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At least 19 records

Measurement and analysis of distribution coefficients in Fe-Ni alloys containing S and/or P. I - K sub Ni and K sub P

The distribution coefficients of Ni and P in Fe-Ni-S-P alloys are determined using a plane front solidification technique. It is found that the distribution coefficient of Ni is altered only when both S and P are present as alloy constituents; the coefficient increases with S and P contents in the liquid alloy and varies from 0.9 to 1.30. The behavior of the distribution coefficient of P is determined by the S/P ratio in the liquid; the coefficient increases with the S/P ratio and varies from 0.25 to 5.8. Expressions are presented which relate the distribution coefficients of Ni and P to the S and P contents in the liquid.

Sellamuthu, R.

Measurement and analysis of distribution coefficients in Fe-Ni alloys containing S and/or P. II - K(Ir), K(Ge), and K(Cu)

Crystals of Fe-Ni-S-P alloys containing Ir, Ge, and Cu in small amounts were grown by plane front solidification. The electron microprobe was used to measure the compositions of these alloys. The Ir, Ge, and Cu distribution coefficients were determined by an analytical procedure from the composition data. The distribution coefficients of Ir, Ge, and Cu vary from 1.20 to 11.0, 0.75 to 2.1, and 0.06 to 0.84, respectively. K(Ir) and K(Ge) increase and K(Cu) decreases with the S content of the liquid. K(Cu) increases and K(Ir) and K(Ge) decrease with the P content of the liquid. Mathematical expressions have been formulated to relate the Ir, Ge, and Cu distribution coefficients to the S and P contents of the liquid. These distribution coefficients are important to the study of the solidification behavior of iron meteorites.

Sellamuthu, R.

Clinopyroxene REE distribution coefficients for shergottites The REE content of the Shergotty melt

Rare-earth element (REE) distribution coefficients were measured between synthetic pyroxenes and melts similar in composition to the Shergotty intercumulus fluid. REE-doped synthetic glass samples were analyzed by means of an automated microbeam electron microprobe. The coefficients were found to exhibit a strong positive correlation with pyroxene wollastonite content. Using distribution coefficients measured for the natural phase compositions, REE abundances for the Shergotty intercumulus melt were computed.

Mckay, G.

Implications of liquid-liquid distribution coefficients to mineral-liquid partitioning

In order to evaluate the influence of a silicate liquid structure on mineral-liquid partitioning, element partitioning data is obtained for coexisting anhydrous immiscible granitic and ferrobasaltic magmas. It is found that: (1) mineral-liquid distribution coefficients indicate the competition of crystal and liquid for cation incorporation, (2) increased polymerization of the residual liquid during crystal-liquid fractionation increases the mineral-liquid distribution coefficients for high-charge-density cations, (3) incompatible element ratios of low- and high-charge-density cations may vary during crystal-liquid fractionation because of changes in the melt composition and structure, (4) relative solubilities of REE's in melts do not vary with melt polymerization, (5) the changes of Sm/Eu ratios during crystal-liquid fractionation depend on the melt composition, and (6) minor components and volatiles can significantly influence the silicate melt structure and the mineral-liquid distribution coefficients.

Ryerson, F. J.

Analysis of segregation trends observed in iron meteorites using measured distribution coefficients

Fe-Ni alloys of meteoritic composition were solidified by a plane front solidification technique. Distribution coefficients of Ni, P, Ir, Ge, and Cu were determined from the composition data of the plane front solidified alloys. Equations that describe the distribution coefficients (P, Ni, Ir, Ge, and Cu) as a function of S and P content as well as S to P ratio were used to calculate solute partitioning between solid and liquid during the solidification of IIAB, IIIAB, and IVA parent bodies. The calculated P versus Ni, Ir versus Ni, Ge versus Ni, and Cu versus Ni trends are in good agreement with the observed meteorite data for each chemical group. It is concluded that each chemical group formed as a single molten pool in a parent body and that solute partitioning that occurred during solidification is responsible for the observed compositional trends within a single meteorite group.

Sellamuthu, R.

