

Peleg, Micha; Normand, Mark D; Dixon, William R; Goulette, Timothy R

2018-06-13

Most published reports on ascorbic acid (AA) degradation during food storage and heat preservation suggest that it follows first-order kinetics. Deviations from this pattern include Weibullian decay, and exponential drop approaching finite nonzero retention. Almost invariably, the degradation rate constant's temperature-dependence followed the Arrhenius equation, and hence the simpler exponential model too. A formula and freely downloadable interactive Wolfram Demonstration to convert the Arrhenius model's energy of activation, E a , to the exponential model's c parameter, or vice versa, are provided. The AA's isothermal and non-isothermal degradation can be simulated with freely downloadable interactive Wolfram Demonstrations in which the model's parameters can be entered and modified by moving sliders on the screen. Where the degradation is known a priori to follow first or other fixed order kinetics, one can use the endpoints method, and in principle the successive points method too, to estimate the reaction's kinetic parameters from considerably fewer AA concentration determinations than in the traditional manner. Freeware to do the calculations by either method has been recently made available on the Internet. Once obtained in this way, the kinetic parameters can be used to reconstruct the entire degradation curves and predict those at different temperature profiles, isothermal or dynamic. Comparison of the predicted concentration ratios with experimental ones offers a way to validate or refute the kinetic model and the assumptions on which it is based.

Comparison of rate constants for (PO3-) transfer by the Mg(II), Cd(II), and Li(I) forms of phosphoglucomutase.

PubMed

Ray, W J; Post, C B; Puvathingal, J M

1989-01-24

Net rate constants that define the steady-state rate through a sequence of steps and the corresponding effective energy barriers for two (PO3-)-transfer steps in the phosphoglucomutase reaction were compared as a function of metal ion, M, where M = Mg2+ and Cd2+. These steps involve the reaction of either the 1-phosphate or the 6-phosphate of glucose 1,6-bisphosphate (Glc-P2) bound to the dephosphoenzyme (ED) to produce the phosphoenzyme (EP) and the free monophosphates, glucose 1-phosphate (Glc-1-P) or glucose 6-phosphate (Glc-6-P): EP.M + Glc-1-P----ED.M.Glc-P2----EP.M.Glc-6-P6. Before this comparison was made, net rate constants for the Cd2+ enzyme, obtained at high enzyme concentration via 31P NMR saturation-transfer studies [Post, C. B., Ray, W. J., Jr., & Gorenstein, D. G. (1989) Biochemistry (preceding paper in this issue)], were appropriately scaled by using the observed constants to calculate both the expected isotope-transfer rate at equilibrium and the steady-state rate under initial velocity conditions and comparing the calculated values with those measured in dilute solution. For the Mg2+ enzyme, narrow limits on possible values of the corresponding net rate constants were imposed on the basis of initial velocity rate constants for the forward and reverse directions plus values for the equilibrium distribution of central complexes, since direct measurement is not feasible. The effective energy barriers for both the Mg2+ and Cd2+ enzymes, calculated from the respective net rate constants, together with previously values for the equilibrium distribution of complexes in both enzymic systems [Ray, W. J., Jr., & Long, J. W. (1976) Biochemistry 15, 4018-4025], show that the 100-fold decrease in the kappa cat for the Cd2+ relative to the Mg2+ enzyme is caused by two factors: the increased stability of the intermediate bisphosphate complex and the decreased ability to cope with the phosphate ester involving the 1-hydroxyl group of the glucose ring. In fact, it

Comparison of in situ and in vitro techniques for measuring ruminal degradation of animal by-product proteins.

PubMed

England, M L; Broderick, G A; Shaver, R D; Combs, D K

1997-11-01

Ruminally undegraded protein (RUP) values of blood meal (n = 2), hydrolyzed feather meal (n = 2), fish meal (n = 2), meat and bone meal, and soybean meal were estimated using an in situ method, an inhibitor in vitro method, and an inhibitor in vitro technique applying Michaelis-Menten saturation kinetics. Degradation rates for in situ and inhibitor in vitro methods were calculated by regression of the natural log of the proportion of crude protein (CP) remaining undegraded versus time. Nonlinear regression analysis of the integrated Michaelis-Menten equation was used to determine maximum velocity, the Michaelis constant, and degradation rate (the ratio of maximum velocity to the Michaelis constant). A ruminal passage rate of 0.06/h was assumed in the calculation of RUP. The in situ and inhibitor in vitro techniques yielded similar estimates of ruminal degradation. Mean RUP estimated for soybean meal, blood meal, hydrolyzed feather meal, fish meal, and meat and bone meal were, respectively, 28.6, 86.0, 77.4, 52.9, and 52.6% of CP by the in situ method and 26.4, 86.1, 76.0, 59.6, and 49.5% of CP by the inhibitor in vitro technique. The Michaelis-Menten inhibitor in vitro technique yielded more rapid CP degradation rates and decreased estimates of RUP. The inhibitor in vitro method required less time and labor than did the other two techniques to estimate the RUP values of animal by-product proteins. Results from in vitro incubations with pepsin.HCl suggested that low postruminal digestibility of hydrolyzed feather meal may impair its value as a source of RUP.

Ascorbate degradation in tomato leads to accumulation of oxalate, threonate and oxalyl threonate.

PubMed

Truffault, Vincent; Fry, Stephen C; Stevens, Rebecca G; Gautier, Hélène

2017-03-01

Ascorbate content in plants is controlled by its synthesis from carbohydrates, recycling of the oxidized forms and degradation. Of these pathways, ascorbate degradation is the least studied and represents a lack of knowledge that could impair improvement of ascorbate content in fruits and vegetables as degradation is non-reversible and leads to a depletion of the ascorbate pool. The present study revealed the nature of degradation products using [ 14 C]ascorbate labelling in tomato, a model plant for fleshy fruits; oxalate and threonate are accumulated in leaves, as is oxalyl threonate. Carboxypentonates coming from diketogulonate degradation were detected in relatively insoluble (cell wall-rich) leaf material. No [ 14 C]tartaric acid was found in tomato leaves. Ascorbate degradation was stimulated by darkness, and the degradation rate was evaluated at 63% of the ascorbate pool per day, a percentage that was constant and independent of the initial ascorbate or dehydroascorbic acid concentration over periods of 24 h or more. Furthermore, degradation could be partially affected by the ascorbate recycling pathway, as lines under-expressing monodehydroascorbate reductase showed a slight decrease in degradation product accumulation. © 2016 The Authors The Plant Journal © 2016 John Wiley & Sons Ltd.

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

Glutaraldehyde degradation in hospital wastewater by photoozonation.

PubMed

Kist, Lourdes Teresinha; Rosa, Ellen Caroline; Machado, Enio Leandro; Camargo, Maria Emilia; Moro, Celso Camilo

2013-01-01

In this paper, we assessed aqueous solutions of glutaraldehyde (GA), a chemical used for the disinfection of hospital materials, using advanced oxidative processes, O3, and UV, and the combination of the latter two. Assays with different ozone concentrations at distinct pH levels were conducted to determine the best treatment process. GA concentrations before and after each treatment were measured by spectrophotometry. The best treatment was that which combined O3 and UV, yielding a degradation of 72.0-75.0% in relation to the initial concentration with pH between 4 and 9. Kinetics demonstrated that GA degradation is not dependent on pH, as there was a first-order reaction with a rate constant of k = 0.0180 min(-1) for initial pH 9 and of k = 0.0179 min(-1) for initial pH 7, that is, the values are virtually the same. Secondary wastewater samples were also analysed using the septic tank/filter system of a regional hospital in Vale do Rio Pardo, state of Rio Grande do Sul, southern Brazil. In this case, the characteristics of the wastewater were described and, after treatment, a GA degradation rate of 23.3% was noted, with reductions of 75% for chemical oxygen demand, 81% for biochemical oxygen demand, 68% for turbidity, 70% for surfactants and total disinfection in terms of thermotolerant coliforms.

Factors controlling the photochemical degradation of methylmercury in coastal and oceanic waters

PubMed Central

DiMento, Brian P.; Mason, Robert P.

