Modeling migration of strontium in sand and gravel aquifer in the candidate VLLW disposal site

Study of fine-particle media, because of their high sorption capacities, is of particular importance for the use as backfill materials in waste repository design, and because argillaceous formations are particularly suitable as host rock formations. In this study, sorption and retardation characteristics of strontium in fine-particle media were studied to evaluate the distribution coefficient (K _d ) and retardation factor (R _d ) of this radioactive element in fine-particle media, which was comprised of selected particles with a diameter less than 1 mm from a candidate site to dispose very low level waste (VLLW). The results indicated that K _d values of strontium under different initial concentrations ranged between 20 and 110. Values of strontium R _d measured from column experiments ranged between 36 and 102, with the corresponding K _d values, determined from solving the inverse problem of R _d calculating formula, ranging between 5 and 20. In conclusion, the K _d value of Sr from the batch tests was found to be higher than these from the column experiments.     

Determining PPARγ-ligand binding affinity using fluorescent assay with cis -parinaric acid as a probe

Upon the study of small-molecules binding to proteins, the traditional methods for calculating dissociation constants (K _d and K _i ) have shortcomings in dealing with the single binding site models. In this paper, two equations have been derived to solve this problem. These two equations are independent of the total concentration or initial degree of saturation of receptor and the activity of the competitive molecule. Through nonlinear fitting against these two equations, K _d value of a probe can be obtained by binding assay, and K _i value of a ligand can be obtained by competitive assay. Moreover, only the total concentrations of receptor([R]_t), ligand([L]_t) and probe([P]_t) are required for the data fitting. In this work, K _i values of some typical ligands of PPARγ were successfully determined by use of our equations, among which the K _i value of PPARγ-LY171883 was reported for the first time.     

Kinetic evaluation of sorption and desorption

Sorption is often quantified by a distribution coefficient, K _d , which is the equilibrium ratio between species sorbed to the rock and species in solution. Traditionally K _d -values are determined in batch experiments from equilibrium concentrations.     

Iranian clinoptilolite-rich tuffs for radionuclide removal from water

Three Iranian natural zeolites were characterized and evaluated for their abilities to take up Ba⁺², Ca⁺², K⁺ and Na⁺ from radioactive waste waters. The distribution coefficient values (K _d ) of the cations were measured and investigated as a function of pH. Four different cationic forms (Na, K, NH₄, and Ca) were also prepared and theirK _d values were determined. Some cations such as potassium presented highK _d values both in natural and exchanged zeolites. In sodium and ammonium exchanged forms theK _d values increased between 7 to 100 times with respect to the untreated zeolite.     

Sorption of Cs,Pu and Am on clay minerals

Performance assessment of radioactive waste disposal requires modeling of long-term migration of radionuclides through the engineered barriers and the geological environment. The chemical complexity of sorption-desorption processes is usually reduced to integrated parameter distribution coefficients (K _d ). There are a great number of publications on K _d determination, however, the existing data on K _d of radionuclides on different geological materials are for general understanding only and are not very useful for performance assessment, since changes of the geological conditions result in variability of K _d values by two orders of magnitude. In order to obtain realistic sorption data sets for safety relevant radionuclides present in a cement/concrete based repository some preliminary studies were carried out. The development of sorption database for the near-surface repository was started with measurements of cesium, plutonium and americium K _d values. Several experiments were performed in order to determine the chemical composition of cement water which could originate from infiltration of precipitation and from contact of groundwater with concrete. More than 100 batch sorption experiments were conducted with two clay samples. Cs, Pu and Am K _d values were determined for rainwater, groundwater and cement-water of different chemical compositions. Cs, Pu, Am K _d values ranged from 450 to 9700, from 15000 to 21000 and 15000 to 80000 ml/g, respectively. Changes in the geochemical conditions resulted in the variability of Cs, Pu and Am K _d values.     

