Migration Behavior of Selenium in the Presence of Iron in Bentonite

2014 ◽  
Vol 1665 ◽  
pp. 157-163
Author(s):  
Kazuya Idemitsu ◽  
Hikaru Kozaki ◽  
Daisuke Akiyama ◽  
Masanao Kishimoto ◽  
Masaru Yuhara ◽  
...  
Keyword(s):  
Oxidation State ◽  
High Level Waste ◽  
Dry Density ◽  
Precipitation Reaction ◽  
Migration Behavior ◽  
Ferrous Ions ◽  
Edge Structure ◽  
Tracer Solution ◽  
High Level ◽  
X Ray Absorption

ABSTRACTSelenium (Se) is an important element for assessing the safety of high-level waste disposal. Se is redox-sensitive, and its oxidation state varies from -2 to 6 depending on the redox conditions and pH of the solution. Large quantities of ferrous ions formed in bentonite due to corrosion of carbon steel overpack after the closure of a repository are expected to maintain a reducing environment near the repository. Therefore, the migration behavior of Se in the presence of Fe in bentonite was investigated by electrochemical experiments. Na2SeO3 solution was used as tracer solution. Dry density range of bentonite was from 0.8 to 1.4 ×103 kg/m3.Results indicated that Se was strongly retained by the processes such as precipitation reaction with ferrous ions in bentonite. Se K-edge X-ray absorption near-edge structure (XANES) measurements were performed at the BL-11 beamline at SAGA Light Source, and the results revealed that the oxidation state of Se in the bentonite remained Se(IV).

Migration behavior of plutonium affected by ferrous ion in compacted bentonite by using electrochemical technique

2014 ◽  
Vol 1665 ◽  
pp. 79-84
Author(s):  
Daisuke Akiyama ◽  
Kazuya Idemitsu ◽  
Yaohiro Inagaki ◽  
Tatsumi Arima ◽  
Kenji Konashi ◽  
...  
Keyword(s):  
Dispersion Coefficient ◽  
Migration Velocity ◽  
Corrosion Products ◽  
High Level Waste ◽  
Dry Density ◽  
Migration Behavior ◽  
Ferrous Ions ◽  
Compacted Bentonite ◽  
Reducing Environment ◽  
Experiment Duration

ABSTRACTThe migration behavior of plutonium is expected to be affected by the corrosion products of carbon steel in compacted bentonite at high-level waste repositories. Electrochemical experiments were carried out to simulate the reducing environment created by ferrous iron ions in equilibrium with anoxic corrosion products of iron. The concentration profiles of plutonium could be described by the convection -dispersion equation to obtain two migration parameters: apparent migration velocity Va and apparent dispersion coefficient Da. The apparent migration velocity was evaluated within 1 nm/s and was found to be independent of the experiment duration and the dry density of bentonite in the interval 0.8-1.4 Mg/m3. The apparent dispersion coefficient increased with the experiment duration at a dry density of 1.4 Mg/m3. The results for other dry densities also showed the same trend. These findings indicate that plutonium migration likely starts after ferrous ions reach the plutonium, in other words, the reducing environment due to ferrous ions could change the chemical form of plutonium and/or the characteristics of compacted bentonite. The apparent diffusion coefficient was estimated to be around 0.5 to 2.2 µm2/s and increased with decreasing the dry density of bentonite.

X-ray Absorption Fine Structure Studies of Speciation of Technetium in Borosilicate Glasses

2003 ◽  
Vol 802 ◽  
Author(s):  
Wayne W. Lukens ◽  
David K. Shuh ◽  
Isabelle S. Muller ◽  
David A. McKeown
Keyword(s):  
Fine Structure ◽  
Oxidation State ◽  
Organic Material ◽  
Glass Frit ◽  
High Level Waste ◽  
Borosilicate Glasses ◽  
X Ray ◽  
Synthesis Conditions ◽  
High Level ◽  
X Ray Absorption

ABSTRACTA series of glass samples were prepared analogously to high level waste glass using either glass frit or glass precursors combined with a high level waste surrogate containing NaTcO4. Three different technetium species were observed in these glasses depending upon the synthesis conditions. If the glasses were prepared by reducing NaTcO4 to TcO2•2H2O with hydrazine or if a large amount of organic material was present, inclusions of TcO2 were observed. If no organic material was present, technetium was incorporated as TcO4−. If only a small amount of organic material was present, isolated Tc(IV) sites were observed in the glass. The relative technetium retention of these glasses was estimated from the Tc K-edge height, and had no correlation with the oxidation state of the technetium. Pertechnetate was well retained in these glasses.

