Redox behavior of Tc(VII)/Tc(IV) under various reducing conditions in 0.1 M NaCl solutions

2013 ◽  
Vol 101 (5) ◽  
pp. 323-332 ◽  
Author(s):  
Taishi Kobayashi ◽  
Andreas C. Scheinost ◽  
D. Fellhauer ◽  
Xavier Gaona ◽  
Marcus Altmaier
2018 ◽  
Vol 106 (4) ◽  
pp. 259-279 ◽  
Author(s):  
Agost Tasi ◽  
Xavier Gaona ◽  
David Fellhauer ◽  
Melanie Böttle ◽  
Jörg Rothe ◽  
...  

AbstractThe solubility and redox behavior of hydrous Pu(IV) oxide was comprehensively investigated by an experimental multi-method approach as a function of different redox conditions in 0.1 M NaCl solutions, allowing a detailed characterization of Pu(IV) and Pu(III) solubility and solid phase stability in these systems. Samples were prepared at ~3≤pHm≤~6 (pHm=–log${{\text{m}}_{{{\text{H}}^{\text{ + }}}}})$and ~8≤pHm≤~13 atT=(22±2)°C under Ar atmosphere. No redox buffer was used in one set of samples, whereas mildly and strongly reducing redox conditions were buffered in two series with hydroquinone or SnCl2, respectively, resulting in (pe+pHm)=(9.5±1) and (2±1). XRD, XANES and EXAFS confirmed the predominance of Pu(IV) and the nanocrystalline character of the original, aged PuO2(ncr,hyd) solid phase used as a starting material. Rietveld analysis of the XRD data indicated an average crystal (domain) size of (4±1) nm with a mean cell parameter of (5.405±0.005) Å. The solubility constant of this solid phase was determined as log$^ * K{^\circ _{{\text{s}},0}}$=–(58.1±0.3) combining solubility data in acidic conditions and redox speciation by solvent extraction and CE–SF–ICP–MS. This value is in excellent agreement with the current thermodynamic selection in the NEA-TDB. Synchrotron-basedin-situXRD, XANES and EXAFS indicate that PuO2(ncr,hyd) is the solid phase controlling the solubility of Pu in hydroquinone buffered samples. Under these redox conditions and ~8≤pHm≤~13, the solubility of Pu is very low (~10−10.5m) and pH-independent. This is consistent with the solubility equilibrium PuO2(am,hyd)+2H2O(l)⇔ Pu(OH)4(aq). Althoughin-situXRD unequivocally shows the predominance of PuO2in Sn(II)-buffered systems, XANES analyses indicate a significant contribution of Pu(III) (30±5%) in the solid phases controlling the solubility of Pu at (pe+pHm)=(2±1). For this system, EXAFS shows a systematic shortening of Pu–O and Pu–Pu distances compared to the starting Pu material and hydroquinone-buffered systems. The solubility of Pu remains very low (~10−10.5m) at pHm>9, but shows a very large scattering (~10−9–10−10.5m) at pHm=8. Experimental observations collected in Sn(II) buffered systems can be explained by the co-existence of both PuO2(ncr,hyd) and Pu(OH)3(am) solid phases, but also by assuming the formation of a sub-stoichiometric PuO2−x(s) phase. This extensive study provides robust upper limits for Pu solubility in alkaline, mildly to strongly reducing conditions relevant in the context of nuclear waste disposal. The potential role of Pu(III) in the solid phases controlling the solubility of Pu under these conditions is analysed and discussed in view of the current NEA-TDB thermodynamic selection, which supports the predominance of PuO2(am,hyd) and constrains the formation of Pu(OH)3(am) at pHm>8 outside the stability field of water.


1988 ◽  
Vol 127 ◽  
Author(s):  
E. Freude ◽  
W. Lutze ◽  
C. Rüssel ◽  
H. A. Schaeffer

ABSTRACTTechnetium is a potentially hazardous radionuclide in the waste vitrification process as its oxides are volatile. Electrochemical measurements, i.e. potentiometry and voltammetry are applied to investigate the redox reactions of Tc in the glass melt. Re is studied for comparison. Under normal oxidizing conditions Tc is in the -T-state, and substancial losses of Tc occur as a result of compound volatility. Reducing conditions lead to the formation of TcO2, which precipitates from the melt. Stronger reducing conditions lead to the formation of metallic Tc


1998 ◽  
Vol 79 (01) ◽  
pp. 177-185 ◽  
Author(s):  
Ashia Siddiqua ◽  
Michael Wilkinson ◽  
Vijay Kakkar ◽  
Yatin Patel ◽  
Salman Rahman ◽  
...  