A multitracer Study on the Adsorption of 36 Elements on a Silica: Effects of pH and Fulvic Acid

The distribution coefficients,K _d of 36 elements from Na to Bi on a silica were determined at pH 4, 7, 9 and in the absence and presence of fulvic acid (FA) using a multitracer technique. The multitracer solution was prepared by irradiation of Th(NO₃)₄ with ⁴⁰Ar ion beam. The effects of pH and fulvic acid on the K _d values of 36 elements were studied. It was found that the sequences of the K _d values of alkali elements (Cs>Rb>K>Na) and of alkaline earth elements(Ba>Ca>Mg) in the absence of FA can be qualitatively explained in terms of chemical bond formation and hydration. Various effects of pH and the negative or positive effect of FA on the adsorption of 36 elements were observed and are probably related to the species of 36 elements in the aqueous solutions containing CO₃ ^2–, OH^–, Cl^– and FA. For most of the elements studied here the K _d values are increased with increasing pH and are decreased with adding FA.     

The distribution coefficient of60Co in sediments from the Solway Firth, UK

The behaviour of⁶⁰Co in sea water and sediments typical of the Solway Firth has been investigated. The distribution coefficient,K _d, of⁶⁰Co²⁺ in sediments was determined using the batch sorption method and theK _d variation with aqueous phase composition, sediment type and pH has been studied. Adsorption of⁶⁰Co by sediments was found to be highest in de-ionised water and lower in NaCl solution (31 salinity). Adsorption was lowest in natural sea water, where theK _d range was 2,270 to 2,750. Variation ofK _d with sediment grain size was observed. It was shown that⁶⁰Co adsorption was strongly dependent on pH in de-ionised water, with less variation in NaCl solution. Variance of⁶⁰CoK _d values were lowest in sea water in the range pH 5–8 indicating a more conservative behaviour of⁶⁰Co than previously recognised. Hence⁶⁰Co dispersion will be predominantly govemed by tidal behaviour.     

Characterisation of the surface of a cellulosic multi-purpose office paper by inverse gas chromatography

The surface of multi-purpose cellulosic office paper has been analysed by inverse gas chromatography (IGC). The parameters determined were the dispersive component of the surface free energy, the enthalpy of adsorption and the entropy of adsorption of polar and apolar probes, the Lewis acidity constant, K _a, and the Lewis basicity constant, K _b. It can be concluded that the dispersive component of the surface free energy, _s ^d decreases with temperature, in the range 50–90°C. The temperature coefficient of _s ^d, d_s ^d/dT, is –0.35 mJm ^–2K^–1. The values of K _a and K _b were determined to be 0.11±0.011 and 0.94±0.211, respectively. The predominant surface basicity agrees with expectation, bearing in mind the presence of calcium carbonate, and of a styrene-acrylic copolymer, in the surface sizing formulation. It is thought that during the drying stages following the surface sizing treatment, the starch used as the binder migrates to the interior of the surface sizing layer and then to the paper bulk itself. This migration contributes to a decrease in the hydrophilicity of the surface, and also results in the surface showing only slight Lewis.     

Quantification of thorium and uranium sorption to contaminated sediments

Desorption tests, using a sequential extraction method, were used to characterize and quantify thorium and uranium sorption to contaminated wetland sediments collected from the Department of Energy's Savannah River Site located in South Carolina. In situ distribution coefficients, or K _d values (K _d = C _solid/C _liquid), were determined. Sequential extraction data were used to assign solid-phase radionuclide concentrations (C _solid) that, by definition, should represent only the reversibly sorbed fraction. A series of selective and sequential extractions was used to determine desorption K _d values. Thorium K _d values ranged from 115 to 2255 ml/g. Uranium K _d values ranged from 170 to 6493 ml/g. Compared to sorption K _d values, these desorption K _d values were appreciably greater because they captured the aging process of the radionuclides with the sediment, making the radionuclide more refractory. Compared to nonsite-specific data, these in situ K _d values improved accuracy, were more defensible, and removed unnecessary conservatism for subsequent transport and risk calculations. Additional tests were conducted to provide geochemical information relevant for selecting appropriate remediation technologies for the contaminated site. Thorium and uranium were associated with labile fractions and were not concentrated with the smaller sediment particles. These findings suggest that phytoremediation or heap leaching, and not soil washing, are viable remediation approaches for this site.     