2018-01-01

Many studies have recognized abiotic photochemical degradation as an important sink of methylmercury (CH3Hg) in sunlit surface waters, but the rate-controlling factors remain poorly understood. The overall objective of this study was to improve our understanding of the relative importance of photochemical reactions in the degradation of CH3Hg in surface waters across a variety of marine ecosystems by extending the range of water types studied. Experiments were conducted using surface water collected from coastal sites in Delaware, New Jersey, Connecticut, and Maine, as well as offshore sites on the New England continental shelf break, the equatorial Pacific, and the Arctic Ocean. Filtered water amended with additional CH3Hg at environmentally relevant concentrations was allowed to equilibrate with natural ligands before being exposed to natural sunlight. Water quality parameters – salinity, dissolved organic carbon, and nitrate – were measured, and specific UV absorbance was calculated as a proxy for dissolved aromatic carbon content. Degradation rate constants (0.87–1.67 day−1) varied by a factor of two across all water types tested despite varying characteristics, and did not correlate with initial CH3Hg concentrations or other environmental parameters. The rate constants in terms of cumulative photon flux values were comparable to, but at the high end of, the range of values reported in other studies. Further experiments investigating the controlling parameters of the reaction observed little effect of nitrate and chloride, and potential for bromide involvement. The HydroLight radiative transfer model was used to compute solar irradiance with depth in three representative water bodies – coastal wetland, estuary, and open ocean – allowing for the determination of water column integrated rates. Methylmercury loss per year due to photodegradation was also modeled across a range of latitudes from the Arctic to the Equator in the three model water types

Sorption and degradation of wastewater-associated pharmaceuticals and personal care products in agricultural soils and sediment.

PubMed

Zhang, Ting; Wu, Bo; Sun, Na; Ye, Yong; Chen, Huaixia

2013-01-01

Pharmaceuticals and personal care products (PPCPs) have drawn popular concerns recently as an emerging class of aquatic contaminants. In this study, adsorption and degradation of four selected PPCPs, metronidazole, tinidazole, caffeine and chloramphenicol, have been investigated in the laboratory using two agricultural soils in China and sediment from Changjiang River. Adsorption tests using a batch equilibrium method demonstrated that adsorption of all tested chemicals in soils could be well described with Freundlich equation, and their adsorption affinity on soil followed the order of chloramphenicol > caffeine > tinidazole > metronidazole. Generally, higher Kf value was associated with soils which had higher organic matter contents (except for caffeine acid in this study). Degradation of selected PPCPs in soils generally followed first-order exponential decay kinetics, and half-lives ranging from 0.97 to 10.21 d. Sterilization generally decreased the degradation rates, indicating that microbial activity played a significant role in the degradation in soils. The degradation rate constant decreased with increasing initial chemical concentrations in soil, implying that the microbial activity was inhibited with high chemical loading levels.

Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

NASA Astrophysics Data System (ADS)

Powell, C. L.; Goltz, M. N.; Agrawal, A.

2014-12-01

Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

Optimization of High-Throughput Sequencing Kinetics for determining enzymatic rate constants of thousands of RNA substrates

PubMed Central

Niland, Courtney N.; Jankowsky, Eckhard; Harris, Michael E.

2016-01-01

Quantification of the specificity of RNA binding proteins and RNA processing enzymes is essential to understanding their fundamental roles in biological processes. High Throughput Sequencing Kinetics (HTS-Kin) uses high throughput sequencing and internal competition kinetics to simultaneously monitor the processing rate constants of thousands of substrates by RNA processing enzymes. This technique has provided unprecedented insight into the substrate specificity of the tRNA processing endonuclease ribonuclease P. Here, we investigate the accuracy and robustness of measurements associated with each step of the HTS-Kin procedure. We examine the effect of substrate concentration on the observed rate constant, determine the optimal kinetic parameters, and provide guidelines for reducing error in amplification of the substrate population. Importantly, we find that high-throughput sequencing, and experimental reproducibility contribute their own sources of error, and these are the main sources of imprecision in the quantified results when otherwise optimized guidelines are followed. PMID:27296633

Rate constants of agonist binding to muscarinic receptors in rat brain medulla. Evaluation by competition kinetics

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

Schreiber, G.; Henis, Y.I.; Sokolovsky, M.

The method of competition kinetics, which measures the binding kinetics of an unlabeled ligand through its effect on the binding kinetics of a labeled ligand, was employed to investigate the kinetics of muscarinic agonist binding to rat brain medulla pons homogenates. The agonists studied were acetylcholine, carbamylcholine, and oxotremorine, with N-methyl-4-(TH)piperidyl benzilate employed as the radiolabeled ligand. Our results suggested that the binding of muscarinic agonists to the high affinity sites is characterized by dissociation rate constants higher by 2 orders of magnitude than those of antagonists, with rather similar association rate constants. Our findings also suggest that isomerization ofmore » the muscarinic receptors following ligand binding is significant in the case of antagonists, but not of agonists. Moreover, it is demonstrated that in the medulla pons preparation, agonist-induced interconversion between high and low affinity bindings sites does not occur to an appreciable extent.« less

Simulation of herbicide degradation in different soils by use of Pedo-transfer functions (PTF) and non-linear kinetics.

PubMed

von Götz, N; Richter, O

1999-03-01

The degradation behaviour of bentazone in 14 different soils was examined at constant temperature and moisture conditions. Two soils were examined at different temperatures. On the basis of these data the influence of soil properties and temperature on degradation was assessed and modelled. Pedo-transfer functions (PTF) in combination with a linear and a non-linear model were found suitable to describe the bentazone degradation in the laboratory as related to soil properties. The linear PTF can be combined with a rate related to the temperature to account for both soil property and temperature influence at the same time.

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.

Nuclear Radiation Degradation Study on HD Camera Based on CMOS Image Sensor at Different Dose Rates

PubMed Central

Wang, Congzheng; Hu, Song; Gao, Chunming; Feng, Chang

2018-01-01

In this work, we irradiated a high-definition (HD) industrial camera based on a commercial-off-the-shelf (COTS) CMOS image sensor (CIS) with Cobalt-60 gamma-rays. All components of the camera under test were fabricated without radiation hardening, except for the lens. The irradiation experiments of the HD camera under biased conditions were carried out at 1.0, 10.0, 20.0, 50.0 and 100.0 Gy/h. During the experiment, we found that the tested camera showed a remarkable degradation after irradiation and differed in the dose rates. With the increase of dose rate, the same target images become brighter. Under the same dose rate, the radiation effect in bright area is lower than that in dark area. Under different dose rates, the higher the dose rate is, the worse the radiation effect will be in both bright and dark areas. And the standard deviations of bright and dark areas become greater. Furthermore, through the progressive degradation analysis of the captured image, experimental results demonstrate that the attenuation of signal to noise ratio (SNR) versus radiation time is not obvious at the same dose rate, and the degradation is more and more serious with increasing dose rate. Additionally, the decrease rate of SNR at 20.0, 50.0 and 100.0 Gy/h is far greater than that at 1.0 and 10.0 Gy/h. Even so, we confirm that the HD industrial camera is still working at 10.0 Gy/h during the 8 h of measurements, with a moderate decrease of the SNR (5 dB). The work is valuable and can provide suggestion for camera users in the radiation field. PMID:29419782

Multiscale analysis of the radiooxidative degradation of EVA/EPDM composites. ATH filler and dose rate effect

NASA Astrophysics Data System (ADS)

Sidi, Ahmedou; Colombani, Juliette; Larché, Jean-François; Rivaton, Agnès

2018-01-01

This study is focused on the radiooxidative degradation of polymeric insulation of electric cables used in Nuclear Power Plants (NPPs). In order to investigate the degradation mechanisms of the insulation, model composites with ATH (Aluminium TriHydrate) filler and blends (without filler) based on a cross-linked mixture of EVA (Ethylene Vinyl Acetate) and EPDM (Ethylene Propylene Diene Monomer) were submitted to gamma-rays. In normal operating conditions of a NPP, the dose rate which electric cables are exposed to is around 0.1 Gy h-1. In this work, artificial accelerated ageing test process has been applied at a relatively low dose rate of 7 Gy h-1. Gamma-irradiations at higher dose rates typically used to accelerate the ageing, in the range 0.2-1 kGy h-1, were also carried out. The first part of the study is focused on irradiations performed at relatively low dose rate and is devoted to the highlighting of the radiooxidative degradation mechanisms of EVA/EPDM blend with and without ATH filler. Correlations between the evolutions of the chemical, morphological and mechanical/electrical properties of the materials occurring after the ageing process are presented. It is shown that the degradation process is governed by radical oxidation mechanism involving chain scissions leading to the formation of carboxylic acids as end-groups. One of the main effects of the ATH filler is the progressive loss of the mechanical properties of the composite upon radiooxidation whereas they are maintained in the case of the unfilled sample. Despite the oxidation of the polymer, no change in the electrical properties of the blend and of the composite could be observed. The second part of the study focuses on the dose rate effect. It is shown that one of the main consequences of an increase of the dose rate from 7 Gy h-1 to 0.2-1 kGy h-1 is a reduction of the chain scission process yield by a factor of about 20. Therefore, an important and consistent finding is that there are some

Effects of ionic strength, temperature, and pH on degradation of selected antibiotics

USGS Publications Warehouse

Loftin, K.A.; Adams, C.D.; Meyer, M.T.; Surampalli, R.

