[보고서]지화학환경 악티나이드 화학 연구

차완식

보고서 정보

주관연구기관

한국원자력연구원
Korea Atomic Energy Research Institute

연구책임자

차완식

참여연구자

김희경 , 정의창 , 조혜륜 , 조혜진 , 김태형 , 유정보 , 박진규 , 이창헌 , 조상기 , 송병철

보고서유형

1단계보고서

발행국가

대한민국

언어

한국어

발행년월

2018-11

과제시작연도

2018

주관부처

과학기술정보통신부
Ministry of Science and ICT

과제관리전문기관

한국연구재단
National Research Foundation of Korea

등록번호

TRKO201900019709

과제고유번호

1711064819

사업명

원자력기술개발사업(R&D)

DB 구축일자

2020-04-11

키워드

악티나이드.지화학환경.열역학 자료.분광학.화학종 규명.가수분해.나노입자.용해도.착물.흡착.산화환원.Actinide.Geochemical environment.Thermodynamic data.Spectroscopy.Chemical speciation.Hydrolysis.Nanoparticle.Solubility.Complex.Adsorption.Redox reaction.

$The concept of KBS-3, a special method for final disposal of spent nuclear fuel(Swedish nuclear fuel and waste management company, SKB). It has three protective barriers: copper canisters, Bentonite clay and the Swedish bedrock (Granite type) which contains groundwater that flows through fractures in the rock[2-1-5]$ 표 The concept of KBS-3, a special method for final disposal of spent nuclear fuel(Swedish nuclear fuel and waste management company, SKB). It has three protective barriers: copper canisters, Bentonite clay and the Swedish bedrock (Granite type) which contains groundwater that flows through fractures in the rock[2-1-5]
표 Peltier-thermostated cell holder (6×6) for Spectrophotometer (CARY5000, Agilent). Temperature range of 5-90 °C
표 Absorption spectra of Pu(VI) in 0.1 M HClO4 measured at various temperatures. Each absorption spectrum at a certain temperature is an average of three repeated absorption measurements
표 Molar absorption coefficient decreases at higher temperature. Error bars represent standard deviation of three different measurements
표 Normalized spectra of Pu(VI) measured at 10 and 90 ℃ (top). The full width at a half maximum of Lorentzian curve linearly increases as a function of temperature(bottom)
표 Absorption spectra of Pu(III) in 0.1 M HClO4 were measured at various temperatures (left) and molar absorption coefficients at 561, 601 and 665 nm were decreased with the increase of temperature(right)
표 Pu3+ ions was quantitatively analyzed by comparing with reference absorption spectrum (gray line in the right). The concentrations of plutonium, Pu3+ ions and Pu(III)-OH species were 0.5, 0.45 and 0.05 mM, respectively
표 The reductive dissolution of PuO2 (s) [2-1-10~11]. Solid curves represent the concentration of Pu(IV) (aq) and Pu(III) (aq) expected with log*K°s,0 = -2.33 ± 0.52 and 15.8 ± 1.5 for PuO2 (am, hyd.) and Pu(OH)3 (am), respectively
표 Solubility products for Eu(III), Am/Cm(III) and Pu(III) hydroxide
표 Formation constants for hydrolysis species of Eu(III), Am/Cm(III) and Pu(III)
표 Species distribution of europium hydrolysis species at [Eu] = 0.02 mM from pH 5 to pH 12
표 Thermodynamic data of Pu(III) reported in the NEA-TDB review [2-1-4] and determined in the previous work [2-1-16]
표 Selected thermodynamic data for plutonium compounds and complexes. All ionic species listed in this table are aqueous species. Unless noted otherwise, all data refer to the reference temperature of 298.15 K and to the standard state, i.e., a pressure of 0.1 MPa and, for aqueous species, infinite dilution (I = 0) [2-1-3]
표 Comparison of temperatures controlled in a reactor and measured in a LWCC
표 A schematic diagram and a photo of electrolysis setup. Pt working (WE), Pt counter (CE) and Ag/AgCl reference (AE) electrodes were applied. A teflon vessel and quartz tubes were applied to minimize adsorption of Pu onto reactor surfaces
표 Experimental setup in an Ar filled glove-box. Temperature controlled water is circulated through a water-jacket surrounded a sample reactor, pH buffer reservoir and copper tubes located up & down sides of LWCC
표 LWCC and a home-made copper tube located at up & down sides of LWCC to maintain temperature during absorption measurement
표 LIBD set-up for monitoring colloidal nanoparticles at a fixed temperature
표 S-curves (BD probability vs. laser pulse energy) of background materials were measured for checking colloidal contaminations before preparing plutonium samples
표 S-curves (BD probability vs. laser pulse energy) of 0.1 M NaClO4, Pu(III) stock solution in 0.1 M HClO4, Pu(III) samples at pH 2.24, 2.84 and 3.58 were measured for comparing colloidal nanoparticles in plutonium samples