Sorption and diffusion processes with134Cs and85Sr in natural sorbents

Sorption and diffusion processes with¹³⁴Cs and⁸⁵Sr in natural bentonites have been investigated. The distribution coefficients (K _d ) have been determined by a batch method. Various factors affecting theK _d value as water-to-bentonite ratio, concentration of the competitive cations in the aqueous phase or bentonite-to-sand ratio in the mixed sorbents have been evaluated. A comparison of the sorption and diffusion data has been made.     

Vertical random variability of the distribution coefficient in the soil and its effect on the migration of fallout radionuclides

In the field, the distribution coefficient, K _d, for the sorption of a radionuclide by the soil cannot be expected to be constant. Even in a well defined soil horizon, K _d will vary stochastically in horizontal as well as in vertical direction around a mean value. The horizontal random variability of K _d produce a pronounced tailing effect in the concentration depth profile of a fallout radionuclide, much less is known on the corresponding effect of the vertical random variability. To analyze this effect theoretically, the classical convection-dispersion model in combination with the random-walk particle method was applied. The concentration depth profile of a radionuclide was calculated one year after deposition assuming (1) constant values of the pore water velocity, the diffusion/dispersion coefficient, and the distribution coefficient (K _d = 100 cm^3.g^-1), and (2) exhibiting a vertical variability for K _d according to a log-normal distribution with a geometric mean of 100 cm^3.g^-1 and a coefficient of variation of CV = 0.53. The results show that these two concentration depth profiles are only slightly different, the location of the peak is shifted somewhat upwards, and the dispersion of the concentration depth profile is slightly larger. A substantial tailing effect of the concentration depth profile is not perceivable. Especially with respect to the location of the peak, a very good approximation of the concentration depth profile is obtained if the arithmetic mean of the K _d-values (K _d = 113 cm^3.g^-1) and a slightly increased dispersion coefficient are used in the analytical solution of the classical convection-dispersion equation with constant K _d. The evaluation of the observed concentration depth profile with the analytical solution of the classical convection-dispersion equation with constant parameters will, within the usual experimental limits, hardly reveal the presence of a log-normal random distribution of K _d in the vertical direction in contrast to the horizontal direction.     

Determination of elastic constants of a binary system (7CPB+9.CN) showing nematic,induced smectic Ad and re-entrant nematic phases

The temperature variation of the splay and bend elastic constants of a binary system exhibiting nematic-induced smectic A_d and re-entrant nematic phases measured by electric field-induced Freedericksz transition method has been reported. As bend deformation is not permitted in the smectic A phase, bend elastic constant (K₃₃) could only be determined in the nematic and re-entrant nematic phases. In both the nematic phases, the splay elastic constant has the same order of magnitude and does not show any pretransitional effect. However, in the induced smectic A_d phase, the value of K₁₁ is about one to two orders higher than that in the nematic phases. The bend elastic constant shows a strong pretransitional effect near the nematic–smectic and smectic–re-entrant nematic phase transitions. The influence of the presence of the induced smectic phase is observed even in those mixtures which have no induced smectic phases. As the smectic phase is approached, the ratio K₃₃/K₁₁ increases rapidly and diverges to infinity.     

A review on distribution coefficient (Kd) of some selected radionuclides in soil/sediment over the last three decades

This review paper presents the different methods to estimate K_d and subsequent compiles of the K_d data on U, Ra, Th, ¹³⁷Cs and ⁶⁰Co in soil/sediment under various aquatic medium based on the extensive literature survey over the last 3-decades (1990–2019). The estimated K_d values show a very wide range and make more difficult to derive generic value. The finding suggests that K_d values are to be estimated for site-specific conditions while assessing the radionuclide transport modeling and risk analysis around the nuclear facilities. Review includes research papers, reports, reviewed papers, dissertations, published compilations and other technical documents.