Acetylated Lysozyme as Impurity in Lysozyme Crystals: Constant Distribution Coefficient

Hen egg white lysozyme (HEWL) was acetylated to modify molecular charge keeping the molecular size and weight nearly constant. Two derivatives, A and B, more and less acetylated, respectively, were obtained, separated, purified and added to the solution from which crystals of tetragonal HEWL crystals were grown. Amounts of the A or B impurities added were 0.76, 0.38 and 0.1 milligram per millimeter while HEWL concentration were 20, 30 and 40 milligram per milliliter. The crystals grown in 18 experiments for each impurity were dissolved and quantities of A or B additives in these crystals were analyzed by cation exchange high performance liquid chromatography. All the data for each set of 18 samples with the different impurity and regular HEWL concentrations is well described by one distribution coefficient K = 2.15 plus or minus 0.13 for A and K = 3.42 plus or minus 0.25 for B. The observed independence of the distribution coefficient on both the impurity concentration and supersaturation is explained by the dilution model described in this paper. It shows that impurity adsorption and incorporation rate is proportional to the impurity concentration and that the growth rate is proportional to the crystallizing protein in solution. With the kinetic coefficient for crystallization, beta = 5.10(exp -7) centimeters per second, the frequency at which an impurity molecule near the growing interface irreversibly joins a molecular site on the crystal was found to be 3 1 per second, much higher than the average frequency for crystal molecules. For best quality protein crystals it is better to have low microheterogeneous protein impurity concentration and high supers aturation.

Thomas, B. R.

129 I, 99 Tc, and U Distribution Coefficients of Subsurface Sediments Collected from the Proposed Site of the Environmental Management Disposal Facility

Performance Assessment calculations were completed in 2020 to evaluate the Environmental Management Disposal Facility (EMDF), a proposed new low-level radioactive waste (LLW) disposal facility on the U.S. Department of Energy’s Oak Ridge Reservation (ORR). Among the large number of input parameters needed for such calculations, are distribution coefficients (K d values; radionuclide concentration solid: liquid ratio) that provide a measure of the tendency of radionuclides to bind to sediments. The objective of this study was to measure K d values of three radionuclides that may pose a disproportionately large amount of risk, U, iodine-129 ( 129 I) and technetium-99 ( 99 Tc). The average 129 I K d value for the 14 geological materials recovered from the proposed EMDF site was 37.8 mL/g and ranged from 0.45 to 140.9 mL/g. These values were consistent, but somewhat larger than previous measurements made with ORR sediments and were about an order of magnitude greater than those used in previous EMDF PA calculations. The median 99 Tc K d value was 365.7 mL/g, much greater than previously reported using ORR geological materials. Five of the 14 tested geological materials sorbed large quantities of 99 Tc, suggesting that the weakly sorbing 99 Tc(VII) species had been reduced to the sparingly soluble 99 Tc(IV) species. The five strongly sorbing sediments had apparent 99 Tc solubility values of approximately <10 -8 mol/L. The median U K d value was 5,726 mL/g. All of the tested geological materials had large K d values, ranging from 625 to >10,208 mL/g. Among the sediment samples that exhibited strong U binding, the apparent solubility value was approximately <10 -9 mol/L. Based on sediment properties and general ORR geological considerations, it was proposed that much of the 129 I and 99 Tc retention could be attributed to the site materials exhibiting low pH (average pH = 4.94), and/or the elevated levels of iron oxides, manganese oxides, and natural organic matter. Similarly, the extremely high U binding measured in these sediments may also be attributed to the low conditions of carbonates, which can complex and therefore solubilize uranyl in these tests due to the low pH, and also the relatively high concentrations of iron and organic coatings on these samples. An implication of this study is that the areas of the EMDF subsurface environment may have natural properties for attenuating 129 I, 99 Tc, and U movement, and potentially other radionuclides, thereby possibly reducing risk posed by burial of LLW at this site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W

Lidar measurements of cloud extinction coefficient distribution and its forward scattering phase function according to multiply scattered lidar returns

The study of the inversion algorithm for the single scatter lidar equation, for quantitative determination of cloud (or aerosol) optical properties, has received much attention over the last thirty years. Some of the difficulties associated with the solution of this equation are not yet solved. One problem is that a single scatter lidar equation has two unknowns. Because of this, the determination of the far-end boundary value, in the case of Klett's algorithm, is a problem if the atmosphere is optically inhomogeneous. Another difficulty concerns multiple scattering. There is a large error in the extinction distribution solution, in many cases, if only the single scattering component is considered, while neglecting the multiple scattering component. However, the use of multiple scattering in the remote sensing of aerosol or cloud optical properties is promising. In our early study, an inversion method for simultaneous determination of the cloud (or aerosol) Extinction Coefficient Distribution (ECD) and its Forward Scattering Phase Function (FSPF) was proposed according to multiply scattered lidar returns with two fields of view for the receiver. The method is based on a parameterized multiple scatter lidar equation. This paper is devoted to further numerical tests and an experimental study of lidar measurements of cloud ECD and FSPF using this method.

