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Chemistry for Sustainable Development

2012 year, number 5

1.
Uranium in Technogenic Aerosol of the Industrial Areas of Novosibirsk

S. YU. ARTAMONOVA
Sobolev Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia),
E-mail: artam@igm.nsc.ru
Keywords: technogenesis, technofilic elements, natural radionuclides, isotopes, aerosol, emission, technogenic pollution, ecological risk
Pages: 457463

Abstract >>
Results of the mineralogical and geochemical investigation of technogenic aerosol samples collected in 2011 in the northeastern direction from Novosibirsk in the plume of the Novosibirsk Chemical Concentrates Plant JSC, as well as aerosol collected near the Novosibirsk Tin Plant JSC and Heat and Electric Power Plant No. 3 are reported for the first time. Uranium content and its mineral formations were determined by means of ICP-MS, ICP-AES and scanning electron microscopy.



2.
Uranium Migration in the Ground Water of the Region of Sludge Dumps of the Angarsk Electrolysis Chemical Combine

A. E. BOGUSLAVSKIY,  O. L. GASKOVA and O. V. SHEMELINA
Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia),
E-mail: boguslav@igm.nsc.ru
Keywords: store of radioactive wastes, uranium migration, pollution of ground water, forms of uranium migration
Pages: 465478

Abstract >>
Ground water in the region of slurry dumps of low-activity wastes from the Angarsk Electrolysis Chemical Combine manufacturing enriched uranium was studied. It was established that the Eh values vary from weakly reductive to oxidative, pH varies from neutral to alkaline values. The presence of a hydrodynamic mound in the region of the slurry field provides vigorous diffluence of the technogenic infiltration runoff, which results in possible local increase in the concentrations of , and in the zone of the hydrodynamic mound above the maximum permissible level. Alkaline sodium nitrate solutions are characterized by higher salt content (up to 9 g/L) but uranium content of all the ground water samples (background, in the region of the stores of solid and liquid radioactive wastes) is below the MPC level. The composition of phases that are able to precipitate from the disposed slurry water after neutralization with ()2 and settling was confirmed with the help of thermodynamic calculations. Possible increase in the concentration of uranium in the interaction of calcium urinates with CO2 (solution) was demonstrated. Limiting concentrations of uranium in solutions were calculated; the limiting values are determined by the s9lubility of uranium-containing minerals formed depending on pH, partial pressure of 2 and the presence of cations (Ca, Si, Al).



3.
Ecological Geochemistry of Mercury and the Methods for Demercurization the Mercury-Containing Solid Wastes under the Conditions of South Siberia (by the Example of the Industrial Area of the JSC Novosibirsk Chemical Concentrates Plant)

A. G. VLADIMIROV1,4,5, A. V. BABUSHKIN2, I. M. BELOZEROV3, YU. V. OSTROVSKIY3, V. G. VLADIMIROV1, M. YU. PODLIPSKIY1 and V. A. MININ1
1 Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia),
E-mail: vladimir@igm.nsc.ru
2 JSC Novosibirsk Chemical Concentrates Plant, Ul. B. Khmelnitskogo 94, Novosibirsk 630110 (Russia),
E-mail: nzhk@nccp.ru
3 JSC State Specialized Design Institute, Novosibirsk VNIPIET, Ul. B. Khmelnitskogo 2, Novosibirsk 630075 (Russia),
E-mail: ost@vnipiet-nsk.ru
4 Novosibirsk National Research State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia),
E-mail: pashkova@lab.nsu.ru
5 National Research Tomsk State University, Pr. Lenina 36, Tomsk 634050 (Russia),
E-mail: labspm@ggf.tsu.ru
Keywords: lithium, chemical and metallurgical industries, mercury-containing solid wastes, demercurization, geological conservation
Pages: 479490

Abstract >>
Results are presented for hydrogeochemical monitoring the industrial area of the JSC Novosibirsk Chemical Concentrates Plant as well as experimental data concerning the demercurization of soils and building materials those were contaminated with mercury. A comprehensive approach to the demercurization and geological conservation of mercury-containing waste is proposed that includes three stages: 1) a centrifugal extraction of mercury from solid wastes including contaminated grounds, soils and building refuse; 2) chemical immobilizing the mercury remaining in the insoluble form (naturally occurring mineral Stchuettite); 3) geological conservation.



