Analysis of the HDO content in heavy water by ATR-FTIR

The applicability of ATR-FTIR for the determination of the HDO content in heavy water (D₂O) was investigated. Two groups of calibration standard solutions, of low contents (0–1 n% H₂O in heavy water) and of higher contents (0–10 n% H₂O in heavy water) were prepared by adding properly calculated amount of H₂O to D₂O by weight. The absorbances at 3400 cm⁻¹ (ν, O–H) against the calibration standards were measured five times using two kinds of interchangeable IREs (1 bound and 9 bound reflections). And four calibration curves were obtained by linear least square fit of the measured absorbances for the four different measurement conditions, which are (1) for low contents group using 1 bound reflection, (2) for low contents group using 9 bound reflections, (3) for higher contents group using 1 bound reflection, (4) for higher contents group using 9 bound reflections. Determined contents (c ₀) of each calibration standards for the four measurement conditions were obtained by the calibration curves and compared to the calculated contents (c _cal). The uncertainty sources were considered when the HDO in heavy water is determined according to the procedure of this work. The uncertainties u(c ₀) of the determined contents (c ₀) for the four different measurement conditions were calculated.     

Determination of water content in silica nanopowder using wavelength-dispersive X-ray fluorescence spectrometer

A wavelength-dispersive X-ray fluorescence (WDXRF) technique that uses the scattered radiation of the X-ray tube lines and the fluorescence radiation of an element present in a powder sample is proposed as a non-destructive method for the determination of the water content in silica powder. Although direct X-ray fluorescence analysis of water using WDXRF is not adequate for the quantitative determination of water in powder, due to the very low fluorescence yield for hydrogen and oxygen, the fluorescence signal of silicon (Si) in silica powder is attenuated by water, and is shown to decrease in proportion to the water content in silica powder. In addition, it is demonstrated that the Compton- and Rayleigh-scattering of the X-ray tube lines is proportional to the water content. The coefficients of determination, R², of the linear regression equations obtained from the calibration curves for all individual scattered radiations and for the fluorescence radiation of Si were > 0.90. The sum of the peak intensities of the four scattering signals, i.e. the Rayleigh-scattered Rh K–L_2,3 and Rh K–M_2,3 lines, and Compton-scattered Rh K–L_2,3 and Rh K–M_2,3 lines, also showed fairly good linearity and sensitivity over a very wide range of water content from 0 wt.% to 61.5 wt.%. However, porosity had a significant effect on the X-ray signal at low water content, in the range from 0 wt.% to 7.5 wt.%, where the sensitivity for the silica nanopowder with well-defined mesopores (~ 3 nm in diameter) decreased to 0.40 kcps/wt.%, from 0.99 kcps/wt.% for the non-porous silica nanopowder. The use of the Si fluorescence signal along with the scattered radiation of the X-ray tube lines expands the applicability of conventional XRF spectrometers to the quantitative determination of water content in silica powder.     

The application of radiochronometry during the 4th collaborative materials exercise of the nuclear forensics international technical working group (ITWG)

Journal of Radioanalytical and Nuclear Chemistry - In a recent international exercise, 10 international nuclear forensics laboratories successfully performed radiochronometry on three low enriched...     

Electronic absorption spectra of U (III) ion in a LiCl–KCl eutectic melt at 450 °C

We have measured the electronic absorption spectra of the U(III) ion in LiCl–KCl eutectic melt at 450 °C to understand its chemical behavior in the context of pyrochemical process of spent nuclear fuel. The UV–VIS spectra of the U(III) ion consist of two main peaks in the range of 400–600 nm which are attributable to the 5f³–5f²6d¹ transitions. With the aid of UV–VIS spectroscopic tool, in-situ measurement of chemical reactions of the U(III) with oxide ion as well as neodymium oxide was successfully achieved. The U(III) ion forms insoluble uranium oxide phases by reacting with oxide ion and lanthanide oxides.     

