scholarly journals Uranium migration through the Swiss Opalinus Clay varies on the metre scale in response to differences of the stability constant of the aqueous, ternary uranyl complex Ca<sub>2</sub>UO<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub>

2021 ◽  
Vol 56 ◽  
pp. 97-105
Author(s):  
Theresa Hennig ◽  
Michael Kühn
Keyword(s):  
Stability Constant ◽  
Host Rock ◽  
Uranyl Complex ◽  
Opalinus Clay ◽  
Double Layers ◽  
Anionic Complex ◽  
Order Of Magnitude ◽  
Uranium Migration ◽  
The Stability ◽  
Exclusion Effect

Abstract. The simulation of uranium migration through the Swiss Opalinus Clay is used as an example to quantify the influence of varying values of a stability constant in the underlying thermodynamic database on the migration lengths for the repository scale. Values for the stability constant of the neutral, ternary uranyl complex Ca2UO2(CO3)3 differ in literature by up to one order of magnitude. Within the studied geochemical system, either the neutral or the anionic complex CaUO2(CO3)32- is the predominant one, depending on the chosen value for the neutral complex. This leads to a changed interaction with the diffuse double layers (DDL) enveloping the clay minerals and thus can potentially influence the diffusive transport of uranium. Hence, two identical scenarios only differing in the value for the stability constant of the Ca2UO2(CO3)3 complex were applied in order to quantify and compare the migration lengths of uranium on the host rock scale (50 m) after a simulation time of one million years. We ran multi-component diffusion simulations for the shaly and sandy facies in the Opalinus Clay. A difference in the stability constant of 1.33 log units changes the migration lengths by 5 to 7 m for the sandy and shaly facies, respectively. The deviation is caused by the anion exclusion effect. However, with a maximum diffusion distance of 22 m, the influence of the stability constant of the Ca2UO2(CO3)3 complex on uranium migration in the Opalinus Clay is negligible on the host rock scale.

Does a stability constant decide on a repository permit?

2021 ◽  
Author(s):  
Theresa Hennig ◽  
Michael Kühn
Keyword(s):  
Stability Constant ◽  
Clay Minerals ◽  
Stability Constants ◽  
Nuclear Waste ◽  
Host Rock ◽  
Mass Action ◽  
Opalinus Clay ◽  
Diffusive Transport ◽  
Predominant Species ◽  
The Stability

&lt;p&gt;Safety of a nuclear waste repository is based to a large extent on the isolation of the radioactive waste within a suitable host rock. Clay rocks provide an option due to their very low hydraulic conductivity only allowing diffusive transport. Diffusion processes in clay formations are complex due to the diffuse double layers (DDL) enveloping the clay minerals to compensate their net surface charge and the associated different migration behaviour for cationic, anionic and neutral species. Therefore, determination of the speciation of an element in the porewater is essential to quantify migration lengths precisely. Safety assessments are based on numerical simulations to cover time periods of up to one million years and thus the predominant species of a radionuclide, dependent on the stability constants within the law of mass action, might be signififcant.&lt;/p&gt;&lt;p&gt;In the present study, we use uranium, one of the main components in spent fuel, as an example for the diffusion in the Swiss Opalinus Clay, a potential host rock for the storage of nuclear waste. In the geochemical system, uranium is mainly present as U(VI) in ternary uranyl complexes with calcium and carbonate, whereby speciation depends on the selected thermodynamic data (Hennig et al., 2020). For instance, the stability constants for the neutral uranyl complex Ca&lt;sub&gt;2&lt;/sub&gt;UO&lt;sub&gt;2&lt;/sub&gt;(CO&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt; differ slightly in literature. Depending on the selected one, either the neutral or the anionic complex CaUO&lt;sub&gt;2&lt;/sub&gt;(CO&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;2-&lt;/sup&gt; is the predominant species in the system with an associated varying interaction with the DDL of the clay minerals. With our one-dimensional, multi-component diffusion models we quantified the effect of the selected stability constant on the diffusion length for the host rock scale.&lt;/p&gt;&lt;p&gt;The chemistry in the porewater of the three facies of the Opalinus Clay, shaly, sandy and carbonate-rich, plays a key role for the sorption processes (Hennig et al., 2020) as well as for the composition and thickness of the DDL and therewith the diffusive transport. Based on our results, we show, that the influence of the predominant uranium species on the migration lengths varies between the individual facies, but is overall negligible for the host rock scale. Consequently, a stability constant is not decisive for the required thickness of the host rock as geological barrier.&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;Hennig, T.; Stockmann, M.; K&amp;#252;hn, M. Simulation of diffusive uranium transport and sorption processes in the Opalinus Clay. Applied Geochemistry 2020, 123. doi:10.1016/j.apgeochem.2020.104777.&lt;/p&gt;

scholarly journals Potential Uranium Migration within the Geochemical Gradient of the Opalinus Clay System at the Mont Terri

