Modelling the Behaviour of Organic Degradation Products

1988 ◽  
Vol 127 ◽  
Author(s):  
J. E. Cross ◽  
F. T. Ewart ◽  
B. F. Greenfield
Keyword(s):  
Organic Waste ◽  
Degradation Products ◽  
Organic Ligand ◽  
Solubility Enhancement ◽  
Major Objective ◽  
Experimental Conditions ◽  
Organic Species ◽  
Ph Values ◽  
Alkaline Conditions ◽  
Significant Factors

ABSTRACTResults are presented from recent studies at Harwell which show that the degradation products which are formed when certain organic waste materials are exposed to the alkaline conditions typical of a cementitious environment, can enhance the solubility of plutonium, even at pH values as high as 12, by significant factors. Characterisation of the degradation products has been undertaken but the solubility enhancement does not appear to be related to the concentration of any of the major organic species that have been identified in the solutions. While it has not been possible to identify by analysis the organic ligand responsible for the increased solubility of plutonium, the behaviour of D-Saccharic acid does approach the behaviour of the degradation products. The PHREEQE code has been used to simulate the solubility of plutonium in the presence of D-Saccharic acid and other model degradation products, in order to explain the solubility enhancement. The extrapolation of the experimental conditions to the repository is the major objective, but in this work the ability of a model to predict the behaviour of plutonium over a range of experimental conditions has been tested.

scholarly journals Photocatalytic Treatment of Wastewater Containing Simultaneous Organic and Inorganic Pollution: Competition and Operating Parameters Effects

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 855
Author(s):  
Ahmed Amine Azzaz ◽  
Salah Jellali ◽  
Nasser Ben Harharah Hamed ◽  
Atef El Jery ◽  
Lotfi Khezami ◽  
...  
Keyword(s):  
Ultra Violet ◽  
Degradation Process ◽  
Molar Ratio ◽  
Experimental Conditions ◽  
Retention Capacity ◽  
Isotherm Study ◽  
Related Data ◽  
Ph Values ◽  
Pseudo Second Order ◽  
Maximum Retention

In the present study, methylene blue (MB) removal from aqueous solutions via the photocatalytic process using TiO2 as a catalyst in the presence of external ultra-violet light (UV) was investigated. The results of adsorption in the absence of UV radiation showed that adsorption reached an equilibrium state at 60 min. The experimental kinetic data were found to be well fitted by the pseudo-second-order model. Furthermore, the isotherm study suggested that dye uptake by TiO2 is a chemisorption process with a maximum retention capacity of 34.0 mg/g. The photodegradation of MB was then assessed under various experimental conditions. The related data showed that dye mineralization decreased when dye concentrations were increased and was favored at high pH values and low salt concentrations. The simultaneous presence of organic and inorganic pollution (Zinc) was also evaluated. The effect of the molar ratio Zn2+/MB+ in the solution at different pH values and NaCl concentrations was also monitored. The corresponding experimental results showed that at low values of Zn2+ in the solution (30 mg/L), the kinetic of the MB removal became faster until reaching an optimum at Zn2+/MB+ concentrations of 60/60 mg/L; it then slowed down for higher concentrations. The solutions’ carbon contents were measured during the degradation process and showed total mineralization after about 5 h for the optimal Zn2+/MB+ condition.

Sorption of radionuclides to a cementitious backfill material under near-field conditions

2012 ◽  
Vol 76 (8) ◽  
pp. 3401-3410 ◽  
Author(s):  
M. Felipe-Sotelo ◽  
J. Hinchliff ◽  
N. Evans ◽  
P. Warwick ◽  
D. Read
Keyword(s):  
Organic Compounds ◽  
Degradation Products ◽  
Cellulose Degradation ◽  
Near Field ◽  
Organic Ligand ◽  
Sorption Isotherms ◽  
Field Conditions ◽  
Sorption Behaviour ◽  
Backfill Material ◽  
Order Of Magnitude