2008-01-01

Aqueous degradation rates, which include hydrolysis and epimerization, for chlorretracycline (CTC), oxytetracycline (OTC), tetracycline (TET), lincomycin (LNC), sulfachlorpyridazine (SCP), sulfadimethoxine (SDM), sulfathiazole (STZ), trimethoprim (TRM), and tylosin A (TYL) were studied as a function of ionic strength (0.0015, 0.050, or 0.084 mg/L as Na2HPO4), temperature (7, 22, and 35??C), and pH (2, 5, 7, 9, and 11). Multiple linear regression revealed that ionic strength did not significantly affect (?? = 0.05) degradation rates for all compounds, but temperature and pH affected rates for CTC, OTC, and TET significandy (?? = 0.05). Degradation also was observed for TYL at pH 2 and 11. No significant degradation was observed for LNC, SCR SDM, STZ, TRM, and TYL (pH 5, 7, and 9) under study conditions. Pseudo first-order rate constants, half-lives, and Arrhenius coefficients were calculated where appropriate. In general, hydrolysis rates for CTC, OTC, and TET increased as pH and temperature increased following Arrhenius relationships. Known degradation products were used to confirm that degradation had occurred, but these products were not quantified. Half-lives ranged from less than 6 h up to 9.7 wk for the tetracyclines and for TYL (pH 2 and 11), but no degradation of LIN, the sulfonamides, or TRM was observed during the study period. These results indicate that tetracyclines and TYL at pH 2 and 11 are prone to pH-mediated transformation and hydrolysis in some cases, but not the sulfonamides, LIN nor TRM are inclined to degrade under study conditions. This indicates that with the exception of CTC OTC, and TET, pH-mediated reactions such as hydrolysis and epimerization are not likely removal mechanisms in surface water, anaerobic swine lagoons, wastewater, and ground water. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Photocatalytic activity of porous multiwalled carbon nanotube-TiO2 composite layers for pollutant degradation.

PubMed

Zouzelka, Radek; Kusumawati, Yuly; Remzova, Monika; Rathousky, Jiri; Pauporté, Thierry

2016-11-05

TiO2 nanoparticles are suitable building blocks nanostructures for the synthesis of porous functional thin films. Here we report the preparation of films using brookite, P25 titania and anatase pristine nanoparticles and of nanocomposite layers combining anatase nanoparticles and multi-walled carbon nanotube (MWCNT) at various concentrations. The structure and phase composition of the layers were characterized by X-ray diffraction and Raman spectroscopy. Their morphology and texture properties were determined by scanning electron microscopy and krypton adsorption experiments, respectively. Additionally to a strong absorption in the UV range, the composites exhibited light absorption in the visible range as well. The photocatalytic performance of the layers was tested in the degradation of aqueous solutions of 4-chlorophenol serving as a model of an eco-persistent pollutant. Besides the determination of the decrease in the concentration of 4-chlorophenol, also the formation of intermediate degradation products, namely hydroquinone and benzoquinone, was followed. The presence of MWCNTs had a beneficial effect on the photocatalytic performance, a marked increase in the photocatalytic degradation rate constant being observed even at very low concentrations of MWCNTs. Compared to a P25 reference layer, the first order rate reaction constant increased by about 100% for the composite films containing MWCNTs at concentrations above 0.6 wt%. The key parameters for the enhancement of the photocatalytic performance are discussed. The presence of carbon nanotubes influences beneficially the degradation of 4-chlorophenol by an attack of the primarily photoproduced hydroxyl radicals onto the 4-chlorophenol molecules. The degradation due to the direct charge transfer is practically not influenced at all. Copyright © 2016 Elsevier B.V. All rights reserved.

Constant strain accumulation rate between major earthquakes on the North Anatolian Fault.

PubMed

Hussain, Ekbal; Wright, Tim J; Walters, Richard J; Bekaert, David P S; Lloyd, Ryan; Hooper, Andrew

2018-04-11

Earthquakes are caused by the release of tectonic strain accumulated between events. Recent advances in satellite geodesy mean we can now measure this interseismic strain accumulation with a high degree of accuracy. But it remains unclear how to interpret short-term geodetic observations, measured over decades, when estimating the seismic hazard of faults accumulating strain over centuries. Here, we show that strain accumulation rates calculated from geodetic measurements around a major transform fault are constant for its entire 250-year interseismic period, except in the ~10 years following an earthquake. The shear strain rate history requires a weak fault zone embedded within a strong lower crust with viscosity greater than ~10 20  Pa s. The results support the notion that short-term geodetic observations can directly contribute to long-term seismic hazard assessment and suggest that lower-crustal viscosities derived from postseismic studies are not representative of the lower crust at all spatial and temporal scales.

Degradation of pyridine and quinoline in aqueous solution by gamma radiation

NASA Astrophysics Data System (ADS)

Chu, Libing; Yu, Shaoqing; Wang, Jianlong

2018-03-01

In present work, the degradation of two N-heteroaromatic pollutants, i.e., pyridine and quinoline was investigated by gamma irradiation in the presence of TiO2 nanoparticle. The experimental results showed that quinoline has a higher degradation rate than pyridine. The removal efficiency of the pollutants, TOC and TN reached 93.0%, 11.9% and 12.0% for quinoline, 71.0%, 10.6% and 4.4% for pyridine, respectively at 7.0 kGy and initial concentration of 50 mg/L. Ammonium was detected for both pyridine and quinoline within the absorbed doses, suggesting that the organic nitrogen was transformed into ammonium. The degradation rate constant of pyridine and quinoline was increased by 1.1-1.5 times with addition of TiO2. TiO2 nanoparticles were especially effective to enhance the mineralization. The removal efficiency of TOC and TN was increased by 15-12% for pyridine and 23-25% for quinoline, respectively in the presence of 2.0 g/L TiO2. Following gamma irradiation, 2-hydroxypyridine, 3-hydroxypyridine, oxalic acid and formic acid were identified for pyridine and the hydroxyl quinoline and formic acid were detected for quinoline. Accordingly, the degradation mechanism of pyridine and quinoline by gamma irradiation was tentatively proposed.

Degradation of diethyl phthalate (DEP) by UV/persulfate: An experiment and simulation study of contributions by hydroxyl and sulfate radicals.

PubMed

Wang, Ziying; Shao, Yisheng; Gao, Naiyun; Lu, Xian; An, Na

2018-02-01

Degradation of diethyl phthalate (DEP) by ultraviolet/persulfate (UV/PS) process at different reaction conditions was evaluated. DEP can be degraded effectively via this process. Both tert-butyl (TBA) and methanol (MeOH) inhibited the degradation of DEP with MeOH having a stronger impact than TBA, suggesting sulfate radical () and hydroxyl radical (HO) both existed in the reaction systems studied. The second-order rate constants of DEP reacting with and HO were calculated to be (6.4±0.3)×10 7 M -1 s -1 and (3.7±0.1)×10 9 M -1 s -1 , respectively. To further access the potential degradation mechanism in this system, the pseudo-first-order rate constants (k o ) and the radical contributions were modeled using a simple steady-state kinetic model involving and HO. Generally, HO had a greater contribution to DEP degradation than . The k o of DEP increased as PS dosages increased when PS dosages were below 1.9 mM. However, it decreased with increasing initial DEP concentrations, which might be due to the radical scavenging effect of DEP. The k o values in acidic conditions were higher than those in alkaline solutions, which was probably caused by the increasing concentration of hydrogen phosphate (with higher scavenging effects than dihydrogen phosphate) from the phosphate buffer as pH values rose. Natural organic matter and bicarbonate dramatically suppressed the degradation of DEP by scavenging and HO. Additionally, the presence of chloride ion (Cl - ) promoted the degradation of DEP at low Cl - concentrations (0.25-1 mM). Finally, the proposed degradation pathways were illustrated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rapid degradation of 2,4-dichlorophenoxyacetic acid facilitated by acetate under methanogenic condition.

PubMed

Yang, Zhiman; Xu, Xiaohui; Dai, Meng; Wang, Lin; Shi, Xiaoshuang; Guo, Rongbo

2017-05-01

Acetate can be used as an electron donor to stimulate 2,4-dichlorophenoxyacetic acid (2,4-D), which has not been determined under methanogenic condition. This study applied high-throughput sequencing and methanogenic inhibition approaches to investigate the 2,4-D degradation process using the enrichments obtained from paddy soil. Acetate addition significantly promoted 2,4-D degradation, which was 5-fold higher than in the acetate-unsupplemented enrichments in terms of the 2,4-D degradation rate constant. Dechloromonas and Pseudomonas were the dominant 2,4-D degraders. Methanogenic inhibition experiments indicated that the 2,4-D degradation was independent of methanogenesis. It was proposed that the accelerated 2,4-D degradation in the acetate-supplemented enrichment involved an unusual interaction, where members of the acetate oxidizers primarily oxidized acetate and produced H 2 . H 2 was utilized by the 2,4-D degraders to degrade 2,4-D, but also partially consumed by the hydrogenotrophic methanogens to produce methane. The findings presented here provide a new strategy for the remediation of 2,4-D-polluted soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

PubMed

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

2015-07-01

Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

Atypical transitions in material response during constant strain rate, hot deformation of austenitic steel

NASA Astrophysics Data System (ADS)

Borah, Utpal; Aashranth, B.; Samantaray, Dipti; Kumar, Santosh; Davinci, M. Arvinth; Albert, Shaju K.; Bhaduri, A. K.