Minerals ◽  
2021 ◽  
Vol 11 (10) ◽  
pp. 1087
Author(s):  
Theresa Hennig ◽  
Michael Kühn
Keyword(s):  
Pore Water ◽  
Host Rock ◽  
Multicomponent Diffusion ◽  
Opalinus Clay ◽  
Potential Host ◽  
In Situ Experiments ◽  
Homogeneous Models ◽  
Uranium Migration ◽  
Clay System ◽  
Mont Terri

Transport properties of potential host rocks for nuclear waste disposal are typically determined in laboratory or in-situ experiments under geochemically controlled and constant conditions. Such a homogeneous assumption is no longer applicable on the host rock scale as can be seen from the pore water profiles of the potential host rock Opalinus Clay at Mont Terri (Switzerland). The embedding aquifers are the hydro-geological boundaries, that established gradients in the 210 m thick low permeable section through diffusive exchange over millions of years. Present-day pore water profiles were confirmed by a data-driven as well as by a conceptual scenario. Based on the modelled profiles, the influence of the geochemical gradient on uranium migration was quantified by comparing the distances after one million years with results of common homogeneous models. Considering the heterogeneous system, uranium migrated up to 24 m farther through the formation depending on the source term position within the gradient and on the partial pressure of carbon dioxide pCO2 of the system. Migration lengths were almost equal for single- and multicomponent diffusion. Differences can predominantly be attributed to changes in the sorption capacity, whereby pCO2 governs how strong uranium migration is affected by the geochemical gradient. Thus, the governing parameters for uranium migration in the Opalinus Clay can be ordered in descending priority: pCO2, geochemical gradients, mineralogical heterogeneity.

Beryllium-chrome-azurol-S complexes

1968 ◽  
Vol 21 (3) ◽  
pp. 603 ◽  
Author(s):  
WG Baldwin ◽  
DR Stranks
Keyword(s):  
Ionic Strength ◽  
Complex Formation ◽  
Ion Exchange ◽  
Stability Constant ◽  
Anionic Complex ◽  
Acidity Constants ◽  
Chrome Azurol S ◽  
Major Species ◽  
The Stability ◽  
Ph Range

Complex formation between the aquated beryllium cation and the tetrabasic dyestuff chrome-azurol-S (H4CAS) has been studied by spectrophotometric, potentiometric, electrophoretic, and ion-exchange techniques. At least two complexes are shown to exist within the pH range 3-6. The major species is the anionic complex BeHCAS- for which log β11, = 4.66 � 0.08 at 25� and at ionic strength 0.lM (NaClO4) Coordination of beryllium is considered to occur at the quinonoid-,). carboxylato site in the HCAS8- ligand. The stability constant for the dinuclear species Be2CASO is shown to be log β21 = 15.8 � 0.1 under the same medium conditions. The dinuclear complex interferes with spectrophotometric measurements at beryllium concentrations exceeding 2.5 x 10-4. The acidity constants of H4CAS were determined at 25� and at an ionic strength 0.IM (NaClO,) as pK2a = 2.25 � 0.10,pK3a, = 4.88 � 0.05, pK4, = 11.75 � 0.05, whilst pK1a = -1.2 � 0.4.

Synthesis and solvatochromic studies of 2- amino-3-phenolazo1-(4-sulfophenyl)-3-methyi-5-pyrozolone and use it for the determination of trace amount of Nickel (II) in blood samples

2016 ◽  
Vol 5 (10) ◽  
pp. 4920
Author(s):  
Amar M. Ali ◽  
Hussain. J. Mohammed*
Keyword(s):  
Stability Constant ◽  
Trace Amount ◽  
Benzenesulfonic Acid ◽  
Determination Method ◽  
Blood Samples ◽  
Determination Of Nickel ◽  
Normal Human ◽  
The Stability ◽  
Normal Human Blood

