Stepan N. Kalmykov

Spatial and vertical distributions of elements in sediments of the Colorado River delta and upper Gulf of California

The abundance of major components (Fe, Ca, K, and organic carbon) and trace elements was analyzed in surface sediments and core samples from the Colorado River delta (CRD) and the Upper Gulf of California (UGC) using instrumental neutron activation analysis. The spatial distribution patterns of the elements studied are consistent with the model of sedimentary dynamics proposed for this area [Mar. Geol. 158 (1999) 125]: intense tidal resuspension of sediments in the delta with subsequent transport of suspended particulate matter in a southerly direction, followed by sedimentation of fine-grained material in a depocenter near the southwestern margin of the UGC. Concentrations of most of the elements are higher in the surface sediments of this depocenter. The gradual mixing of terrigenous and marine biogenic materials, normally expected for the estuarine sediments, was not detected in the CRD–UGC system because of homogenization of the sediments by tides and wind. Vertical profiles of element contents in samples of the sediment core collected in the depocenter area revealed (i) almost no anthropogenic contamination of the area by environmentally important trace elements such as Cr, Co, Sb, and As; (ii) a twofold decrease of Fe, Sc, Cr, and Co in upper core sediments; and (iii) the enrichment of the sediments at 60–62 cm depth in the core, in calcium carbonate, Ca, Sr, and the Eun/Smn shale-normalized ratio along with a depletion in this layer of Fe, Sc, Cr, Co, light rare-earth elements (REEs), and some other elements of terrigenous origin, presumably caused by the dilution of fluvial terrigenous material by biogenic carbonates, which were probably introduced at this level in the sediments by the action of a strong episodic winter storm, followed by the advective transport of shell fragments from the coastal clam banks or as a result of strong planktonic bloom. D 2002 Elsevier Science B.V. All rights reserved.

Plutonium sorption onto hematite colloids at femto- and nanomolar concentrations

Abstract The surface-mediated reduction of Pu(VI) upon sorption onto hematite colloids is addressed in the paper that bring some new light on the mechanisms of interaction of Pu in high valence states with different Fe(III) oxides. We study the sorption of Pu taken at two different total concentrations around 10−9 and 10−14 M using 239Pu and short-lived 237Pu tracer. In order to conclude on the mechanisms of Pu sorption onto hematite, the kinetics of sorption of Pu(IV) and Pu(VI) at two concenrations is studied as well as its leching behavior. The rate limiting step in Pu(VI) sorption is its surface-mediated reduction. The experimental evidence of the polymerization of Pu(IV) on the surface taken at Pu total concentration of ∼10−9 M is presented based on the kinetics of sorption and leaching behavior.

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.

Production of actinium, thorium and radium isotopes from natural thorium irradiated with protons up to 141 MeV

Abstract Cross sections of 225Ac, 227Ac, 227Th and 228Th in thorium-232 targets irradiated with protons in the energy range 21–141 MeV have been measured. Based on these data, production yields of 225Ac and 223Ra in thick thorium targets have been calculated. It is possible to produce in proton energy range 60–140 MeV about 96 GBq (2.6 Ci) 225Ac per 10-d irradiation with 100 μA proton beam current and 10-d decay, and much higher amount of 223Ra. The impurities of 227Ac and 224Ra are important and need to be assessed for further medical applications.

Production of 225Ac and 223Ra by irradiation of Th with accelerated protons

The possibility of producing 225Ac and 223Ra by irradiation of natural 232Th with medium-energy protons was examined. Thorium foils were irradiated with 90-, 110-, and 135-MeV protons at the accelerator of the Institute for Nuclear Research, Russian Academy of Sciences, in Troitsk (Moscow oblast). The cumulative production cross sections for 225Ac were 6.7 ± 0.9, 9.8 ± 1.9, and 13.9 ± 1.5 mb, and for 227Th (223Ra precursor), 43 ± 5, 37 ± 6, and 35 ± 4 mb, respectively. Based on the experimental data and theoretical calculations, the possible yields of 225Ac and 223Ra in irradiation of thick thorium targets at various accelerators were determined. An efficient procedure was suggested for isolating the products from the irradiated targets: 225Ac, by liquid extraction and extraction chromatography, and 223Ra, by sublimation from a thorium-lanthanum melt followed by thermochromatographic separation in metallic titanium columns and extraction-chromatographic isolation of radium. The procedure allows production of large (units of curies) amounts of radiochemically pure 225Ac and 223Ra, which is promising for wide use of these radionuclides in nuclear medicine.