AbstractThe sorption behaviour of I−, Cs+, Ni2+, Eu3+, Th4+ and UO2+2on NRVB (Nirex reference vault backfill) a possible vault backfill, at pH 12.8 was studied. Sorption isotherms generated were compared to results obtained in the presence of cellulose degradation products (CDP). Whereas Cs was not affected by the presence of the organic compounds, a notable reduction in the sorption of Th and Eu to cement was observed. The results also indicated limited removal of Ni from solution (with or without an organic ligand) by sorption, the concentration in solution seemingly being determined solely by solubility processes. In the case of uranium, the presence of CDP increased the sorption to cement by almost one order of magnitude. Further studies into the uptake of CDP by cement are being undertaken to identify the mechanism(s) responsible.

Validation of Analytical Methods for Tacrolimus Determination in Poly(ε-caprolactone) Nanocapsules and Identification of Drug Degradation Products

2021 ◽  
Vol 21 (12) ◽  
pp. 5920-5928
Author(s):  
Guilherme A. Camargo ◽  
Amanda M. Lyra ◽  
Fernanda M. Barboza ◽  
Barbara C. Fiorin ◽  
Flávio L. Beltrame ◽  
...  
Keyword(s):  
Liquid Chromatography ◽  
High Performance ◽  
Degradation Products ◽  
Multiple Reaction Monitoring ◽  
Forced Degradation ◽  
Alkaline Stress ◽  
Drug Degradation ◽  
Relative Standard ◽  
Polymeric Nanocapsules ◽  
Alkaline Conditions

The aim of this paper was to use chromatographic tools for validating an analytical method for the tacrolimus (TAC) determination in polymeric nanocapsules and for identifying the drug degradation products after alkaline stress. A rapid Ultra-High-Performance Liquid Chromatography coupled with photo-diode array (UHPLC-PDA) method was successfully performed using the following chromatographic conditions: the Shimadzu Shim-pack XR-ODS III C18 column (100 mm×2.00 mm, 2.2 μm), the mobile phase consisting of methanol and acidified ultrapure water (89:11 v/v), the flow rate of 0.55 mL·min−1, and the ultraviolet (UV) detection at 235 nm. This method was validated as per International Council for Harmonisation (ICH) guidelines. In addition, a TAC forced degradation assay was carried out after alkaline stress and its degradation products were investigated using Liquid Chromatography coupled tandem mass spectroscopy (LC-MS/MS). The calibration curve was linear in the range of 100.0–300.0 μg·mL−1 (r >0.9999). Accuracy was confirmed by the TAC recovery of 96.55 to 98.19%. Precision (intraday and interday) were demonstrated by relative standard deviation lower than 0.89% and 3.25%, respectively. Selectivity and robustness were also proved. The method developed it was successfully applied to quantify TAC from polymeric nanocapsules, showing a high loading efficiency rate (>96.47%). The main drug degradation product observed in a multiple reaction monitoring (MRM) experiment was m/z 844, confirming the susceptibility of TAC under alkaline conditions; this finding was first time described.

The Effect of a Single Oral Morning Dose of Nizatidine and Ranitidine on Intragastric pH under Basal Conditions and after Pentagastrin Stimulation

1992 ◽  
Vol 20 (6) ◽  
pp. 454-460 ◽  
Author(s):  
M Lazzaroni ◽  
O Sangaletti ◽  
G Bianchi Porro
Keyword(s):  
Drug Administration ◽  
Inhibitory Action ◽  
Glass Electrode ◽  
Intragastric Ph ◽  
Morning Dose ◽  
Experimental Conditions ◽  
Duodenal Ulcers ◽  
Ph Values ◽  
Antisecretory Activity ◽  
Single Blind