     

Movement of Phosphamidon in Soil Columns

Abstract

Adsorption and movement of phosphamidon, a systemic non-ionic insecticide, was studied using two different types of Indian soil, clay loam and silt loam, of alluvial origin. Equilibrium adsorption coefficient, K, values determined by batch slurry technique were in the order: clay loam>silt loam. The distribution coefficient, K_d , for both soils in batch adsorption as well as in columns was also calculated. The phosphamidon movement measured in soil columns during water infiltration was in the order: silt loam > clay loam. This order was anticipated from the K and K_d values. A larger amount of water was needed for leaching the phosphamidon to 60 inches in clay loam than in silt loam soil.     

Extrapolation studies on adsorption of thorium and uranium at different solution compositions on soil sediments

Study on adsorption of thorium and uranium radionuclides by a soil sediment as a function of ionic composition of Ca, Mg and Na has been carried out. Experimentally determined slopes represents an average of adsorption on soil sediments having different relative affinities for thorium, uranium, calcium and magnesium. Both thorium and uranium were found to be adsorbed to ion-exchange sites together with calcium and magnesium cations as effective competitors An extrapolated equation for the distribution coefficientK _d was formed for both radionuclides thorium and uranium at the specified site where the soil sediments were sampled. The combined cation concentration of both calcium and magnesium in solution correlates linearly with the measuredK _d ^Th,U values.     

A Highly K+‐Selective Two‐Photon Fluorescent Probe

A highly K⁺‐selective two‐photon fluorescent probe for the in vitro monitoring of physiological K⁺ levels in the range of 1–100 mM is reported. The two‐photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K⁺, independently of one‐photon (OP, 430 nm) or two‐photon (TP, 860 nm) excitation and comparable K⁺‐induced FEs in the presence of competitive Na⁺ ions. The estimated dissociation constant (K_d) values in Na⁺‐free solutions (K_d^OP=(28±5) mM and K_d^TP=(36±6) mM ) and in combined K⁺/Na⁺ solutions (K_d^OP=(38±8) mM and K_d^TP=(46±25) mM ) reflecting the high K⁺/Na⁺ selectivity of the fluorescent probe. The TP absorption cross‐section (σ_2PA) of the TPEF probe+160 mM K⁺ is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K⁺.     

A Highly K+‐Selective Fluorescent Probe – Tuning the K+‐Complex Stability and the K+/Na+ Selectivity by Varying the Lariat‐Alkoxy Unit of a Phenylaza[18]crown‐6 Ionophore

A desirable goal is to synthesize easily accessible and highly K⁺/Na⁺‐selective fluoroionophores to monitor physiological K⁺ levels in vitro and in vivo. Therefore, highly K⁺/Na⁺‐selective ionophores have to be developed. Herein, we obtained in a sequence of only four synthetic steps a set of K⁺‐responsive fluorescent probes 4 , 5 and 6 . In a systematic study, we investigated the influence of the alkoxy substitution in ortho position of the aniline moiety in π‐conjugated aniline‐1,2,3‐triazole‐coumarin‐fluoroionophores 4 , 5 and 6 [R=MeO ( 4 ), EtO ( 5 ) and iPrO ( 6 )] towards the K⁺‐complex stability and K⁺/Na⁺ selectivity. The highest K⁺‐complex stability showed fluoroionophore 4 with a dissociation constant K_d of 19 mm , but the K_d value increases to 31 mm in combined K⁺/Na⁺ solutions, indicating a poor K⁺/Na⁺ selectivity. By contrast, 6 showed even in the presence of competitive Na⁺ ions equal K_d values (K_d^K+=45 mm and K_d^K+/Na+=45 mm ) and equal K⁺‐induced fluorescence enhancement factors (FEFs=2.3). Thus, the fluorescent probe 6 showed an outstanding K⁺/Na⁺ selectivity and is a suitable fluorescent tool to measure physiological K⁺ levels in the range of 10–80 mm in vitro. Further, the isopropoxy‐substituted N‐phenylaza[18]crown‐6 ionophore in 6 is a highly K⁺‐selective building block with a feasible synthetic route.     