Overall approaches and experiences of first-time participants in the Nuclear Forensics International Technical Working Group’s Fourth Collaborative Material Exercise (CMX-4)

Journal of Radioanalytical and Nuclear Chemistry - The Fourth Collaborative Material Exercise (CMX-4) of the Nuclear Forensics International Technical Working Group (ITWG) registered the largest...     

The influence of humic acid on the pH-dependent sorption of americium(III) onto kaolinite

This work investigates the sorption of americium [Am(III)] onto kaolinite and the influence of humic acid (HA) as a function of pH (3–11). It has been studied by batch experiments (V/m = 250:1 mL/g, C _Am(III) = 1 × 10⁻⁵ mol/L, C _HA = 50 mg/L). Results showed that the Am(III) sorption onto the kaolinite in the absence of HA was typical, showing increases with pH and a distinct adsorption edge at pH 3–5. However in the presence of HA, Am sorption to kaolinite was significantly affected. HA was shown to enhance Am sorption in the acidic pH range (pH 3–4) due to the formation of additional binding sites for Am coming from HA adsorbed onto kaolinite surface, but reduce Am sorption in the intermediate and high pH above 6 due to the formation of aqueous Am-humate complexes. The results on the ternary interaction of kaolinite–Am–HA are compared with those on the binary system of kaolinite–HA and kaolinite–Am and adsorption mechanism with pH are discussed. Effect of different molecular weight of HA, with three HA fractions separated by ultrafiltration techniques, on the Am sorption to kaolinite were also studied. The results showed that the enhancement of the sorption of Am onto kaolinite at the acidic pH conditions (pH 3–4) was higher with HA fractions of higher molecular weight. Also, the Am sorption over a pH range from 6 to 10 decreased with decreasing molecular weight of HA.     

Application of laser photoacoustic spectroscopy for the detection of water vapor near 1.38 μm

Laser photoacoustic (PA) spectroscopy is applied for the determination of the trace content of water vapor using a differential Helmholtz resonant (DHR) cell and a narrow bandwidth diode laser operating near 1380 nm. The PA spectroscopy revealed a rich absorption spectra in this wavelength region and the observed result was compared with the HITRAN database. A multipass optical system was also developed by adopting one aluminum-coated flat mirror with a small uncoated spot for the laser introduction to the detection chamber and one aluminum-coated concave mirror. The multipass optical system enabled the enhancement of the PA signal up to eight times when compared to the single pass case. The calibration curve was plotted by measuring PA signals for various pressures of the water vapor. The sensitivity of the PA detection system is estimated as 7.3×10¹² molecules cm⁻³ with a signal-to-noise ratio (SNR) of 1.     

Optimization study on sample pretreatment of spent fuel storage rack

In order to evaluate radionuclide inventories as an essential item for the permanent disposal of spent fuel storage racks, chemical conditions for a sample pretreatment of a spent fuel storage rack were studied. Especially, the surface microstructure and the radionuclide distributions for the spent fuel storage rack were investigated by using a SEM–EDX and γ-spectrometer for minimizing the matrix effect which could affect a chemical separation process of some β-emitting radionuclides. The samples were pretreated with a mixed solution of 5 M HCl and 2 M HNO₃ by an ultrasonic surface leaching method. Some radionuclides in the raw racks showed the radioactivity of 10²–10³ Bq for about 10 g of sample weight. From the sample pretreatment, it was confirmed that almost all radionuclides in the rack were completely extracted from the rack when the dissolved thickness of the rack became a maximum 15 μm by the ultrasonic surface leaching method. The established pretreatment method was applied for all spent fuel storage rack generated from Korean NPPs to determine the scaling factor. The radioactivities of ⁶⁰Co and ¹³⁷Cs radionuclides in the pretreated solutions were in the range of 4.9E−1~1.5E+2 and 1.2E−1~9.0E+0 Bq/g, respectively.