A resistivity-based approach to determining the rates of groundwater seepage into buffer materials

2019 ◽  
Vol 482 (1) ◽  
pp. 205-212 ◽  
Author(s):  
T. Ishii ◽  
M. Kawakubo ◽  
H. Asano ◽  
I. Kobayashi ◽  
P. Sellin ◽  
...  
Keyword(s):  
Water Solution ◽  
High Level Waste ◽  
Dry Density ◽  
Chemical Alteration ◽  
Constant Rate ◽  
Buffer Material ◽  
The Status ◽  
Engineered Barriers ◽  
High Level ◽  
Saturation Front

AbstractBentonite-based buffer materials play an important safety role in engineered barriers planned for use in geological disposal repositories for radioactive high-level waste (HLW) in Japan. The effectiveness of buffer materials is dependent on the status of groundwater saturation during resaturation of the repository. Accordingly, it is important to determine the behaviour of buffer materials during saturation and predict post-saturation conditions such as the distribution of residual dry density and chemical alteration.In this study, the rate of groundwater uptake into a buffer material was determined to clarify the behaviour of the material during the saturation process. As mechanical changes and chemical alteration of buffer materials are generated by groundwater permeation, knowledge of the water uptake rate is necessary for the prediction of post-permeation conditions. In the experiment reported here, one-dimensional permeation by distilled water and a NaCl water solution at a constant rate was monitored over a period of more than seven years. The results indicated that the seepage and saturation front moved in proportion to the square root of the seepage time. The coefficient of the relationships between the seepage and the saturation fronts with time of the reference bentonite used in Japan was determined.

Oxygen Reduction Effect on T’-Pr2-xCexCuO4 Nanopowders in the Underdoped Regime Studied by X-Ray Absorption near Edge Structure

2018 ◽  
Vol 936 ◽  
pp. 93-97 ◽  
Author(s):  
Irfanita Resky ◽  
Putu Eka Dharma Putra ◽  
Triono Bambang ◽  
Saiyasombat Chatree ◽  
Kamonsuangkasem Krongthong ◽  
...  
Keyword(s):  
Oxidation State ◽  
Oxidation States ◽  
Edge Structure ◽  
X Ray ◽  
Reduction Annealing ◽  
Gas Atmosphere ◽  
Reduction Effect ◽  
Ar Gas ◽  
X Ray Absorption ◽  
Cu Ions

This research is aimed to examine oxidation state of Copper (Cu) in both as-synthesized and reduced T’-Pr2-xCexCuO4 (T’-PCCO) with x = 0, 0.10, and 0.15 using Cu K-edge x-ray absorption near edge structure (XANES). The T‘-PCCO nanopowders were successfully synthesized by the chemically dissolved method with HNO3 as a dissolving agent continued by calcination at 1000°C for 15 h. The reduced T’-PCCO nanopowders were obtained by reduction annealing process at 700°C for 5 h under Ar gas atmosphere. The analyses of XANES spectra show that oxidation states of the Cu ions in all of the T'-PCCO nanopowders have values between +1 and +2. This indicates the existence of electron doping in the CuO2 planes, even in the undoped T’-structure. It is found that the oxidation states of the Cu ions change after reduction annealing depending on the existence of apical oxygen in the T'-structure. Based on the XANES analyses, it is revealed that the change of oxidation state is influenced by the presence of both electron and hole carriers in the two-carrier model of T’-structure.

Using X-ray absorption near edge structure (XANES) spectroscopy to determine selenium oxidation states in animal mineral supplements and feeds

2004 ◽  
Vol 84 (2) ◽  
pp. 171-175 ◽  
Author(s):  
C. R. Christensen ◽  
J. N. Cutler ◽  
D. A. Christensen
Keyword(s):  
Oxidation State ◽  
Animal Feed ◽  
Xanes Spectroscopy ◽  
Elemental Selenium ◽  
Selenium Speciation ◽  
Edge Structure ◽  
X Ray ◽  
Mineral Supplements ◽  
Animal Feeds ◽  
X Ray Absorption

Synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy is a relatively new technique within the life sciences. XANES has been utilized to identify the location, oxidation state and spatial distribution of heavy metal elements in plants , neurons, blood and DNA, but has not been widely used in the animal sciences. Selenium content in animal feeds is monitored, as both selenium deficiencies and toxicities are associated with physiological disorders. Selenium is available as an animal feed in both inorganic and organic states. The bioavailability of selenium species has been tested in numerous animal trials; however, a simple, non-destructive test for selenium speciation is not available. The objective of this study was to determine whether XANES spectroscopy could be used to determine the selenium oxidation state found in various commercial animal feed products. A comparison of absorption spectra indicated that the animal mineral supplements contained an organoselenium or selenite. The processed animal feeds had a spectral profile similar to that of elemental selenium. Further experiments are necessary to determine the implication of selenium speciation on animal physiology. Key words: Selenium speciation, mineral supplements, ruminants, non-ruminants, synchrotron, XANES, X-ray

Oxidation State of Ti Atoms and Ti-O Bond Length on Natural Sapphire Gem-Materials Probed by X-Ray Absorption Spectroscopy

2017 ◽  
Vol 737 ◽  
pp. 585-589 ◽  
Author(s):  
Natthapong Monarumit ◽  
Wiwat Wongkokua ◽  
Somruedee Satitkune
Keyword(s):  
Bond Length ◽  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Germanium Detector ◽  
Blue Color ◽  
Edge Structure ◽  
X Ray ◽  
Fe Content ◽  
X Ray Absorption ◽  
Exafs Spectra

Sapphire, an inorganic gem-material in a variety of corundum, mainly consists of alpha-alumina (α-Al2O3) structure. The geological origins of sapphire are related to either basaltic or metamorphic rocks. The causes of the color on sapphire are some trace elements such as Cr, Fe, and Ti. It could be mentioned that Ti atoms have cooperated with Fe atoms for creating the blue color. In this study, X-ray absorption spectroscopy (XAS) technique focused on the x-ray absorption near edge structure (XANES) and the extended x-ray absorption fine structure (EXAFS) is employed to identify the oxidation state of Ti atoms and Ti-O bond length on sapphire samples. The Ti K-edge XANES and EXAFS spectra of natural sapphires were carried out using the 13-channel array germanium detector in fluorescence mode. The XANES spectra showed that the oxidation state of Ti was Ti4+ regardless of Fe content. Moreover, the Ti-O bond length on a-Al2O3 was equal to the Ti-O bond length on rutile (TiO2) analyzed from the EXAFS spectra. From these results, it could be concluded that the oxidation state of Ti atoms on natural sapphires was Ti4+ which substitutes Al3+ on the sapphire structure.

Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES)

2007 ◽  
Vol 103 (6) ◽  
pp. 568-571 ◽  
Author(s):  
Yasuhiro Konishi ◽  
Takeshi Tsukiyama ◽  
Norizoh Saitoh ◽  
Toshiyuki Nomura ◽  
Shinsuke Nagamine ◽  
...  
Keyword(s):  
Oxidation State ◽  
Direct Determination ◽  
Gold Deposits ◽  
Edge Structure ◽  
X Ray ◽  
Shewanella Algae ◽  
X Ray Absorption

Migration Behaviour of Lanthanides in Compacted Bentonite with Iron Corrosion Product Using Electrochemical Method

2012 ◽  
Vol 1475 ◽  
Author(s):  
Kazuya Idemitsu ◽  
Daisuke Akiyama ◽  
Yoshihiko Matsuki ◽  
Yusuke Irie ◽  
Yaohiro Inagaki ◽  
...  
Keyword(s):  
Carbon Steel ◽  
Dispersion Coefficient ◽  
Reference Electrode ◽  
High Level Waste ◽  
Dry Density ◽  
Migration Behavior ◽  
Iron Corrosion ◽  
Compacted Bentonite ◽  
Steel Coupon ◽  
Best Fit

ABSTRACTAfter the closure of a high-level waste repository, corrosion of the carbon steel overpack will occur. The corrosion products can then migrate into bentonite and affect the migration behavior of radionuclides in bentonite. Therefore, electrochemical experiments, with Fe2+ supplied by anodic corrosion of carbon steel, were carried out to study trivalent lanthanides in compacted bentonite. The interface between a carbon steel coupon and bentonite (dry density, 1.5 Mg/m3) was spiked with a tracer solution containing Nd(NO3)3, Eu(NO3)3, Dy(NO3)3, and Er(NO3)3. The carbon steel coupon was connected as the working electrode to a potentiostat and held at a constant potential between -550 and 0 mV (vs. Ag/AgCl reference electrode) for 7 days. A model using dispersion and electromigration could explain the measured profiles in the bentonite specimens. The best-fit electromigration velocity was related to the applied electric potential and was 1.0–3.8 nm/s for Nd, Eu, Dy, and Er ions. For these lanthanides, the best-fit dispersion coefficient was also related to the applied potential and was 0.8–1.6 μm2/s, and the dispersion length was calculated as 0.2 mm from the linear relationship between the dispersion coefficient and electromigration velocity. Finally, the apparent diffusion coefficient for these lanthanides was estimated as 0.6–0.9 μm2/s.