4.
Investigation of the Properties of Hydroxyapatite Extracted from the Bone Tissue of Agricultural Animals

E. A. ZELICHENKO,  V. V. GUZEEV,  A. S. ROGULINA,  O. A. GUROVA and YA. B. KOVALSKAYA
Seversk Technological Institute, Branch State Budget Educational Institution of Higher Professional Education National Research Nuclear University MEPhI, Pr. Kommunisticheskiy 65, Seversk, Tomskaya obl. 636036 (Russia),
E-mail: zelichenko65@mail.ru
Keywords: calcium phosphate compounds, deposition, dispersity, phase composition, stoichiometry
Pages: 491496

Abstract >>
Dependence of the properties of calcium phosphate compounds on the method of their isolation from biological raw material was studied. Physicochemical studies of the properties of resulting materials were carried out. The proposed procedure allows one to obtain ultrafine powders of biological hydroxyapatite with controllable particle size and composition maximally approaching the composition of bone tissue. It was established that the calcium phosphate compound deposited from the solution that was obtained by demineralization with the solution containing hydrogen chloride 1 mol/L is most close to the mineral matrix of bone tissue.



5.
Determining the Sorption Capacity of Modified Carbon Sorbents Using X-ray Fluorescence Analysis

YA. B. KOVALSKAYA,  E. A. ZELICHENKO,  L. D. AGEEVA,  V. V. GUZEEV,  A. S. ROGULINA and  O. A. GUROVA
Seversk Technological Institute, Branch State Budget Educational Institution of Higher Professional Education National Research Nuclear University MEPhl, Pr. Kommunisticheskiy 65, Seversk, Tomskaya obl. 636036 (Russia),
E-mail: yana-sti@bk.ru
Keywords: modified materials, chitosan, carbon material, sorption, gold, X-ray fluorescence analysis
Pages: 497501

Abstract >>
Physicochemical properties inherent in chitosan-containing solutions as well as the sorption properties of carbon materials modified with chitosan were studied. It has been found that the composites obtained exhibit anion-exchange properties. The chitosan-containing materials have been shown to exhibit a sufficiently high sorption capacity, which makes them efficient as sorbents for the concentration and extraction of gold, and other heavy and radioactive metals in the future.



6.
Cerium (III) Sorption by Naturally Occurring Clinoptilolite Containing Tuff

N. M. KOZHEVNIKOVA
Baikal Institute of Nature Management, Siberian Branch of the Russian Academy of Sciences, Ul. Sakhyanovoy 8, Ulan Ude 670047 (Russia),
E-mail: nicas@binm.bscnet.ru
Keywords: naturally occurring zeolite, cerium (III) ions, sorption capacity, sorption kinetics and equilibrium
Pages: 503506

Abstract >>
Cerium sulphate ion-exchange sorption by containing naturally occurring clinoptilolite tuff from aqueous solutions was studied within a wide range of concentration values (10-5-10-2mol/l). Adsorption isotherms and kinetic parameters have been determined.



7.
Effect of Different Activation Methods on the Composition, Structure and Reactivity of Aspen Wood

B. N. KUZNETSOV1,2, V. I. SHARYPOV1,2, S. A. KUZNETSOVA1,2, S. V. BARYSHNIKOV1, V. G. DANILOV1, O. V. YATSENKOVA1 and N. M. IVANCHENKO1
1 Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Ul. K. Marksa 42, Krasnoyarsk 660049 (Russia),
E-mail: bnk@icct.ru
2 Siberian Federal University, Pr. Svobodny 79, Krasnoyarsk 664041 (Russia)
Keywords: aspen wood, mechanical activation, explosive autohydrolysis, catalytic oxidation, structure, composition, reactivity
Pages: 507513

Abstract >>
An effect of different methods for aspen wood activation (grinding in the mills of different types, explosive autohydrolysis, catalytic oxidation by hydrogen peroxide and the combination of these methods) exerted on the structure, chemical composition and reactivity of activated wood was studied. It has been found that all the methods of aspen wood mechanical pretreatment result in changing the supramolecular structure, chemical composition and reactivity thereof: activated samples exhibit increasing the content of readily hydrolysable polysaccharides, with reducing the concentration of polysaccharides difficult to hydrolyze and of residual lignin, as well as with increasing the rate of polysaccharide acidic hydrolysis into monosaccharides and the rate of lignin oxidation by hydrogen peroxide.