Enzymatic hydrolysis of protein: Mechanism and kinetic model

The bioreaction mechanism and kinetic behavior of protein enzymatic hydrolysis for preparing active peptides were investigated to model and characterize the enzymatic hydrolysis curves. Taking into account single-substrate hydrolysis, enzyme inactivation and substrate or product inhibition, the reaction mechanism could be deduced from a series of experimental results carried out in a stirred tank reactor at different substrate concentrations, enzyme concentrations and temperatures based on M-M equation. An exponential equation dh/dt = aexp(-bh) was also established, where parameters a and b have different expressions according to different reaction mechanisms, and different values for different reaction systems. For BSA-trypsin model system, the regressive results agree with the experimental data, i.e. the average relative error was only 4.73%, and the reaction constants were determined as K _m = 0.0748 g/L, K _s = 7.961 g/L, k _d = 9.358/min, k ₂ = 38.439/min, E _a = 64.826 kJ/mol, E _d = 80.031 kJ/mol in accordance with the proposed kinetic mode. The whole set of exponential kinetic equations can be used to model the bioreaction process of protein enzymatic hydrolysis, to calculate the thermodynamic and kinetic constants, and to optimize the operating parameters for bioreactor design. __________ Translated from Journal of Tianjin University, 2005, 38(9) (in Chinese)     

A new langbeinite‐type phosphate K2GdHf(PO4)3: synthesis,crystal structure,band structure and luminescence properties

Langbeinite‐type compounds are a large family that include phosphates, sulfates and arsenates, and which are accompanied by interesting physical properties. This work reports a new disordered langbeinite‐type compound, K₂GdHf(PO₄)₃ [dipotassium gadolinium hafnium tris(phosphate)], and its structure as determined by single‐crystal X‐ray diffraction. Theoretical studies reveal that K₂GdHf(PO₄)₃ is an insulator with a direct band gap of 4.600 eV and that the optical transition originates from the O‐2p→Hf‐5d transition. A Ce³⁺‐doped phosphor, K₂Gd_0.99Ce_0.01Hf(PO₄)₃, was prepared and its luminescence properties studied. With 324 nm light excitation, a blue emission band was observed due to the 5d¹→4f¹ transition of Ce³⁺. The average luminescence lifetime was calculated to be 5.437 µs and the CIE chromaticity coordinates were (0.162, 0.035). One may expect that K₂Gd_0.99Ce_0.01Hf(PO₄)₃ can be used as a good blue phosphor for three‐colour white‐light‐emitting diodes (WLEDs).     

Sorption and diffusion of HTO and cesium in crushed granite compacted to different lengths

In this study, batch and through-diffusion experiments have been performed in order to determine the distribution coefficients (K _d ), apparent diffusion coefficients (D _a ) and retardation factor (Rf), respectively. Both apparent and effective diffusion coefficient (D _a and D _e ) of Cs were obtained by accumulative concentration method developed by Crank (1975). In addition, a non-reactive radionuclide, HTO, was initially conducted in through-diffusion experiment for assessing the ability of radionuclide retardation. The distribution coefficients (K _d ) obtained by batch tests in 14 days under aerobic and anaerobic systems were 2.06 and 3.52 ml/g. Moreover, it is found in through-diffusion test that Rf = 4.12 and 4.40 and K _d = 0.97 and 1.06 of Cs did not have an obvious discrepancy in a length/diameter/ (L/D) ratio of 0.44 and 1.78. However, Rf and K _d revealed a larger difference in an L/D ratio closing to 1 due to the geometric change of one-dimension diffusive hypothesis. Therefore, it demonstrates that Rf and K _d obtained by through-diffusion experiments only could be achieved at a lower or larger L/D ratio and would be reliable for long-term performance assessment.