NMR Study of Interlayer and Non-interlayer Porewater in Water-saturated Bentonite and Montmorillonite

2013 ◽  
Vol 1518 ◽  
pp. 167-172
Author(s):  
Torbjörn Carlsson ◽  
Arto Muurinen ◽  
Andrew Root
Keyword(s):  
Spent Nuclear Fuel ◽  
Relative Volume ◽  
High Level Waste ◽  
Proton Relaxation ◽  
Dry Density ◽  
Nmr Study ◽  
Important Barrier ◽  
Relaxation Curves ◽  
High Level ◽  
Water Saturated

ABSTRACTBentonite is planned to be used in many countries as an important barrier in high-level waste repositories. Assessment of the barrier with regard to, inter alia, its ability to hinder transport of dissolved radionuclides leaking from a damaged canister containing spent nuclear fuel, requires quantitative data about the pore structure inside bentonite. The present NMR study was made in order to determine the number of distinguishable porewater phases in compacted water-saturated samples of MX-80 bentonite and Na-montmorillonite. The samples were compacted to dry densities in the interval 0.7-1.6 g/cm3 and subsequently saturated with Milli-Q water or 0.1 M NaCl solution in equilibrium cells. The NMR measurements were performed with a high-field 270 MHz NMR spectrometer using a short inter-pulse CPMG method to study proton T1ρ relaxation. The measured relaxation curves were found to consist of one faster and one slower proton relaxation. Subsequent analysis of the data indicated that the faster relaxation was associated with interlayer (IL) water between montmorillonite unit layers, while the slower one was associated with non-interlayer (non-IL) water located outside the interlayer spaces. The results indicate for compacted samples with a dry density of ≥ 1.0 g/cm3, that Na montmorillonite contains a larger relative volume of non-IL water than the corresponding MX-80 bentonite. This in turn, suggests that the stacking number in Na-montmorillonite is smaller than in MX-80 bentonite. Changing the porewater chemistry seemed to have some effect on the non-IL water content in the Na montmorillonite but not in the MX-80 bentonite.

scholarly journals A compact furnace for in situ X-ray absorption spectroscopy: design, fabrication and study of cationic oxidation states in Pr6O11 and NiO

2021 ◽  
Vol 28 (2) ◽  
pp. 455-460
Author(s):  
Suchinda Sattayaporn ◽  
Somboonsup Rodporn ◽  
Pinit Kidkhunthod ◽  
Narong Chanlek ◽  
Chutarat Yonchai ◽  
...  
Keyword(s):  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Heating Temperature ◽  
Reduction Process ◽  
Oxidation States ◽  
Quartz Tube ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

A well designed compact furnace has been designed for in situ X-ray absorption spectroscopy (XAS). It enables various heat ramps from 300 K to 1473 K. The furnace consists of heaters, a quartz tube, a circulated refrigerator and a power controller. It can generate ohmic heating via an induction process with tantalum filaments. The maximum heating rate exceeds 20 K min−1. A quartz tube with gas feedthroughs allows the mixing of gases and adjustment of the flow rate. The use of this compact furnace allows in situ XAS investigations to be carried out in transmission or fluorescence modes under controlled temperature and atmosphere. Moreover, the furnace is compact, light and well compatible to XAS. The furnace was used to study cationic oxidation states in Pr6O11 and NiO compounds under elevated temperature and reduced atmosphere using the in situ X-ray absorption near-edge structure (XANES) technique at beamline 5.2 SUT-NANOTEC-SLRI of the Synchrotron Light Research Institute, Thailand. At room temperature, Pr6O11 contains a mixture of Pr3+ and Pr4+ cations, resulting in an average oxidation state of +3.67. In situ XANES spectra of Pr (L 3-edge) show that the oxidation state of Pr4+ cations was totally reduced to +3.00 at 1273 K under H2 atmosphere. Considering NiO, Ni2+ species were present under ambient conditions. At 573 K, the reduction process of Ni2+ occurred. The Ni0/Ni2+ ratio increased linearly with respect to the heating temperature. Finally, the reduction process of Ni2+ was completely finished at 770 K.

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