A comparison was made of the antisecretory activity of orally administered nizatidine and ranitidine by measuring intragastric pH under basal conditions and during and after pentagastrin stimulation. Intragastric pH values were measured with a bipolar glass electrode in 10 patients with healed duodenal ulcers treated with nizatidine or ranitidine according to a randomized single-blind design. The antisecretory activity of the two drugs was similar during the 4 h of monitoring following drug administration. Nizatidine, however, showed a more rapid inhibitory action than ranitidine, producing a significantly greater increase in pH with respect to basal values during pentagastrin infusion. In the period following infusion the pH values observed with ranitidine were higher than with nizatidine, but not significantly so. Under these experimental conditions, therefore, the antisecretory activity of nizatidine was shown to be more rapid than that of ranitidine and equally effective.

scholarly journals Mechanism of the process of decomposition of apatitis with phosphoric acid

2019 ◽  
Vol 81 (1) ◽  
pp. 294-297
Author(s):  
R. F. Sabirov ◽  
A. F. Makhotkin ◽  
Yu. N. Sakharov ◽  
I. A. Makhotkin ◽  
I. Yu. Sakharov
Keyword(s):  
Phosphoric Acid ◽  
Ph Value ◽  
Batch Reactor ◽  
Experimental Studies ◽  
Hydrogen Ions ◽  
Experimental Conditions ◽  
Monocalcium Phosphate ◽  
Ph Values ◽  
Whole Process ◽  
Proportional Increase

Experimental studies of the kinetics and mechanism of the process, decomposition of apatite by phosphoric acid, in the Apatite-H3PO4-H2O system without the addition of sulfuric acid have been performed. The study of the decomposition process of Kovdorsky apatite with certain particle sizes was carried out in a batch reactor with a volume of 1 dm3 with stirring of the reaction mixture, and an initial concentration of phosphoric acid of 17% by weight, at a temperature of 78–82 °C. Observation of the process was carried out by determining the concentration of phosphoric acid and the concentration of monocalcium phosphate. The acidity of the reaction mixture was determined by the pH meter readings (pH-105 MA with a glass combined-ESC-10603 electrode). It was shown that during the whole process a constant smooth increase in the pH value of the reaction mixture to pH 6 occurs. Comparison of the pH values of the reaction mixture during the actual at the time of determining the concentration of phosphoric acid and pH of phosphoric acid of the corresponding concentration in the aqueous solution shows that the pH value of the reaction mixture is significantly affected by the presence of monocalcium phosphate gel. During the process, during the first thirty minutes, the concentration of phosphoric acid decreases from 17 to 10% by weight, the corresponding quantitative formation of monocalcium phosphate gel and a proportional increase in the pH of the reaction mixture. Then, as the concentration of phosphoric acid decreases, the process slows down and does not proceed to the end under the experimental conditions. The dependence of the concentration of hydrogen ions in the reaction mixture on the time of the process of decomposition of apatite in phosphoric acid, which is presented in logarithmic coordinates, shows that the mechanism of formation of hydrogen ions during the whole process does not change. Thus, it is shown that the process of decomposition of apatite by phosphoric acid in the Apatite-H3PO4-H2O system proceeds with the formation of an intermediate product - monocalcium phosphate gel. When this occurs, a corresponding significant change in the pH values of the reaction mixture occurs. During the whole process there is a constant decrease in the concentration of phosphoric acid.

scholarly journals Pulverized river shellfish shells as a 904 cheap adsorbent for removing of malathion from water: Examination of the isotherms, kinetics, thermodynamics and optimization of the experimental conditions by the response surface method

2021 ◽  
Vol 69 (4) ◽  
pp. 871-904
Author(s):  
Zlate Veličković ◽  
Bogdan Vujičić ◽  
Vladica Stojanović ◽  
Predrag Stojisavljević ◽  
Zoran Bajić ◽  
...  
Keyword(s):  
Response Surface ◽  
Response Surface Method ◽  
Organophosphorus Pesticide ◽  
Isothermal Model ◽  
Experimental Conditions ◽  
Langmuir Adsorption ◽  
Ph Values ◽  
Surface Method ◽  
Adsorption Data ◽  
Pseudo Second Order