표 pH, [Pu3+]Abs. determined by analysis of absorption spectra, [Pu]LSC measured by LSC and [Pu3+]/[Pu] ratio of different Pu samples at 40°C
표 Absorbance of Pu(III) samples for the initial concentration of 0.5 mM increased with increase of pH. The plutonium concentration of samples in a reactor was increased by evaporating water at high temperature due to un-tight sealing of the reactor
표 LIBD measurement. Plutonium colloids were slightly formed at pH 4.95 and size and concentration of colloids increased with pH
표 Absorption spectra (left) and s-curves measured by LIBD (right). Concentration of plutonium was 0.22 mM. Temperature of samples was 40 ℃ and maintains constant during absorption and LIBD measurements
표 Absorption spectra (left) and s-curves measured by LIBD (right). Concentration of plutonium was 0.202 mM. Temperature of samples was 60 ℃ and maintains constant during absorption and LIBD measurements
표 Absorption spectra (left) and s-curves measured by LIBD (right). Concentration of plutonium was 0.53 mM. Temperature of samples was 80 ℃ and maintains constant during absorption and LIBD measurements
표 Absorption spectra (left) were measured for one sample as a function of time and decreases of [Pu3+] in solution (right) were observed due to oxidation of Pu(III)
표 Absorption spectra (left) and s-curves measured by LIBD (right). Concentration of plutonium at 0.16 mM and temperature of samples at 10 ℃ maintain constant during absorption and LIBD measurements
표 Absorbance decrease with increasing pH. oncentration of plutonium at 0.16 mM and temperature of samples at 10 ℃ maintain constant during absorption measurements
표 Absorption spectra of a Pu sample at pH 6.16 ([Pu]=0.165 mM) as a function of time
표 Relative amounts of Pu3+ ions rapidly decreased in a few hours and maintained within 2 weeks
표 Nuclear properties of americium isotopes [2-2-1, 2-2-2]
표 A representative LSC analysis of the purified 241Am. The sample was 10 μL of 175 μM 241Am solution (counting time: 10 min)
표 Representative γ-spectra of (a) approximately 10 nM 241Am solution in 20 mL of 0.1 M HClO4 and (b) approximately 50 nM 243Am solution in 20 mL of 0.1 M HClO4 (counting time: 100 min)
표 A representative α-spectrum of 1 mL of a diluted (~0.2 nM) solution spiked with 243Am standard (counting time: 86000 sec)
표 Absorption spectrum of purified Am3+ stock solution in 0.1 M HClO4. Inset is a zoomed-in absorption spectrum of diluted Am3+ solution in 0.1 M HClO4
표 (a) Concentration dependent absorption spectra of Am3+ in 0.1 M HClO4. (b) Absorbance at 503 nm as a function of concentrations of Am(III) that were determined by LSC. Absorbance was measured by using Cary 5000 in a quartz cell with a 1 cm path-length
표 (a) Concentration-dependent luminescence spectra of Am(III) in 0.1 M HClO4. (b) Luminescence intensity (peak area) plot as a function of Am(III) concentration that were determined by LSC. Luminescence was measured with an excitation laser wavelength of 503 nm
표 Formation constants of Am(III) hydrolysis and solubility constant [2-2-19]
표 Ion interaction coefficients and calculated activity coefficients [2-2-19]
표 pH-dependent Am(III) species distribution at 9 µM Am(III) in 0.1 M NaClO4
표 (a) pH-dependent absorption spectra of 9 µM Am(III) in 0.1 M NaClO4. (b) Normalized absorption spectra of the same samples. A path-length was 1 cm
표 Normalized absorption spectra of Am(III) before (red) and after (blues) ultrafiltration with 10 kDa membranes. (a) Am(III) sample at pH ~8.1 before filtration; Am(III) concentration that filtered through was 1.9 μM. (b) Am(III) sample at pH ~8.4; Am(III) concentration that filtered through was 0.4 μM. Absorbance was measured with 100 cm LWCC
표 (a) Time-dependent absorption spectral change of 9 μM Am(III) sample under a pH 8.1 condition. Absorbance was measured with 1 cm quartz cell. (b) absorbance ratio change of 503 nm to 506 nm as a function of time. pH of the sample was also changed along with the spectral change
표 (a) pH-dependent luminescence spectral changes and (b) corresponding luminescence decay curves
표 Summary of spectroscopic characteristics of Am(III) species investigated in this study