2017-10-01

Work hardening, dynamic recovery and dynamic recrystallization (DRX) occurring during hot working of austenitic steel have been extensively studied. Various empirical models describe the nature and effects of these phenomena in a typical framework. However, the typical model is sometimes violated following atypical transitions in deformation mechanisms of the material. To ascertain the nature of these atypical transitions, researchers have intentionally introduced discontinuities in the deformation process, such as interrupting the deformation as in multi-step rolling and abruptly changing the rate of deformation. In this work, we demonstrate that atypical transitions are possible even in conventional single-step, constant strain rate deformation of austenitic steel. Towards this aim, isothermal, constant true strain rate deformation of austenitic steel has been carried out in a temperature range of 1173-1473 K and strain rate range of 0.01-100 s-1. The microstructural response corresponding to each deformation condition is thoroughly investigated. The conventional power-law variation of deformation grain size (D) with peak stress (σp) during DRX is taken as a typical model and experimental data is tested against it. It is shown that σp-D relations exhibit an atypical two-slope linear behaviour rather than a continuous power law relation. Similarly, the reduction in σp with temperature (T) is found to consist of two discrete linear segments. In practical terms, the two linear segments denote two distinct microstructural responses to deformation. As a consequence of this distinction, the typical model breaks down and is unable to completely relate microstructural evolution to flow behaviour. The present work highlights the microstructural mechanisms responsible for this atypical behavior and suggests strategies to incorporate the two-slope behaviour in the DRX model.

The effect of poly-β-hydroxyalkanoates degradation rate on nitrous oxide production in a denitrifying phosphorus removal system.

PubMed

Wei, Yan; Wang, Shuying; Ma, Bin; Li, Xiyao; Yuan, Zhiguo; He, Yuelan; Peng, Yongzhen

2014-10-01

Poly-β-hydroxyalkanoates (PHAs) and free nitrous acid (FNA) have been revealed as significant factors causing nitrous oxide (N2O) production in denitrifying phosphorus removal systems. In this study, the effect of PHA degradation rate on N2O production was studied at low FNA levels. N2O production always maintained at approximately 40% of the amount of nitrite reduced independent of the PHA degradation rate. The electrons distributed to nitrite reduction were 1.6 times that to N2O reduction. This indicated that electron competition between these two steps was not affected by the PHA degradation rate. Continuous feed of nitrate was proposed, and demonstrated to reduce N2O accumulation by 75%. While being kept low, a possible compounding effect of a low-level FNA could not be ruled out. The sludge used likely contained both polyphosphate- and glycogen-accumulating organisms, and the results could not be simply attributed to either group of organisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

SU-G-201-06: Directional Low-Dose Rate Brachytherapy: Determination of the TG-43 Dose-Rate Constant Analog for a New Pd-103 Source

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

Aima, M; Culberson, W; Hammer, C

Purpose: The aim of this work is to determine the TG-43 dose-rate constant analog for a new directional low-dose rate brachytherapy source based on experimental methods and comparison to Monte Carlo simulations. The CivaSheet™ is a new commercially available planar source array comprised of a variable number of discrete directional source elements called “CivaDots”. Given the directional nature and non-conventional design of the source, modifications to the AAPM TG-43 protocol for dosimetry are required. As a result, various parameters of the TG-43 dosimetric formalism have to be adapted to accommodate this source. This work focuses on the dose-rate constant analogmore » determination for a CivaDot. Methods: Dose to water measurements of the CivaDot were performed in a polymethyl methacrylate phantom (20×20×12 cm{sup 3}) using thermoluminescent dosimeters (TLDs) and Gafchromic EBT3 film. The source was placed in the center of the phantom, and nine TLD micro-cubes were irradiated along its central axis at a distance of 1 cm. For the film measurements, the TLDs were substituted by a (3×3) cm{sup 2} EBT3 film. Primary air-kerma strength measurements of the source were performed using a variable-aperture free-air chamber. Finally, the source was modeled using the Monte Carlo N-Particle Transport Code 6. Results: Dose-rate constant analog observed for a total of eight CivaDots using TLDs and five CivaDots using EBT3 film was within ±7.0% and ±2.9% of the Monte Carlo predicted value respectively. The average difference observed was −4.8% and −0.1% with a standard deviation of 1.7% and 2.1% for the TLD and the film measurements respectively, which are both within the comparison uncertainty. Conclusion: A preliminary investigation to determine the doserate constant analog for a CivaDot was conducted successfully with good agreement between experimental and Monte Carlo based methods. This work will aid in the eventual realization of a clinically

Testing the ecotoxicology of vegetable versus mineral based lubricating oils: 1. Degradation rates using tropical marine microbes.

PubMed

Mercurio, Philip; Burns, Kathryn A; Negri, Andrew

2004-05-01

Vegetable-derived lubricants (VDL) might be more biodegradable than mineral-derived lubricants (MDL) due to the absence of high molecular weight aromatics, but this remains largely untested in tropical conditions. In this laboratory study, the degradation rates of 2-stroke, 4-stroke and hydraulic VDLs were compared with their MDL counterparts in the presence of mangrove and coral reef microbial communities. While MDLs were comprised largely of unresolved saturated and some aromatic hydrocarbons, their VDL counterparts contained, potentially more degradable, fatty acid methyl esters. Degradation of some VDL was observed by day 7, with the 2-stroke VDL markedly consumed by mangrove microorganisms and the hydraulic VDL degraded by both microorganism communities after this short period. All of the VDL groups were significantly more degraded than the comparable MDLs mineral oil lubricants over 14 days in the presence of either mangrove or coral reef microbial communities. In general the mangrove-sourced microorganisms more efficiently degraded the lubricants than reef-sourced microorganisms.

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

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron.

PubMed

Zhang, Xianlan; Deng, Baolin; Guo, Jing; Wang, Yang; Lan, Yeqing

2011-04-01

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT. Copyright © 2010 Elsevier Ltd. All rights reserved.

The aqueous degradation of bisphenol A and steroid estrogens by ferrate.

PubMed

Li, C; Li, X Z; Graham, N; Gao, N Y

2008-01-01

The aqueous reactivity of five prominent endocrine disrupting chemicals (EDCs) with potassium ferrate has been studied. The degradation kinetics and reaction pathways for bisphenol A (BPA) have been considered in detail, and the reaction rate constants for 17alpha-ethynylestradiol (EE2), estrone (E1), beta-estradiol (E2), and estriol (E3) have been determined, from tests carried out in the pH range of 8-12 and at different reactant molar ratios. The rate constants were determined by a kinetic model incorporating the various species equilibria for the EDC compounds and ferrate, using observations of the temporal reduction in EDC and ferrate concentrations. In agreement with other studies, the oxidation of the EDCs was found to be greater for mono-protonated ferrate, HFeO(4)(-), than for non-protonated ferrate, FeO(4)(2-). Among the five EDCs, all of which have phenol moieties, the ferrate oxidation of the four steroid estrogens (each incorporating the cyclopentanoperhydrophenanthrene ring) had higher reaction rates than BPA. The by-products of BPA degradation by ferrate were analyzed by liquid chromatography/mass spectrometry-mass spectrometry (LC/MS-MS) and gas chromatography/mass spectrometry-mass spectrometry (GC/MS-MS) and nine specific compounds were identified, including p-isopropylphenol, 4-isopropanolphenol, p-isopropenylphenol, and some dicarboxylic acids, etc. It is concluded that ferrate oxidation could be an effective treatment method for the purification of waters containing these particular EDCs.

Etude hydromecanique d'une fracture en cisaillement sous contrainte normale constante

NASA Astrophysics Data System (ADS)

Lamontagne, Eric

This research study deals with the effects of shear direction and injection flow rate on the flow directional anisotropy for a given normal stress. It presents experimental works on hydromechanical shear behaviour of a fracture under constant normal stress conditions that permits the characterisation of the intrinsic hydraulic transmissivity in relation with the directional anisotropy of the roughness morphology on the fracture surfaces. Tests were performed on mortar replicas of a natural fracture so that the fracture roughness and void space geometry were kept the same for each test. The experimental work program was performed through direct shear tests on the fracture replicas in four shear directions under four constant normal stress levels. The application of the normal stress was followed by several injections of fluid under constant flow rate. Then, for each defined shear displacement, several injections of fluid were done at different flow rate but under constant flow rate. The test results show that: (1) for the whole shear tests, the global intrinsic transmissivity is included within an enveloping zone of about one order of size. The transmissivity curves within the enveloping zone has a particularity to increase about two orders of size in the first millimetre of shear displacement and subsequently stabilised rapidly; (2) the highest dilatancy do not correspond necessarily with the highest intrinsic transmissivity so that, the behaviour of the global intrinsic transmissivity is not directly proportional to the fracture dilatancy during shear; (3) after the peak shear stress, the divergence is more marked between the global intrinsic transmissivity curves at various flow rate; (4) after peak shear strength and the beginning of asperity degradation, the gradual passage to residual friction shear behaviour causes a directional flow anisotropy and a reorientation of the flow chenalisation direction sub perpendicularly to the shear direction; (5) the

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 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

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

Rate constants for the quenching of metastable O2 (1Sigma g +) molecules

NASA Technical Reports Server (NTRS)

Kwang, Y. C.; Leu, M.-T.