Introduction/purpose: In this study, we investigated the possibility of removing the organophosphorus pesticide malathion from water using a new adsorbent based on the biowaste of river shell shards from the Anodonta Sinadonta woodiane family, a material that accumulates in large quantities as waste on the banks of large rivers. Two adsorbents were tested - mechanically comminuted river shells (MRM) and mechanosynthetic hydroxyapatite from comminuted river shells (RMHAp). Methods: The obtained adsorbents were characterized and tested for the removal of the organophosphorus pesticide malathion from water. In order to predict the optimal adsorption conditions using the Response Surface Method (RSM), the authors investigated the influence of variable factors (adsorption conditions), pH values, adsorbent doses, contact times, and temperatures on the adsorbent capacity. Results: The best adsorption of malathion was achieved at mean pH values between 6.0 and 7.0. The adsorption data for malathion at 25, 35, and 45 °C were compared using the Langmuir, Freundlich, DubininRadushkevich (DR), and Temkin isothermal models, as well as pseudofirst order, pseudo-second order and Elovic kinetic models for modeling adsorption kinetics. The maximum Langmuir adsorption capacity for MRM and RMHAp at 25 °C was 46,462 mg g-1 and 78,311 mg g-1 , respectively. Conclusion: The results have showed that malathion adsorption on both adsorbents follows the pseudo-second kinetic model and the Freundlich isothermal model. The thermodynamic parameters indicate the endothermic, feasible, and spontaneous nature of the adsorption process.

scholarly journals First-Principles Mechanistic Insights into the Hydrogen Evolution Reaction on Ni2P Electrocatalyst in Alkaline Medium

Catalysts ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 307
Author(s):  
Russell W. Cross ◽  
Nelson Y. Dzade
Keyword(s):  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Density Functional ◽  
Hydrogen Adsorption ◽  
Density Functional Theory Calculations ◽  
Transition Metal Doping ◽  
Experimental Conditions ◽  
Functional Theory ◽  
Alkaline Conditions ◽  
Modification Of The Surface

Nickel phosphide (Ni2P) is a promising material for the electrocatalytic generation of hydrogen from water. Here, we present a chemical picture of the fundamental mechanism of Volmer–Tafel steps in hydrogen evolution reaction (HER) activity under alkaline conditions at the (0001) and (10 1 ¯ 0) surfaces of Ni2P using dispersion-corrected density functional theory calculations. Two terminations of each surface (Ni3P2- and Ni3P-terminated (0001); and Ni2P- and NiP-terminated (10 1 ¯ 0)), which have been shown to coexist in Ni2P samples depending on the experimental conditions, were studied. Water adsorption on the different terminations of the Ni2P (0001) and (10 1 ¯ 0) surfaces is shown to be exothermic (binding energy in the range of 0.33−0.68 eV) and characterized by negligible charge transfer to/from the catalyst surface (0.01−0.04 e−). High activation energy barriers (0.86−1.53 eV) were predicted for the dissociation of water on each termination of the Ni2P (0001) and (10 1 ¯ 0) surfaces, indicating sluggish kinetics for the initial Volmer step in the hydrogen evolution reaction over a Ni2P catalyst. Based on the predicted Gibbs free energy of hydrogen adsorption (ΔGH*) at different surface sites, we found that the presence of Ni3-hollow sites on the (0001) surface and bridge Ni-Ni sites on the (10 1 ¯ 0) surface bind the H atom too strongly. To achieve facile kinetics for both the Volmer and Heyrovsky–Tafel steps, modification of the surface structure and tuning of the electronic properties through transition metal doping is recommended as an important strategy.

scholarly journals 14C content in CANDU spent fuel cladings and its release under alkaline conditions

Radiocarbon ◽  
2018 ◽  
Vol 60 (6) ◽  
pp. 1773-1786 ◽  
Author(s):  
C Bucur ◽  
M Fulger ◽  
I Florea ◽  
A Tudose
Keyword(s):  
Nuclear Power ◽  
Impurity Content ◽  
Spent Fuel ◽  
Acid Dissolution ◽  
Gaseous Species ◽  
Accelerated Corrosion ◽  
Organic Species ◽  
Accelerated Corrosion Tests ◽  
Alkaline Conditions ◽  
Chemical Conditions