표 Adsorption efficiency of 6 µM Am(III) onto silica nanoparticles (1 mg/1 mL) in 0.1 M NaClO4
표 (a) Luminescence spectral change of Am(III) as increasing adsorption ratio onto silica surface. (b) Normalized luminescence spectra of Am(III) at pH 2.5 (0% adsorption) and pH 7.73 (100 % adsorption)
표 (a) Luminescence decay curve in natural log scale as a function of ICCD gate delay time. (b) pH-dependent luminescence lifetimes of Am(III) in solution (black circles) and adsorbed on silica surface (red squares). The number of inner-sphere coordinated water molecules are also displayed on the right axis
표 TEM images of U(IV) primary nanoparticles (a) and U(IV) nanoparticle clusters
표 Zeta potential measurement results of aqueous solutions of U(IV) nanoparticle colloid in the presence of PVP and humic acid
표 ATR-FT-IR spectra obtained from a series of aqueous solution of U(IV) nanoparticles containing 0.25%(w/w) PVP (MW, 40,000). Initial U(IV) concentration during nanoparticle synthesis varied from 0 to 5 mM
표 FFF analysis results regarding the change of U(IV) nanoparticle size depending on the concentration of humic acid (HA) in the aqueous colloid system of U(IV) nanoparticles
표 FT-IR spectra of KBr-U(IV) nanoparticle containing three different anions; sulfate (a), nitrate (b) and perchlorate (c). Spectra were taken in a transparent mode
표 Comparison of kinetic data of U(IV) and other metal ions induced hydrolysis
표 Absorption spectra of 50 µM of free NPP (red), 50 µM of free NP (blue), and reaction mixture (black) collected for initial 600 s ([NPP] = 50 μM, [U(IV)NPs] = 100 μM in 0.1 M NaClO4, pH = 7.5, 50 °C); (a) dashed lines: initial transition between two intermediates adsorbed on the surfaces of U(IV)NPs; (b)solid black lines: reduction of intermediate and formation of reaction product NP
표 Proposed mechanism for the hydrolysis of NPP
표 ATR-FTIR spectra of reaction mixture exhibiting SEIRA effects at pH 5.2; (a) a new peak at 1034 cm-1 noted as ‘*’ is observed in the spectrum of NPP in the presence of U(IV)NPs(solid) comparing to that of free NPP(dashed); (b) expanded spectra at 1300–1400 cm-1 (dashed line : 0.1 mM NPP without U(IV)NPs; solid lines : upon addition of 0.1–2 mM U(IV)NPs to 0.1 mM NPP (pH 3.2–2.0)
표 ATR-FTIR spectra of dried precipitates(reaction mixture, 100 % conversion): adsorbed phosphate species on the surface of U(IV) nanoparticles. [U(IV)NPs] = 1.5 mM, [Substrate] = 0.15 mM, I = 0.1 M NaClO4 at pH 7, 25 °C, 24 h
표 Physicochemical parameters and concentrations of major components of KURT groundwater samples
표 (a) Luminescence lifetimes of Ca2UO2(CO3)3(aq) in groundwater measured as a function of sample temperature. The inset shows luminescence spectra measured at two different sample temperatures at 1 and 23 °C. (b) Luminescence intensity of Ca2UO2(CO3)3(aq) in groundwater measured as a function of luminescence lifetime
표 Luminescence intensity changes as a function of U(VI) concentration. The circles The difference in luminescence intensities between three solutions suggests the interaction of U(VI) species with the NOMs in groundwater. The luminescence spectra were measured at 1 °C
표 Luminescence spectra of groundwater samples S4 and S5 measured by using the synchronous scan technique. The peak in S4 designated as the asterisk means that the natural organic matters in S4 are different from those in S5
표 Luminescence spectra of groundwater sample S4 measured by using the synchronous scan technique. Natural organic matters in groundwater show very sensitive photochemical reactions. The new luminescence peak appears as a result of the photochemical reactions
표 (a) EEM spectrum measured from raw groundwater S5. (a) EEM spectrum measured from groundwater S5. The emission at the visible wavelength region appeared after 1 hour irradiation by a UV light
표 Excitation and emission spectra of EEM plot. Peak wavelengths appear at 270 and 293 nm, respectively for excitation and emission spectra
표 EEM characteristics of well-known NOMs
표 SiO2 powders used in this study
표 (a) Photographs of luminescence measured from the suspended and sunken silica samples. (b) Schematic diagram of the experimental setup for TRLFS. For the LPAS experiment, the PZT was attached to the sample cell and the signal that was generated from the PZT was amplified using a low-noise preamplifier. The output of the amplifier was monitored using an oscilloscope, and a boxcar average system was used to measure the LPAS signal magnitude