SummaryWe report the characterization of a monoclonal antibody (MAb) PM6/13 which recognises glycoprotein IIIa (GPIIIa) on platelet membranes and in functional studies inhibits platelet aggregation induced by all agonists examined. In platelet-rich plasma, inhibition of aggregation induced by ADP or low concentrations of collagen was accompanied by inhibition of 5-hydroxytryptamine secretion. EC50 values were 10 and 9 [H9262]g/ml antibody against ADP and collagen induced responses respectively. In washed platelets treated with the cyclooxygenase inhibitor, indomethacin, PM6/13 inhibited platelet aggregation induced by thrombin (0.2 U/ml), collagen (10 [H9262]g/ml) and U46619 (3 [H9262]M) with EC50 = 4, 8 and 4 [H9262]g/ml respectively, without affecting [14C]5-hydroxytryptamine secretion or [3H]arachidonate release in appropriately labelled cells. Studies in Fura 2-labelled platelets revealed that elevation of intracellular calcium by ADP, thrombin or U46619 was unaffected by PM6/13 suggesting that the epitope recognised by the antibody did not influence Ca2+ regulation. In agreement with the results from the platelet aggregation studies, PM6/13 was found to potently inhibit binding of 125I-fibrinogen to ADP activated platelets. Binding of this ligand was also inhibited by two other MAbs tested, namely SZ-21 (also to GPIIIa) and PM6/248 (to the GPIIb-IIIa complex). However when tested against binding of 125I-fibronectin to thrombin stimulated platelets, PM6/13 was ineffective in contrast with SZ-21 and PM6/248, that were both potent inhibitors. This suggested that the epitopes recognised by PM6/13 and SZ-21 on GPIIIa were distinct. Studies employing proteolytic dissection of 125I-labelled GPIIIa by trypsin followed by immunoprecipitation with PM6/13 and analysis by SDS-PAGE, revealed the presence of four fragments at 70, 55, 30 and 28 kDa. PM6/13 did not recognize any protein bands on Western blots performed under reducing conditions. However Western blotting analysis with PM6/13 under non-reducing conditions revealed strong detection of the parent GP IIIa molecule, of trypsin treated samples revealed recognition of an 80 kDa fragment at 1 min, faint recognition of a 60 kDa fragment at 60 min and no recognition of any product at 18 h treatment. Under similar conditions, SZ-21 recognized fragments at 80, 75 and 55 kDa with the 55kDa species persisting even after 18 h trypsin treatment. These studies confirm the epitopes recognised by PM6/13 and SZ-21 to be distinct and that PM6/13 represents a useful tool to differentiate the characteristics of fibrinogen and fibronectin binding to the GPIIb-IIIa complex on activated platelets.


MRS Advances ◽  
2020 ◽  
Vol 5 (61) ◽  
pp. 3123-3131
Author(s):  
Mario Flores Nicolas ◽  
Marina Vlasova ◽  
Pedro Antonio Márquez Aguilar ◽  
Mykola Kakazey ◽  
Marcos Mauricio Chávez Cano ◽  
...  

AbstractThe low-temperature synthesis of bricks prepared from high-siliceous clays by the method of plastic molding of blanks was used. For the preparation of brick blanks, binary and ternary mixtures of high-siliceous clays, black sand, and bottle glass cullet were used. Gray-black low-porosity and high-porosity ceramics was obtained by sintering under conditions of oxygen deficiency. It has been established that to initiate plastic in mixtures containing high-siliceous clay, it is necessary to add montmorillonite/bentonite additives, carry out low-temperature sintering, and introduce low-melting glass additives with a melting point ranging from 750 to 800 °C. The performed investigations have shown that the sintering of mixtures with a total content of iron oxide of about 5 wt% under reducing conditions at Tsint. = 800°C for 8 h leads to the formation of glass ceramics consisting of quartz, feldspars, and a phase. The main sources of the appearance of a dark color is the formation of [Fe3+O4]4- and [Fe3+O6]9- anions in the composition of the glass phase and feldspars. By changing the contents of clay, sand, and glass in sintering, it is possible to obtain two types of ceramic materials: (a) in the form of building bricks and (b) in the form of porous fillers.


1995 ◽  
Vol 31 (1) ◽  
pp. 117-128 ◽  
Author(s):  
Jean-Pierre Arcangeli ◽  
Erik Arvin

This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols, chlorophenols, nitrophenol, chlorobenzenes and aromatic nitrogen-, sulphur- or oxygen-containing heterocyclic compounds (NSO-compounds). Furthermore, a comparison with degradation rates observed for easily degradable organics is also presented. At concentrations below 20-100 μg/l the degradation of the aromatic compounds was typically controlled by first order kinetics. The first-order surface removal rate constants were surprisingly similar, ranging from 2 to 4 m/d. It appears that NSO-compounds inhibit the degradation of aromatic hydrocarbons, even at very low concentrations of NSO-compounds. Under nitrate-reducing conditions, toluene was easily biodegraded. The xylenes and ethylbenzene were degraded cometabolically if toluene was used as a primary carbon source; their removal was influenced by competitive inhibition with toluene. These interaction phenomena are discussed in this paper and a kinetic model taking into account cometabolism and competitive inhibition is proposed.


Author(s):  
So Jeong Park ◽  
Min Hee Joo ◽  
Ju Hyun Yang ◽  
Sung-Min Hong ◽  
Choong Kyun Rhee ◽  
...  
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