1985-01-01

The O2 (1Sigma g +) rates for CO2, H2, N2, Cl2, CO, O3, and 2,3 DMB-2 are determined by monitoring the 762-nm emission in a fast-flow-discharge chemiluminescence detection system (Leu, 1984; Leu and Smith, 1981). The results are presented in tables and graphs and briefly characterized. The rate constants (in cu cm/s x 10 to the -16th) are 4600 + or - 500 for CO2, 7000 + or - 300 for H2, 17 + or - 1 for N2, 4.5 + or - 0.8 for Cl2, 45 + or - 5 for CO, 220,000 + or - 30,000 for O3, and 6000 + or - 100 for 2,3 DMB-2. The temperature dependence of the CO2 and O3 quenching reactions at 245-362 K is found to be negligible.

Sedative and cardiorespiratory effects of detomidine constant rate infusion in sheep.

PubMed

de Moura, Rauane Sousa; Bittar, Isabela Plazza; da Silva, Luiz Henrique; Villela, Ana Carolina Vasquez; Dos Santos Júnior, Marcelo Borges; Borges, Naida Cristina; Franco, Leandro Guimarães

2018-02-01

The use of sheep in experiments is widespread and is increasing worldwide, and so is the need to develop species-specific anaesthetic techniques to ensure animal safety. Previous studies have mentioned several protocols involving the administration of alpha-2 adrenergic agonists in sheep; however, assessment of the efficacy and safety of these infusion techniques is still relatively new. Thus, the aim of the present study is to assess the effectiveness of detomidine constant rate infusion (CRI) in sheep by measuring the cardiovascular and respiratory parameters, blood gas variables and sedation scores. Eight adult female Santa Inês sheep received 20 µg/kg of detomidine hydrochloride intravenously as a bolus loading dose, followed by an infusion rate of 60 µg/kg/h. The heart rates and respiratory rates changed continuously during the CRI period. No arrhythmias were observed. The reduction in arterial partial pressure of oxygen (PaO 2 ) was not significant, but one animal showed signs of hypoxaemia (minimum PaO 2 of 66.9 mmHg). The arterial partial pressure of carbon dioxide (PaCO 2 ) increased, but the animals did not become hypercapnic. The bicarbonate (HCO 3- ), pH and base excess (BE) tended towards metabolic alkalosis. The cardiac output (CO), stroke volume (SV), cardiac index (CI) and ejection fraction (EF%) showed no significant changes. The fractional shortening (FS%) decreased slightly, starting at T 45min . Sedation scores varied between 3 (0/10) after sedation and during recovery and 7 (0/10) during CRI. We concluded that administering detomidine at an infusion rate of 60 µg/kg/h in Santa Inês sheep is a simple technique that produces satisfactory sedation for minimally invasive procedures.

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

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

Degradation and annealing studies on gamma rays irradiated COTS PPD CISs at different dose rates

NASA Astrophysics Data System (ADS)

Wang, Zujun; Ma, Yingwu; Liu, Jing; Xue, Yuan; He, Baoping; Yao, Zhibin; Huang, Shaoyan; Liu, Minbo; Sheng, Jiangkun

2016-06-01

The degradation and annealing studies on Colbalt-60 gamma-rays irradiated commercial-off-the-shelf (COTS) pinned photodiode (PPD) CMOS image sensors (CISs) at the various dose rates are presented. The irradiation experiments of COTS PPD CISs are carried out at 0.3, 3.0 and 30.0 rad(Si)/s. The COTS PPD CISs are manufactured using a standard 0.18-μm CMOS technology with four-transistor pixel PPD architecture. The behavior of the tested CISs shows a remarkable degradation after irradiation and differs in the dose rates. The dark current, dark signal non-uniformity (DSNU), random noise, saturation output, signal to noise ratio (SNR), and dynamic range (DR) versus the total ionizing dose (TID) at the various dose rates are investigated. The tendency of dark current, DSNU, and random noise increase and saturation output, SNR, and DR to decrease at 3.0 rad(Si)/s are far greater than those at 0.3 and 30.0 rad(Si)/s. The damage mechanisms caused by TID irradiation at the various dose rates are also analyzed. The annealing tests are carried out at room temperature with unbiased conditions after irradiation.

Chemical Composition, In vitro Gas Production, Ruminal Fermentation and Degradation Patterns of Diets by Grazing Steers in Native Range of North Mexico

PubMed Central

Murillo, M.; Herrera, E.; Carrete, F. O.; Ruiz, O.; Serrato, J. S.

2012-01-01

The objective of the study was to quantify annual and seasonal differences in the chemical composition, in vitro gas production, in situ degradability and ruminal fermentation of grazing steers’ diets. Diet samples were collected with four esophageal cannulated steers (350±3 kg BW); and four ruminally cannulated heifers (342±1.5 kg BW) were used to study the dry matter degradation and fermentation in rumen. Data were analyzed with repeated measurements split plot design. The crude protein, in vitro dry matter digestibility and metabolizable energy were higher during the first year of trial and in the summer (p<0.01). The values of calcium, phosphorus, magnesium, zinc and copper were higher in summer (p<0.05). The gas produced by the soluble and insoluble fractions, as well as the constant rate of gas production were greater in summer and fall (p<0.01). The ammonia nitrogen (NH3N) and total volatile fatty acids concentrations in rumen, the soluble and degradable fractions, the constant rate of degradation and the effective degradability of DM and NDF were affected by year (p<0.05) and season (p<0.01). Our study provides new and useful knowledge for the formulation of protein, energetic and mineral supplements that grazing cattle need to improve their productive and reproductive performance. PMID:25049495

Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

NASA Astrophysics Data System (ADS)

Halder, S.; Fruehan, R. J.

2008-12-01

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R; Gokoglu, S.; Hegde, U.

2009-01-01

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

PubMed

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

Characterization of a Pyrethroid-Degrading Pseudomonas fulva Strain P31 and Biochemical Degradation Pathway of D-Phenothrin.

PubMed

Yang, Jingjing; Feng, Yanmei; Zhan, Hui; Liu, Jie; Yang, Fang; Zhang, Kaiyang; Zhang, Lianhui; Chen, Shaohua

2018-01-01

D-phenothrin is one of the most popular pyrethroid insecticides for its broad spectrum and high insecticidal activity. However, continuous use of D-phenothrin has resulted in serious environmental contamination and raised public concern about its impact on human health. Biodegradation of D-phenothrin has never been investigated and its metabolic behaviors remain unknown. Here, a novel bacterial strain P31 was isolated from active sludge, which completely degraded (100%) D-phenothrin at 50 mg⋅L -1 in 72 h. Based on the morphology, 16S rRNA gene and Biolog tests, the strain was identified as Pseudomonas fulva . Biodegradation conditions were optimized as 29.5°C and pH 7.3 by utilizing response surface methodology. Strain P31 depicted high tolerance and strong D-phenothrin degradation ability through hydrolysis pathway. Strain P31 degraded D-phenothrin at inhibition constant ( K i ) of 482.1673 mg⋅L -1 and maximum specific degradation constant ( q max ) of 0.0455 h -1 whereas critical inhibitor concentration remained as 41.1189 mg⋅L -1 . The 3-Phenoxybenzaldehyde and 1,2-benzenedicarboxylic butyl dacyl ester were identified as the major intermediate metabolites of D-phenothrin degradation pathway through high-performance liquid chromatography and gas chromatography-mass spectrometry. Bioaugmentation of D-phenothrin-contaminated soils with strain P31 dramatically enhanced its degradation, and over 75% of D-phenothrin was removed from soils within 10 days. Moreover, the strain illustrated a remarkable capacity to degrade other synthetic pyrethroids, including permethrin, cyhalothrin, β-cypermethrin, deltamethrin, fenpropathrin, and bifenthrin, exhibiting great potential in bioremediation of pyrethroid-contaminated environment.