표 Representative luminescence spectra of U(VI) surface species measured using an ICCD system at td = 1 μs and tw = 1000 μs for the sunken silica sample (Powder No. 2) at pH 7.1. The laser-induced reaction is accompanied by a rapid decrease of the luminescence intensities after irradiation of 15 minutes by a lser pulse energy of 2.0 mJ
표 Representative laser-induced reaction effect on the luminescence intensity measured using an ICCD system at td = 1 μs and tw = 1000 μs for the sunken silica sample at pH 7.1. The luminescence intensities were obtained from the integration of the signal from 475–600 nm in the luminescence spectrum that was measured at various laser pulse energies. The solid lines represent the result of fitting the data to the single exponential decay equation
표 The PA signal waveforms generated from PZT are monitored using an oscilloscope. The peak-to-peak value of the signal waveform is defined as the PA signal magnitude. The PA signal magnitude is much stronger at the laser excitation wavelength of 220 nm than that of 420 nm
표 (a) PA signal magnitude measured from the sunken silica samples as a function of the incident laser wavelength at the laser pulse energy of 0.2 mJ. The squares and circles represent the PA signal magnitude measured from the bare silica (pH 4.5) and the silica adsorbed with uranium (pH 6.9), respectively. (b) Laser-induced reaction measured from the sunken silica sample (pH 7.0). Under the same laser pulse energy of 0.8 mJ; the reaction occurs only at 220 nm
표 (a) Desorbed U(VI) quantities during the laser irradiation are compared with the decrease of the luminescence intensity for suspended silica samples at pH 6.2 and 7.2 (powder No. 3). The solid line is obtained by fitting the data to a linear regression. (b) The comparison of the normalized luminescence spectrum of the desorbed U(VI) species in the filtrated supernatant with that of the U(VI) species adsorbed onto a suspended silica sample at pH 7.2
표 The luminescence lifetime of the desorbed U(VI) species in the filtrated supernatant is compared with that of the U(VI) surface species adsorbed onto a suspended silica sample (powder No. 3) at pH 7.2. The solid line represents the result of fitting the data to a linear regression. The slope of the solid line (1/t) can be used to determine the luminescence lifetime of 51.8 ± 16.9 μs. The lifetime of the adsorbed species that is designated as circles is much longer than this value
표 Normalized luminescence spectra of U(VI) adsorbed onto the high SSA silica samples (powder No. 1) under various pH conditions. The spectra were measured at td = 1 μs and 2501 μs with the same gate width of 1000 μs. (a) The change of the V/P intensity ratio indicates the overlap of the spectra between the short- and long-lived U(VI) surface species. (b) Almost identical spectral shapes show a V/P intensity ratio of approximately 0.6 for the high SSA silica samples
표 Symbols represent the normalized luminescence intensity in the natural logarithmic scale for U(VI) adsorbed onto a sunken silica sample at pH 7.3. The kinetic mode of the ICCD was used with td = 1 μs, tw = 1000 μs, and a gate delay step of 50 μs for the luminescence lifetime measurement. The solid lines represent the fitting data calculated using Eq. (1). The luminescence lifetime of the long-lived species measured at 2.5 mJ became shortened due to the laser-induced reaction
표 Summary of the luminescence lifetimes of the U(VI) surface species determined from 36 suspended and 17 sunken silica samples (powder No. 1 and 2) under the pH conditions of 3.1–7.9. All measurements were performed within 10 minutes at the laser pulse energy of 0.1 mJ to avoid the laser-induced reaction effect on the luminescence intensity. The lifetimes of the short- and long-lived species were determined to be 230.6 ± 21.4 and 657.5 ± 16.9 μs, respectively, in the low and high pH region
표 Luminescence lifetimes for U(VI)adsorbed onto silica surface reported in previous studies

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