Qiu, Jinhuan

Partitioning of Ni/2+/ between basaltic and synthetic melts and olivines An experimental study

Olivine/liquid distribution coefficients for Ni in basaltic and simple synthetic melts are found in the 1400-1070 C temperature range. The results suggest that: (1) the Ni distribution coefficients and NiO activity coefficients are strongly temperature dependent, (2) the Ni distribution coefficients are functions of melt composition and structure at a constant temperature although the dependence is small for most basaltic magmas, (3) differences in melt composition do not significantly influence generally 'basaltic' melts, (4) the Ni distribution coefficients may be used as geothermometers to predict the olivine crystallization temperatures of basaltic magmas to within plus or minus 50 C, (5) the Ni distribution coefficients are greater than one at all natural magmatic temperatures, and (6) the Ni distribution coefficients do not significantly vary as functions of the Ni content of the melt to at least one mole percent.

Leeman, W. P.

Experimental and theoretical study of the formation of the 2AB, 3AB, and 9A meteorite chemical groups from the parent liquid

Segregation of solute elements was measured in plane front solidified Fe-Ni-S-P alloys of meteoritic composition containing Ir, Ge and/or Cu. The Ni and P contents reach maximum values of 10.5 wt% and 1.1 wt%, respectively, in austenite (taenite) at the end of primary solidification. Distribution coefficients of Ni, P, Ir, Ge and Cu were determined from the solidified alloys. The distribution coefficients vary with the S and P content of the liquid. In addition the distribution coefficients of Ni, P, Ir and Ge increase and the distribution coefficient of Cu decreases with the S to P ratio. Equations that describe the concentration dependence of the distribution coefficients were developed and used to calculate solute redistribution during the solidification of IIAB, IIIAB and IVA parent bodies. The calculated P vs Ni, Ir vs Ni and Ge vs Ni trends are in good agreement with the observed meteoritic data. Since the calculated value of the maximum solid solubility of P agrees well with the observed maximum P composition data for IIAB and IIIAB irons, it is concluded that complete crystallization of the parent liquids of IIAB and IIIAB had occurred before any fragmentation of the solidified body.

Sellamuthu, R.

Machine Learning-Driven Solvent Screening for Biobased 2,3-Butanediol Extraction

Biobased 2,3-butanediol (2,3-BDO) is a valuable biomass-derived chemical due to its versatility in being transformed into a wide variety of products. However, the separation and purification of 2,3-BDO from fermentation broth remain a significant challenge owing to its high boiling point and hydrophilic nature. Herein, we developed a machine learning (ML)-based screening workflow that uses molecular calculations as training data and requires only a small number of experimental measurements for validation to identify alternative solvent candidates for the liquid–liquid extraction (LLE) of 2,3-BDO from aqueous solution. In particular, 130 density functional theory (DFT) calculations with the implicit solvation method not only built a correlation between the computational partition coefficient and the experimental distribution coefficient of 2,3-BDO but also parameterized an Extra-Trees ML model to screen the distribution coefficient for a wider range of 6717 organic solvents. The experimental measurements of only 24 solvents were needed to validate the computational results. A list of 50 prioritized solvents was proposed for 2,3-BDO LLE, and seven additional experimental measurements were conducted to further verify our selected solvents. The impact of the extraction temperature and solvent-to-feed ratio was also investigated for selected solvents in experiments. Furthermore, this work suggested alternative solvents for 2,3-BDO LLE and proposed a versatile workflow that requires fewer experiments and can be applied to a broader range of LLE studies.

Extraction

Fractional crystallization of iron meteorites, an experimental study

Measurements of the distribution coefficients of various elements (Ni, Co, P, Pt, Ir, Ge, Cr, and Au) between solid and liquid phases were made for FeNi alloys. A high thermal gradient crystal growing furnace was employed in order to promote plane front solidification, rapid mixing in the liquid and a minimum of diffusion in the solid. Eight measurements of the nickel distribution coefficient gave an average value of 0.91 plus or minus 0.03 and this value was independent of the Ni concentration in the range 5.5 to 8.75 wt. % Ni. Equilibrium distribution coefficients were also calculated by correcting for the diffusion boundary layer present in the liquid. These values are within 20% of the measured distribution coefficient values. Except for Co and Ni, all the measured distribution coefficient values are closer to 1.0 than those calculated by Scott (1972) for the IIIAB irons. Using the experimental values and the calculated equilibrium values for ternary additions to FeNi melts, it appears that fractional crystallization processes will not explain the observed chemical variations in the major iron meteorite groups. Alternative explanations are suggested which also recognize the fact that cooling rates vary widely in several chemical groups.

Goldstein, J. I.