The Effect of Static Stretch on Elastin Degradation in Arteries

PubMed Central

Chow, Ming-Jay; Choi, Myunghwan; Yun, Seok Hyun; Zhang, Yanhang

2013-01-01

Previously we have shown that gradual changes in the structure of elastin during an elastase treatment can lead to important transition stages in the mechanical behavior of arteries [1]. However, in vivo arteries are constantly being loaded due to systolic and diastolic pressures and so understanding the effects of loading on the enzymatic degradation of elastin in arteries is important. With biaxial tensile testing, we measured the mechanical behavior of porcine thoracic aortas digested with a mild solution of purified elastase (5 U/mL) in the presence of a static stretch. Arterial mechanical properties and biochemical composition were analyzed to assess the effects of mechanical stretch on elastin degradation. As elastin is being removed, the dimensions of the artery increase by more than 20% in both the longitude and circumference directions. Elastin assays indicate a faster rate of degradation when stretch was present during the digestion. A simple exponential decay fitting confirms the time constant for digestion with stretch (0.11±0.04 h−1) is almost twice that of digestion without stretch (0.069±0.028 h−1). The transition from J-shaped to S-shaped stress vs. strain behavior in the longitudinal direction generally occurs when elastin content is reduced by about 60%. Multiphoton image analysis confirms the removal/fragmentation of elastin and also shows that the collagen fibers are closely intertwined with the elastin lamellae in the medial layer. After removal of elastin, the collagen fibers are no longer constrained and become disordered. Release of amorphous elastin during the fragmentation of the lamellae layers is observed and provides insights into the process of elastin degradation. Overall this study reveals several interesting microstructural changes in the extracellular matrix that could explain the resulting mechanical behavior of arteries with elastin degradation. PMID:24358135

Creatine kinase rate constant in the human heart measured with 3D‐localization at 7 tesla

PubMed Central

Robson, Matthew D.; Neubauer, Stefan; Rodgers, Christopher T.

2016-01-01

Purpose We present a new Bloch‐Siegert four Angle Saturation Transfer (BOAST) method for measuring the creatine kinase (CK) first‐order effective rate constant kf in human myocardium at 7 tesla (T). BOAST combines a variant of the four‐angle saturation transfer (FAST) method using amplitude‐modulated radiofrequency pulses, phosphorus Bloch‐Siegert B1+‐mapping to determine the per‐voxel flip angles, and nonlinear fitting to Bloch simulations for postprocessing. Methods Optimal flip angles and repetition time parameters were determined from Monte Carlo simulations. BOAST was validated in the calf muscle of two volunteers at 3T and 7T. The myocardial CK forward rate constant was then measured in 10 volunteers at 7T in 82 min (after 1H localization). Results BOAST kfCK values were 0.281 ± 0.002 s−1 in the calf and 0.35 ± 0.05 s−1 in myocardium. These are consistent with literature values from lower fields. Using a literature values for adenosine triphosphate concentration, we computed CK flux values of 4.55 ± 1.52 mmol kg−1 s−1. The sensitive volume for BOAST depends on the B1 inhomogeneity of the transmit coil. Conclusion BOAST enables measurement of the CK rate constant in the human heart at 7T, with spatial localization in three dimensions to 5.6 mL voxels, using a 10‐cm loop coil. Magn Reson Med 78:20–32, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:27579566

Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

PubMed Central

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

2015-01-01

ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

THE EFFECT OF CHLORINE DEMAND ON INACTIVATION RATE CONSTANT

EPA Science Inventory

Ct (disinfectant concentration multiplied by exposure time) values are used by the US EPA to evaluate the efficacy of disinfection of microorganisms under various conditions of drinking water treatment conditions. First-order decay is usually assumed for the degradation of a disi...

Photocatalytic degradation of an azo textile dye (C.I. Reactive Red 195 (3BF)) in aqueous solution over copper cobaltite nanocomposite coated on glass by Doctor Blade method.

PubMed

Habibi, Mohammad Hossein; Rezvani, Zoya

2015-08-05

The degradation of C.I. Reactive Red 195 (3BF) in aqueous solution using copper cobaltite nanocomposite coated on glass by Doctor Blade method was studied. Structural, optical and morphological properties of nanocomposite coatings were characterized by X-ray powder diffractometry (XRD), diffuse reflectance spectroscopy (DRS) and field emission scanning electron microscopy (FESEM). The nanoparticles exhibit a particle size of 31 nm, showing a good nanoscale crystalline morphology. The photocatalytic activity of copper cobaltite nanocomposite coated on glass was studied by performing the photocatalytic degradation of 3BF at different irradiation time. The effect of irradiation time on the degradation of 3BF was studied and the results showed that more than 85% of the 3BF was degraded in 45 min of irradiation. The pseudo-first-order kinetic models were used and the rate constants were evaluated with pseudo first order rate constants of 4.10 × 10(-2) min(-1). The main advantage of the photocatalyst coated on glass overcomes the difficulties in separation and recycle of photocatalyst suspensions. Copyright © 2015 Elsevier B.V. All rights reserved.

Photocatalytic degradation of an azo textile dye (C.I. Reactive Red 195 (3BF)) in aqueous solution over copper cobaltite nanocomposite coated on glass by Doctor Blade method

NASA Astrophysics Data System (ADS)

Habibi, Mohammad Hossein; Rezvani, Zoya

2015-08-01

The degradation of C.I. Reactive Red 195 (3BF) in aqueous solution using copper cobaltite nanocomposite coated on glass by Doctor Blade method was studied. Structural, optical and morphological properties of nanocomposite coatings were characterized by X-ray powder diffractometry (XRD), diffuse reflectance spectroscopy (DRS) and field emission scanning electron microscopy (FESEM). The nanoparticles exhibit a particle size of 31 nm, showing a good nanoscale crystalline morphology. The photocatalytic activity of copper cobaltite nanocomposite coated on glass was studied by performing the photocatalytic degradation of 3BF at different irradiation time. The effect of irradiation time on the degradation of 3BF was studied and the results showed that more than 85% of the 3BF was degraded in 45 min of irradiation. The pseudo-first-order kinetic models were used and the rate constants were evaluated with pseudo first order rate constants of 4.10 × 10-2 min-1. The main advantage of the photocatalyst coated on glass overcomes the difficulties in separation and recycle of photocatalyst suspensions.

Rate constant for the reaction of OH with CH3CCl2F (HCFC-141b) determined by relative rate measurements with CH4 and CH3CCl3

NASA Technical Reports Server (NTRS)

Huder, Karin; Demore, William B.

1993-01-01

Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.

Determination of the strong coupling constant from jet rates in deep inelastic scattering

NASA Astrophysics Data System (ADS)