A new, simple, sensitive and rapid spectrophotometric method is proposed for the determination of trace amount of Nickel (II). The method is based on the formation of a 1:2 complex with 4-(4-((2-hydroxy-6-nitrophenyl) diazenyl) -3-methyl-5-oxo-2, 5-dihydro-1H-pyrazol-1-yl) benzenesulfonic acid (2-ANASP) as a new reagent is developed. The complex has a maximum absorption at 516 nm and εmax of 1. 84 X 105 L. mol-1. cm-1. A linear correlation (0. 25 – 4. 0μg. ml-1) was found between absorbance at λmax and concentration. The accuracy and reproducibility of the determination method for various known amounts of Nickel (II) were tested. The results obtained are both precise (RSD was 1. 2 %) and accurate (relative error was 0. 787 %). The effect of diverse ions on the determination of Nickel (II) to investigate the selectivity of the method were also studied. The stability constant of the product was 0. 399 X 106 L. mol-1. The proposed method was successfully applied to the analysis of diabetes blood and normal human blood. 

Electrolysis soy protein isolate-based oleogels prepared with an emulsion-templated approach

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Dianyu Yu ◽  
Yan Chen ◽  
Xing Chen ◽  
Yunyan Huang ◽  
Liqi Wang ◽  
...  
Keyword(s):  
Soy Protein ◽  
Xanthan Gum ◽  
Binding Capacity ◽  
Soy Protein Isolate ◽  
Single Layer ◽  
Protein Isolate ◽  
Regulatory Limits ◽  
Order Of Magnitude ◽  
The Stability ◽  
Oil Binding

Abstract This research focuses on the use of protein-polyphenol complex and protein-polyphenol: polysaccharide complexes to prepare oleogels through an emulsion-templated approach. Electrolysis soy protein isolate (ESPI) could be effectively adsorbed on the surface of a single-layer emulsion to increase the particle size. The order of the negative charges of the emulsion after adding polysaccharides was xanthan gum (XG)> pectin> carboxymethyl cellulose (CMC). Rheological behavior showed that the stability of the double-layer emulsions increased, and the viscoelasticity increased around one order of magnitude with the addition of polysaccharides. The oil binding capacity (OBC) of the oleogel prepared by adding polysaccharides increased to more than 97%. The peroxide value (PV) and anisidine value (AV) of XG oleogel were the minimum values in all samples. The AV and POV were within the regulatory limits of China after storage for 21 days. This provides a reference to design of ESPI-based oleogel for different applications.

Determination of the Stability Constant of the Calcium Dioxalate Complex

Urolithiasis ◽  
1981 ◽  
pp. 447-451
Author(s):  
John R. Burns ◽  
Birdwell Finlayson ◽  
Arthur Smith
Keyword(s):  
Stability Constant ◽  
The Stability

SODIUM CHELATES OF ETHYLENEDIAMINETETRAACETIC ACID

1963 ◽  
Vol 41 (1) ◽  
pp. 18-20 ◽  
Author(s):  
Vladimir Palaty
Keyword(s):  
Stability Constant ◽  
Stability Constants ◽  
Ethylenediaminetetraacetic Acid ◽  
Glass Electrode ◽  
Neutral Solution ◽  
Experimental Conditions ◽  
The Stability ◽  
Sensitive Method

The stability constant of the sodium chelate of EDTA was determined by means of a sodium-sensitive glass electrode. It appears that a hydrogen chelate of the formula NaHY2− is formed in the neutral solution of EDTA, but is very unstable. The stability constants, pKNaY = −2.61 and pKNaHY = 0.03, are comparable to the value obtained by Schwarzenbach and Ackermann under different experimental conditions by a less sensitive method.

scholarly journals New Spectrophotometric Method for Determination of Cadmium

2009 ◽  
Vol 6 (s1) ◽  
pp. S496-S500
Author(s):  
K. S. Parikh ◽  
R. M. Patel ◽  
K. N. Patel
Keyword(s):  
Stability Constant ◽  
Spectrophotometric Method ◽  
Basic Medium ◽  
Buffer Solution ◽  
Solution Ph ◽  
Yellow Colour ◽  
Maximum Absorbance ◽  
The Stability

The reagent 2-hydroxy-4-n-butoxy-5-bromopropiophenone thiosemicarbazone (HBBrPT) has been used for the determination of Cd(II) by using spectrophotometric method. The reagent HBBrPT gave an intense yellow colour with Cd(II) solution in basic medium. The maximum absorbance was observed at 440 nm, in basic buffer solution (pH 10.00). The molor absorptivity and Sandell’s sensitivity of Cd(II)-HBBrPT complex were 4035 mol-1cm-1and 0.02765 μg cm-2respectively. The stability constant of 1:2 Cd(II)-HBBrPT complex was 8.46×106. The effect of various iron was also studied.

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