8.
Studies on a Three-Phase Extraction Nickel in the Systems with Cyanex 301

M. N. LESKIV,  V. I. KUZMIN  and  S. N. KALYAKIN
Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Ul. K. Marksa 42, Krasnoyarsk 660049 (Russia),
E-mail: leskivmv@inbox.ru
Keywords: Cyanex 301, nickel, three-phase extraction, binary extraction, concentrating the extraction agent
Pages: 515521

Abstract >>
Phase formation was studied for the systems of Cyanex 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid)organic solvent (toluene, heptane, octane)sodium hydroxidewatertrioctylamine. It is demonstrated that the Cyanex 301 transition into a salt form (three-phase extraction) results in achieving the separation of the organic extraction agent solution into the solvent phase and a cation-exchange extraction agent. The sodium salt of Cyanex 301 is almost completely transformed into a new aqueous micellar solution. Conditions have been determined for the efficient separation of the organic phase components and for the isolation concentrated Cyanex 301. An effect of trioctylamine additives exerted on nickel extraction in the systems with Cyanex 301 was studied. A scheme has been proposed for the extraction of nickel using a three-phase extraction, wherein nickel is extracted by means of the concentrated solution of Cyanex 301 from acidic solutions resulted from leaching the ore, the extract is mixed with an organic amine solution to be re-extracted with sulphuric acid, whereas the organic phase is separated into initial components via treatment by sodium hydroxide solutions.



9.
Obtaining Bismuth-Potassium Citrate

E. S. NAIDENKO, YU. M. YUKHIN, L. I. AFONINA and K. B. GERASIMOV
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia),
E-mail: vivienne@ngs.ru
Keywords: bismuth-potassium citrate, synthesis, aqueous solutions
Pages: 523528

Abstract >>
The interaction of bismuth (III) citrate BiC6H5O7 with the aqueous solutions of potassium hydroxide in different concentrations was studied by means of X-ray phase analysis, IR spectroscopy, thermogravimetry and chemical analysis. The conditions for the formation of the potassium salt of bismuth (III) citrate having the composition KBiC6H4O7 · H2O were determined. Reasonability of obtaining this compound through the interaction of the aqueous solution of potassium hydroxide with bismuth (III) citrate with their molar and mass ratio equal to 1.0 was shown.



10.
Modifying the Coal of the Sergeevo Deposit by Means of Liquid-Phase Catalytic Alkylation with Isopropyl Alcohol

L. P. NOSKOVA and I. F. SAVCHENKO
Amur Integrated Research Institute, Far East Branch of the Russian Academy of Sciences, Per. Relochny 1, Amurskaya obl., Blagoveshchensk 675000 (Russia),
E-mail: noskova@ascnet.ru
Keywords: alkylation, isopropyl alcohol extraction, bitumen, waxes, lignite
Pages: 529535

Abstract >>
Modifying the low-calorific lignite from the Sergeevo deposit by means of liquid-phase catalytic alkylation with isopropyl alcohol was performed. The basic processes involved in the interaction of the coal under investigation with isopropyl alcohol were described. A positive effect of the alkylation treatment exerted on the coal bituminosity, the componential composition and the physicochemical characteristics of modified products obtained has been revealed.



11.
Obtaining New Biologically Active Compounds from 2-Vinyloxyethylisothiocyanate

O. A. NURKENOV,   I. V. KULAKOV,   S. D. FAZYLOV and   A. ZH. SARSENBEKOVA
Institute of Organic Synthesis and Coal Chemistry, NAS of Kazakhstan, Ul. Alikhanova 1, Karaganda 100008 (Kazakhstan),
E-mail: kulakov_iv@mail.ru
Keywords: vinyloxyethylisothiocyanate, alkaloids, cytisine, anabasine, l-ephedrine, d-pseudoephedrine, XRD structural analysis
Pages: 537545

Abstract >>
Via the reaction of alkaloid cytisine, l-ephedrine, d-pseudoephedrine as well as glucosylbenzylamine and xylosylbenzylamine aminoglycosides with vinyloxyethylisothiocyanate and its acetal derivatives, we synthesized and characterized novel 2-vinyl-, N-1-propargyl-, 1-N-phenyloxyethoxyethylo-N-aminothiourea species. By the example of the N-vinylethoxythiocarbamoyl derivatives of l-ephedrine and d-pseudoephedrine is demonstrated that the mentioned thiourea species could quite readily undergo hydrolyzing in the presence of acids. On the basis of salicylic acid hydrazide we have synthesized and studied the acidic hydrolysis of corresponding vinyloxyethylthiosemicarbazide. The composition and the structure of the thiourea derivatives synthesized were confirmed by IR spectroscopy, 1H NMR, 13C NMR and mass spectrometry as well as by XRD structural analysis.