Ahmed, T.; Aid, S.; Andreev, V.; Andrieu, B.; Appuhn, R.-D.; Arpagaus, M.; Babaev, A.; Baehr, J.; Bán, J.; Baranov, P.; Barrelet, E.; Bartel, W.; Barth, M.; Bassler, U.; Beck, H. P.; Behrend, H.-J.; Belousov, A.; Berger, Ch.; Bergstein, H.; Bernardi, G.; Bernet, R.; Bertrand-Coremans, G.; Besançon, M.; Beyer, R.; Biddulph, P.; Bizot, J. C.; Blobel, V.; Borras, K.; Botterweck, F.; Boudry, V.; Braemer, A.; Brasse, F.; Braunschweig, W.; Brisson, V.; Bruncko, D.; Brune, C.; Buchholz, R.; Büngener, L.; Bürger, J.; Büsser, F. W.; Buniatian, A.; Burke, S.; Buschhorn, G.; Campbell, A. J.; Carli, T.; Charles, F.; Clarke, D.; Clegg, A. B.; Clerbaux, B.; Colombo, M.; Contreras, J. G.; Cormack, C.; Coughlan, J. A.; Courau, A.; Coutures, Ch.; Cozzika, G.; Criegee, L.; Cussans, D. G.; Cvach, J.; Dagoret, S.; Dainton, J. B.; Danilov, M.; Dau, W. D.; Daum, K.; David, M.; Deffur, E.; Delcourt, B.; Del Buono, L.; De Roeck, A.; De Wolf, E. A.; Di Nezza, P.; Dollfus, C.; Dowell, J. D.; Dreis, H. B.; Droutskoi, A.; Duboc, J.; Düllmann, D.; Dünger, O.; Duhm, H.; Ebert, J.; Ebert, T. R.; Eckerlin, G.; Efremenko, V.; Egli, S.; Ehrlichmann, H.; Eichenberger, S.; Eichler, R.; Eisele, F.; Eisenhandler, E.; Ellison, R. J.; Elsen, E.; Erdmann, M.; Erdmann, W.; Evrard, E.; Favart, L.; Fedotov, A.; Feeken, D.; Felst, R.; Feltesse, J.; Ferencei, J.; Ferrarotto, F.; Flamm, K.; Fleischer, M.; Flieser, M.; Flügge, G.; Fomenko, A.; Fominykh, B.; Forbush, M.; Formánek, J.; Foster, J. M.; Franke, G.; Fretwurst, E.; Gabathuler, E.; Gabathuler, K.; Gamerdinger, K.; Garvey, J.; Gayler, J.; Gebauer, M.; Gellrich, A.; Genzel, H.; Gerhards, R.; Goerlach, U.; Goerlich, L.; Gogitidze, N.; Goldberg, M.; Goldner, D.; Gonzalez-Pineiro, B.; Gorelov, I.; Goritchev, P.; Grab, C.; Grässler, H.; Grässler, R.; Greenshaw, T.; Grindhammer, G.; Gruber, A.; Gruber, C.; Haack, J.; Haidt, D.; Hajduk, L.; Hamon, O.; Hampel, M.; Hanlon, E. M.; Hapke, M.; Haynes, W. J.; Heatherington, J.; Heinzelmann, G.; Henderson, R. C. W.; Henschel, H.; Herma, R.; Herynek, I.; Hess, M. F.; Hildesheim, W.; Hill, P.; Hill, K. H.; Hilton, C. D.; Hladký, J.; Hoeger, K. C.; Höppner, M.; Horisberger, R.; Huet, Ph.; Hufnagel, H.; Ibbotson, M.; Itterbeck, H.; Jabiol, M.-A.; Jacholkowska, A.; Jacobsson, C.; Jaffre, M.; Janoth, J.; Jansen, T.; Jönsson, L.; Johannsen, K.; Johnson, D. P.; Johnson, L.; Jung, H.; Kalmus, P. I. P.; Kant, D.; Kaschowitz, R.; Kasselmann, P.; Kathage, U.; Kaufmann, H. H.; Kazarian, S.; Kenyon, I. R.; Kermiche, S.; Keuler, C.; Kiesling, C.; Klein, M.; Kleinwort, C.; Knies, G.; Ko, W.; Köhler, T.; Köhne, J. H.; Kolanoski, H.; Kole, F.; Kolya, S. D.; Korbel, V.; Korn, M.; Kostka, P.; Kotelnikov, S. K.; Krämerkämper, T.; Krasny, M. W.; Krehbiel, H.; Krücker, D.; Krüger, U.; Krüner-Marquis, U.; Kubenka, J. P.; Küster, H.; Kuhlen, M.; Kurča, T.; Kurzhöfer, J.; Kuznik, B.; Lacour, D.; Lamarche, F.; Lander, R.; Landon, M. P. J.; Lange, W.; Lanius, P.; Laporte, J.-F.; Lebedev, A.; Leverenz, C.; Levonian, S.; Ley, Ch.; Lindner, A.; Lindström, G.; Linsel, F.; Lipinski, J.; List, B.; Loch, P.; Lohmander, H.; Lopez, G. C.; Lubimov, V.; Lüke, D.; Magnussen, N.; Malinovski, E.; Mani, S.; Maraček, R.; Marage, P.; Marks, J.; Marshall, R.; Martens, J.; Martin, R.; Martyn, H.-U.; Martyniak, J.; Masson, S.; Mavroidis, T.; Maxfield, S. J.; McMahon, S. J.; Mehta, A.; Meier, K.; Mercer, D.; Merz, T.; Meyer, C. A.; Meyer, H.; Meyer, J.; Mikocki, S.; Milstead, D.; Moreau, F.; Morris, J. V.; Müller, G.; Müller, K.; Murín, P.; Nagovizin, V.; Nahnhauer, R.; Naroska, B.; Naumann, Th.; Newman, P. R.; Newton, D.; Neyret, D.; Nguyen, H. K.; Niebergall, F.; Niebuhr, C.; Nisius, R.; Nowak, G.; Noyes, G. W.; Nyberg-Werther, M.; Oakden, M.; Oberlack, H.; Obrock, U.; Olsson, J. E.; Panaro, E.; Panitch, A.; Pascaud, C.; Patel, G. D.; Peppel, E.; Perez, E.; Phillips, J. P.; Pichler, Ch.; Pitzl, D.; Pope, G.; Prell, S.; Prosi, R.; Rädel, G.; Raupach, F.; Reimer, P.; Reinshagen, S.; Ribarics, P.; Rick, H.; Riech, V.; Riedlberger, J.; Riess, S.; Rietz, M.; Robertson, S. M.; Robmann, P.; Roloff, H. E.; Roosen, R.; Rosenbauer, K.; Rostovtsev, A.; Rouse, F.; Royon, C.; Rüter, K.; Rusakov, S.; Rybicki, K.; Rylko, R.; Sahlmann, N.; Sanchez, E.; Sankey, D. P. C.; Savitsky, M.; Schacht, P.; Schiek, S.; Schleper, P.; von Schlippe, W.; Schmidt, C.; Schmidt, D.; Schmidt, G.; Schöning, A.; Schröder, V.; Schuhmann, E.; Schwab, B.; Schwind, A.; Seehausen, U.; Sefkow, F.; Seidel, M.; Sell, R.; Semenov, A.; Shekelyan, V.; Sheviakov, I.; Shooshtari, H.; Shtarkov, L. N.; Siegmon, G.; Siewert, U.; Sirois, Y.; Skillicorn, I. O.; Smirnov, P.; Smith, J. R.; Soloviev, Y.; Spitzer, H.; Starosta, R.; Steenbock, M.; Steffen, P.; Steinberg, R.; Stella, B.; Stephens, K.; Stier, J.; Stiewe, J.; Stösslein, U.; Strachota, J.; Straumann, U.; Struczinski, W.; Sutton, J. P.; Tapprogge, S.; Taylor, R. E.; Tchernyshov, V.; Thiebaux, C.; Thompson, G.; Truöl, P.; Turnau, J.; Tutas, J.; Uelkes, P.; Usik, A.; Valkár, S.; Valkárová, A.; Vallée, C.; Van Esch, P.; Van Mechelen, P.; Vartapetian, A.; Vazdik, Y.; Vecko, M.; Verrecchia, P.; Villet, G.; Wacker, K.; Wagener, A.; Wagener, M.; Walker, I. W.; Walther, A.; Weber, G.; Weber, M.; Wegener, D.; Wegner, A.; Wellisch, H. P.; West, L. R.; Willard, S.; Winde, M.; Winter, G.-G.; Wright, A. E.; Wünsch, E.; Wulff, N.; Yiou, T. P.; Žáček, J.; Zarbock, D.; Zhang, Z.; Zhokin, A.; Zimmer, M.; Zimmermann, W.; Zomer, F.; Zuber, K.; H1 Collaboration

1995-02-01

Jet rates in deep inelastic electron proton scattering are studied with the H1 detector at HERA for momentum transfers squared between 10 and 4000 GeV 2. It is shown that they can be quantitatively described by perturbative QCD in next to leading order making use of the parton densities of the proton and with the strong coupling constant αs as a free parameter. The measured value, αs( MZ2) = 0.123 ± 0.018, is in agreement both with determinations from e+e- annihilation at LEP using the same observable and with the world average.

Rate constant for the reaction NH2 + NO from 216 to 480 K

NASA Technical Reports Server (NTRS)

Stief, L. J.; Brobst, W. D.; Nava, D. F.; Borkowski, R. P.; Michael, J. V.

1982-01-01

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

The effects of cutting or of stretching skeletal muscle in vitro on the rates of protein synthesis and degradation

NASA Technical Reports Server (NTRS)

Seider, M. J.; Kapp, R.; Chen, C.-P.; Booth, F. W.

1980-01-01

Skeletal muscle preparations using cut muscle fibers have often been used in studies of protein metabolism. The present paper reports an investigation of the effect of muscle cutting or stretching in vitro on the rates of protein synthesis and/or degradation. Protein synthesis and content, and ATP and phosphocreatine levels were monitored in soleus and extensor digitorum longus muscles from the rat with various extents of muscle fiber cuts and following stretching to about 120% the resting length. Rates of protein synthesis are found to be significantly lower and protein degradation higher in the cut muscles than in uncut controls, while ATP and phosphocreatine concentrations decreased. Stretched intact muscles, on the other hand, are observed to have higher concentrations of high-energy phosphates than unstretched muscles, while rates of protein degradation were not affected. Results thus demonstrate that the cutting of skeletal muscle fibers alters many aspects of muscle metabolism, and that moderate decreases in ATP concentration do not alter rates of protein concentration in intact muscles in vitro.

Effect of pH on the adsorption and photocatalytic degradation of sulfadimidine in Vis/g-C3N4 progress.

PubMed

Yang, Bin; Mao, Xuhui; Pi, Liu; Wu, Yixiao; Ding, Huijun; Zhang, Weihao

2017-03-01

In this study, g-C 3 N 4 was synthesized by thermal polycondensation of melamine and was characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, UV-visible diffuse reflection spectroscopy, and scanning electron microscopy. Results showed that g-C 3 N 4 degraded sulfadimidine (SMD) under visible light, in which the adsorption and photocatalytic degradation was influenced by pH. The maximum adsorption capacity was achieved at approximately pH 5. The highest degradation rate constant was obtained at strong acid and alkali. In addition, the degradation mechanism of g-C 3 N 4 was evaluated with the help of quencher agents. The intermediates, degradation pathways, and mineralization of SMD were also determined to evaluate the degradation and oxidation ability of g-C 3 N 4 .