Actinide Nanoparticle Research

Actinide - nanoparticle interaction. Generation, stability and mobility.- Section 1. Methods for actinide nanoparticle characterization: Scanning transmission electron microscopy and related techniques for research on actinide and radionuclide nanomaterials.- Resonant inelastic soft x-ray scattering spectroscopy of light-actinide materials.- Characterization of colloid borne actinides by Flow Field-Flow Fractionation (FlFFF) Multi Detector Analysis (MDA).- Actinide nanoparticle characterization by mass spectrometry.- Synchrotron-based X-ray spectromicroscopy of organic nanoparticles complexing actinides.- Section 2. Modeling of actinide nanoparticle structure and behavior: From molecules to nano-particles - A computational chemists point of view.- Theoretical analysis of colloid-facilitated transport of radionuclides by groundwater.- Section 3. Interfacial phenomena and formation of actinide nanoparticles: Nanoscale chemistry of uranyl selenates.- Actinide thin films as surface models.- Sorption and speciation of uranium on silica colloids.- Section 4. Environmental behavior of actinide colloids and nanoparticles: Radioactive particles released into the environment from nuclear events.- Effect of redox conditions on actinide speciation and partitioning with colloidal matter.- X-ray absorption spectroscopy of plutonium particles at the Rocky Flats US Nuclear Weapons Production Site.- Colloid facilitated transport of plutonium at the Nevada Test Site, NV USA.- Speciation of actinides in granite subjected to tracer studies.

Microorganisms in a Disposal Site for Liquid Radioactive Wastes and Their Influence on Radionuclides

Deep subsurface horizons used for the disposal of liquid low- and intermediate-level radioactive wastes of the Siberian Chemical Complex (SCC, Russia) were studied by microbiological, radioisotope, and molecular biological methods. It was shown that a diverse microbial community inhabited the groundwater. The cell numbers of microorganisms of the major metabolic groups and the rates of sulfate reduction, denitrification, and methanogenesis in natural groundwater were low and increased in the zone of wastes dispersion. More than 40 strains belonging to the genera Kocuria, Microbacterium, Pseudomonas, Pantoea, Acinetobacter, Enterobacter, Klebsiella, Stenotrophomonas, Sphingomonas, Staphylococcus, Acidivorax, Shewanella, and Desulfosporosinus were isolated from the disposal sites. Among the isolates, the microorganisms were found that were able to concentrate actinides and other transuranium elements. Aerobic bacteria were able to sorb various radionuclides in laboratory experiments; however, biosorption was low in sample of groundwater and in carbonate solutions containing several radionuclides. Reduction of U(VI) by a sulfate-reducing enrichment culture from the site and reduction of U(VI) and Np(V) by an isolate Shewanella were observed in the presence of various organic substrates. These results show the necessity of further ecosystem characterization based on microbiological and radiochemical studies and modeling of biogeochemical processes at the deep disposal sites for liquid radioactive wastes.

XPS Study of Ion Irradiated and Unirradiated UO2 Thin Films

XPS determination of the oxygen coefficient kO = 2 + x and ionic (U(4+), U(5+), and U(6+)) composition of oxides UO2+x formed on the surfaces of differently oriented (hkl) planes of thin UO2 films on LSAT (Al10La3O51Sr14Ta7) and YSZ (yttria-stabilized zirconia) substrates was performed. The U 4f and O 1s core-electron peak intensities as well as the U 5f relative intensity before and after the (129)Xe(23+) and (238)U(31+) irradiations were employed. It was found that the presence of uranium dioxide film in air results in formation of oxide UO2+x on the surface with mean oxygen coefficients kO in the range 2.07-2.11 on LSAT and 2.17-2.23 on YSZ substrates. These oxygen coefficients depend on the substrate and weakly on the crystallographic orientation. On the basis of the spectral parameters it was established that uranium dioxide films AP2,3 on the LSAT substrates have the smallest kO values, and from the XRD and EBSD results it follows that these samples have a regular monocrystalline structure. The XRD and EBSD results indicate that samples AP5-7 on the YSZ substrates have monocrystalline structure; however, they have the highest kO values. The observed difference in the kO values was probably caused by the different nature of the substrates: the YSZ substrates provide 6.4% compressive strain, whereas (001) LSAT substrates result only in 0.03% tensile strain in the UO2 films. (129)Xe(23+) irradiation (92 MeV, 4.8 × 10(15) ions/cm(2)) of uranium dioxide films on the LSAT substrates was shown to destroy both long-range ordering and uranium close environment, which results in an increase of uranium oxidation state and regrouping of oxygen ions in uranium close environment. (238)U(31+) (110 MeV, 5 × 10(10), 5 × 10(11), 5 × 10(12) ions/cm(2)) irradiations of uranium dioxide films on the YSZ substrates were shown to form the lattice damage only with partial destruction of the long-range ordering.

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln3+) and 5f-elements (actinides, An3+) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln3+ and An3+ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu3+/Am3+ model pair cations (SFAm/Eu) in extraction experiments on a semi-quantitative level. The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]3+, (H2O)nM(NO3)3 (n = 3, 4), and LM(NO3)3 (M = Eu, Am). Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln3+ and An3+ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An3+ and Ln3+ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation. Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An3+/Ln3separation selectivity in the series of dipicolinic acid diamides.