ABSTRACTThe total 14C content and its partition between inorganic and organic species were measured on irradiated Zy-4 samples from a CANDU spent fuel rod transferred from Cernavoda Nuclear Power Plant (NPP). Long-term leaching tests and accelerated corrosion tests were carried out to measure the 14C release and corrosion rate, respectively, in chemical conditions relevant to cementitious environment. Experimentally measured 14C inventory was compared to the theoretically one predicted based on the irradiation history and impurity content of Zy-4 by means of ORIGEN computations. CANDU SF claddings have a 14C content of around 2 × 104 Bq/g of Zy-4, mainly as organic compounds (more than 99%). The total 14C content measured by acid dissolution/wet oxidation method is in good agreement with the value estimated by ORIGEN simulations for an average burn-up of 7 MWd/kgU. The total 14C released as dissolved species after 18 days and 18 months of Zy-4 immersing in alkaline solution are similar, indicating that a small amount of 14C was available as instant release fraction (0.05% from the initial 14C content) followed by a very low release rate that could not be measured by liquid scintillation counting. In alkaline conditions, 14C is released predominantly (∼70%) as soluble species, but also inorganic 14C was measured as gaseous species. From the soluble 14C released during leaching test, more than 60% was found to be as organic species. Generally, corrosion rates values ranging between 46 and 130 nm/yr were measured by the linear polarization resistance method. In addition, defects and cracks were observed on the oxide layer by scanning electron microscopy (SEM) investigation.

Relation between Surface Area and Surface Potential Change during (co)Polyesters Degradation as Langmuir Monolayer

MRS Advances ◽  
2019 ◽  
Vol 5 (12-13) ◽  
pp. 667-677
Author(s):  
Natalia A. Tarazona ◽  
Rainhard Machatschek ◽  
Andreas Lendlein
Keyword(s):  
Surface Area ◽  
Surface Potential ◽  
Degradation Products ◽  
Degradation Mechanism ◽  
Langmuir Monolayers ◽  
Langmuir Monolayer ◽  
Potential Change ◽  
Alkaline Conditions ◽  
Hydrolysis Of ◽  
Random Scission

ABSTRACTPolyhydroxyalkanoates (PHAs) are degradable (co)polyesters synthesized by microorganisms with a variety of side-chains and co-monomer ratios. PHAs can be efficiently hydrolyzed under alkaline conditions and by PHA depolymerase enzymes, altering their physicochemical properties. Using 2D Langmuir monolayers as model system to study the degradation behavior of macromolecules, we aim to describe the the interdependency between the degradation of two PHAs and the surface potential, which influences material-proteins interaction and cell response. We hypothesize that the mechanism of hydrolysis of the labile ester bonds in (co)polyesters defines the evolution of the surface potential, owing to the rate of accumulation of charged insoluble degradation products. The alkaline hydrolysis and the enzymatically catalyzed hydrolysis of PHAs were previously defined as chain-end scission and random-scission mechanisms, respectively. In this study, these two distinct scenarios are used to validate our model. The surface potential change during the chain-end scission of poly(3-R-hydroxybutyrate) (PHB) under alkaline conditions was compared to that of the enzymatically catalyzed hydrolysis (random-scission) of poly[(3-R-hydroxyoctanoate)-co-(3-R-hydroxyhexanoate)] (PHOHHx), using the Langmuir monolayer technique. In the random-scission mechanism the dissolution of degradation products, measured as a decrease in the area per molecule, was preceded by a substantial change of the surface potential, provoked by the negative charge of the broken ester bonds accumulated in the air-water interface. In contrast, when chains degraded via the chain-ends, the surface potential changed in line with the dissolution of the material, presenting a kinetic dependent on the surface area of the monolayers. These results provide a basis for understanding PHAs degradation mechanism. Future research on (co)polymers with different main-chain lengths might extend the elucidation of the surface potential development of (co)polyesters as Langmuir monolayer.

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