[Evaluation of the influence of humidity and temperature on the drug stability by initial average rate experiment].

PubMed

He, Ning; Sun, Hechun; Dai, Miaomiao

2014-05-01

To evaluate the influence of temperature and humidity on the drug stability by initial average rate experiment, and to obtained the kinetic parameters. The effect of concentration error, drug degradation extent, humidity and temperature numbers, humidity and temperature range, and average humidity and temperature on the accuracy and precision of kinetic parameters in the initial average rate experiment was explored. The stability of vitamin C, as a solid state model, was investigated by an initial average rate experiment. Under the same experimental conditions, the kinetic parameters obtained from this proposed method were comparable to those from classical isothermal experiment at constant humidity. The estimates were more accurate and precise by controlling the extent of drug degradation, changing humidity and temperature range, or by setting the average temperature closer to room temperature. Compared with isothermal experiments at constant humidity, our proposed method saves time, labor, and materials.

Inflation with a smooth constant-roll to constant-roll era transition

NASA Astrophysics Data System (ADS)

Odintsov, S. D.; Oikonomou, V. K.

2017-07-01

In this paper, we study canonical scalar field models, with a varying second slow-roll parameter, that allow transitions between constant-roll eras. In the models with two constant-roll eras, it is possible to avoid fine-tunings in the initial conditions of the scalar field. We mainly focus on the stability of the resulting solutions, and we also investigate if these solutions are attractors of the cosmological system. We shall calculate the resulting scalar potential and, by using a numerical approach, we examine the stability and attractor properties of the solutions. As we show, the first constant-roll era is dynamically unstable towards linear perturbations, and the cosmological system is driven by the attractor solution to the final constant-roll era. As we demonstrate, it is possible to have a nearly scale-invariant power spectrum of primordial curvature perturbations in some cases; however, this is strongly model dependent and depends on the rate of the final constant-roll era. Finally, we present, in brief, the essential features of a model that allows oscillations between constant-roll eras.

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.

Hydroxyapatite degradation and biocompatibility

NASA Astrophysics Data System (ADS)

Wang, Haibo

Hydroxyapatite (HA) is widely used as a bioactive ceramics since it forms a chemical bonding to bone. The disadvantage of this material is its poor mechanical properties. HA can be degraded in body, which is the reason for its bioactivity, but too fast degradation rate could cause negative effects, such as macrophage present, particle generation, and even implant clinical failure. HA degradation rate will be greatly changed under many conditions: purity, HA form (i.e. bulk form, porous form, coating, or HA/polymer composites), microstructure, implant site, body conditions, etc. Although much work has been done in HA properties and application areas, the HA degradation behavior and mechanism under these different conditions are still not clear. In this research, three aspects of HA degradation have been studied: (1) Two very common impurities---Tri-Calcium Phosphate (TCP) and Calcium Oxide and their influences on HA degradation in vitro and in vivo, (2) influence of HA/polymer composite form on HA degradation, (3) HA material particle generation and related mechanism. From the in vitro and in vivo tests on bulk HA disks with various Ca/P ratios, HA degradation can clearly be found. The degradation level is different in different Ca/P ratio samples as well as in different test environments. In same test environment, non-stoichiometric HA samples have higher degradation rate than stoichiometric HA. HA/PMMA composite design successfully intensifies HA degradation both in vitro and in vivo. Grain boundary damage can be found on in vivo test samples, which has not been clearly seen on bulk HA degraded surface. HA particle generation is found in in vitro and in vivo HA/PMMA composite surface and in vivo bulk HA surface. Sintering temperature and time does affect HA grain size, and this affect HA degradation rate. Intergranular fracture is found in a several micron zone close to the Ca/P ratio 1.62 and 1.67 sample degraded surfaces. At Ca/P ratio greater than 1.667, after

SU-F-T-344: Commissioning Constant Dose Rate VMAT in the Raystation Treatment Planning System for a Varian Clinac IX

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

Pursley, J; Gueorguiev, G; Prichard, H

Purpose: To demonstrate the commissioning of constant dose rate volumetric modulated arc therapy (VMAT) in the Raystation treatment planning system for a Varian Clinac iX with Exact couch. Methods: Constant dose rate (CDR) VMAT is an option in the Raystation treatment planning system, enabling VMAT delivery on Varian linacs without a RapidArc upgrade. Raystation 4.7 was used to commission CDR-VMAT for a Varian Clinac iX. Raystation arc model parameters were selected to match machine deliverability characteristics. A Varian Exact couch model was added to Raystation 4.7 and commissioned for use in VMAT optimization. CDR-VMAT commissioning checks were performed on themore » linac, including patient-specific QA measurements for 10 test patients using both the ArcCHECK from Sun Nuclear Corporation and COMPASS from IBA Dosimetry. Multi-criteria optimization (MCO) in Raystation was used for CDR-VMAT planning. Results: Raystation 4.7 generated clinically acceptable and deliverable CDR-VMAT plans for the Varian Clinac. VMAT plans were optimized including a model of the Exact couch with both rails in the out positions. CDR-VMAT plans generated with MCO in Raystation were dosimetrically comparable to Raystation MCO-generated IMRT plans. Patient-specific QA measurements with the ArcCHECK on the couch showed good agreement with the treatment planning system prediction. Patient-specific, structure-specific, multi-statistical parameter 3D QA measurements with gantry-mounted COMPASS also showed good agreement. Conclusion: Constant dose rate VMAT was successfully modeled in Raystation 4.7 for a Varian Clinac iX, and Raystation’s multicriteria optimization generated constant dose rate VMAT plans which were deliverable and dosimetrically comparable to IMRT plans.« less

Degradation of methadone by the sunlight/FC process: Kinetics, radical species participation and influence of the water matrix.

PubMed

Hsieh, Ming-Chi; Panchangam, Sri Chandana; Lai, Webber Wei-Po; Lin, Angela Yu-Chen

2018-06-12

Free chlorine sunlight photolysis (sunlight/FC) markedly enhances the degradation rate of methadone, a synthetic opioid used medically, over that obtained using sunlight alone. The pseudo-first-order rate constants of methadone degradation under acidic conditions ([methadone] = 0.2 μM, [free chlorine] = 4 μM, and pH = 4) for sunlight/FC and sunlight photolysis are 7.0 ± 1.1 × 10 -2  min -1 and 1.4 ± 0.2 × 10 -2  min -1 , respectively. The improved methadone degradation can be attributed to the production of HO and reactive chlorine species (RCS) during sunlight/FC photolysis. HO and RCS predominantly accounted for degradation during sunlight/FC photolysis under acidic and neutral conditions, while direct photolysis was the major contributor towards methadone degradation in alkaline conditions. The initial pH (pH 4-11) and free chlorine concentration (1-6 μM) significantly influenced the overall degradation efficiency of methadone. The presence of HCO 3 - , Cl - and dissolved organic matters, which may competitively react with HO and RCS, retard the degradation of methadone in synthetic wastewater. Consequently, a 50% lower methadone degradation rate was observed when deionized (DI) water was replaced with tap water. These results emphasize the need to consider different water matrices when applying sunlight/FC photolysis for water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

NASA Technical Reports Server (NTRS)

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

1980-01-01

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-Dichlorophenanthrene.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Wang, Wenxing

2015-02-01

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl₂Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl₂Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35 × 10(-12)cm(3) molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of 9,10-Cl₂Phe determined by OH radicals is about 5.05 days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl₂Phe and should contribute to clarifying its atmospheric fate. Copyright © 2014 Elsevier B.V. All rights reserved.

Real-time motion-based H.263+ frame rate control

NASA Astrophysics Data System (ADS)

Song, Hwangjun; Kim, JongWon; Kuo, C.-C. Jay

1998-12-01

Most existing H.263+ rate control algorithms, e.g. the one adopted in the test model of the near-term (TMN8), focus on the macroblock layer rate control and low latency under the assumptions of with a constant frame rate and through a constant bit rate (CBR) channel. These algorithms do not accommodate the transmission bandwidth fluctuation efficiently, and the resulting video quality can be degraded. In this work, we propose a new H.263+ rate control scheme which supports the variable bit rate (VBR) channel through the adjustment of the encoding frame rate and quantization parameter. A fast algorithm for the encoding frame rate control based on the inherent motion information within a sliding window in the underlying video is developed to efficiently pursue a good tradeoff between spatial and temporal quality. The proposed rate control algorithm also takes the time-varying bandwidth characteristic of the Internet into account and is able to accommodate the change accordingly. Experimental results are provided to demonstrate the superior performance of the proposed scheme.