12.
Effect of Oxidative Modifying on the Chemical Composition and Properties of Coal from the Khushuut Deposit (Mongolia)

S. A. SEMENOVA1, N. I. FEDOROVA1, D. P. IVANOV2, A. N. ZAOSTROVSKY1 and Z. R. ISMAGILOV1,2
1 Institute of Coal Chemistry and Material Science, Siberian Branch of the Russian Academy of Sciences, Sovetskiy Pr.18, Kemerovo 650000 (Russia),
E-mail: iuxm@yandex.ru
2 Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia),
-mail: bic@catalysis.ru
Keywords: Mongolian coal, ozonation, treatment with nitrogen (I) oxide, oxidation in oxygen plasma
Pages: 547553

Abstract >>
Results of the comparative analysis of the effect of oxidative modifying performed using ozone, nitrogen (I) oxide and low-temperature oxygen plasma, on the chemical composition of coal from the Khushuut deposit (Mongolia) and its ability to thermal destruction are reported.



13.
Studying the Dynamics of Changing the Concentration of Acetate Ions in the Blood of Patients in the Course Dialysis Method Using Capillary Electrophoresis

Z. M. UNAROKOV1, O. V. SHUVAEVA2 and T. V. MUKHOEDOVA1
1 Meshalkin Novosibirsk Research Institute of Circulation Patology, Ul. Rechkunovskaya 15, Novosibirsk 630055 (Russia),
E-mail: jovi33@rambler.ru
2 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia)
Keywords: capillary electrophoresis, acetate ion, acetate-free dialysis, SLED
Pages: 555560

Abstract >>
The content of acetate ions in the blood of patients after cardiac surgery in the course of hemodialysis using different dialyzing solutions was investigated for the first time. Using the method of capillary electrophoresis it was revealed that in the case when the bicarbonate dialysate contains acetate ions in a small amount (3 mmol/L), the concentration thereof in blood exhibits a 12-fold increase, which causes enhancing the risk of cardiovascular instability in  the course of hemodialysis.



14.
Current State of the Selenga River Waters in the Russian Territory Concerning Major Components and Trace Elements

E. P. CHEBYKIN1,2, L. M. SOROKOVIKOVA1, I. V TOMBERG1, S. V. RASSKAZOV2, T. V. KHODZHER1 and M. A. GRACHEV1
1 Limnological Institute, Siberian Branch of the Russian Academy of Sciences, Ul. Ulan-Batorskaya 3, Irkutsk 664033 (Russia),
E-mail: cheb@lin.irk.ru
2 Institute of the Earths Crust, Siberian Branch of the Russian Academy of Sciences, Ul. Lermontova 128, Irkutsk 664033 (Russia)
Keywords: Selenga River, major ions, trace elements, ICP-MS analysis
Pages: 561580

Abstract >>
Studies were performed concerning the seasonal dynamics of major ions (Na+, Mg2+, K+, Ca2+, SO42-, Cl-, HCO3-), Si, 52 trace elements, organic carbon, pH, O2 in the Selenga River, the main tributary of Lake Baikal and the rivers flowing into the Selenga in the Russian territory, the flow paths and lakes of the delta within the barrier area of Lake Baikal (up to 7 km from the mouth of the Selenga River). Using the factor analysis we revealed four main groups, those differ from each other in the spatial and temporal distribution of the components in the Selenga River. The first group comprises the water salinity, the major ions and trace elements, some conservative trace elements (B, Br, Sr, Mo, Ba, Re, U). The concentration values for these components are maximal within the ice period (March) and minimal within the flood period (May), exhibit an increase on the frontier with Mongolia reducing towards the mouth as being diluted by less saline water of the tributaries of the Selenga River. The elements of the second group are connected with the content of dissolved organic matter capable of mobilizing difficultly soluble and almost insoluble elements (Be, Al, Ti, Fe, Ni, Cu, Ga, Y, Zr, Nb, Hf, REE, Pb, Th) to produce fine-dispersed organomineral complexes. The concentration values for these elements demonstrate increasing in the spring, in the course of the snowmelt and of an active removal of organic matter from the catchment area. The third group of the elements (Si, Li, Cr, Mn, Co, Zn, Ge, Rb, Ag, Cd, Sn, Cs, Bi) reflects the processes of water acidifying against the background of seasonal dynamics inherent in the dissolved oxygen. Concentration values for these elements increase towards the mouth (except for Co within the period of spring and autumn, as well as Ge in winter), being to a significant extent increased in the winter. The fourth group of the elements (V, As, Sb, I, W, Cu) represents a marker of a weak cross-border transfer in summer. Increased concentration values of these elements are observed in July, especially on the upper section of the river (0120 km from the frontier with Mongolia). The maximum and average weighted concentrations of the most of trace elements in the Selenga River are lower than those inherent in the global natural river background. Exceeding the maximum background concentration values is observed for Mo (10 %), Mn (10 %) and Ge (60 %). Average weighted background concentration values exhibit a 2- to 5-fold exceeding in Zr (2.1), Nb (2.1), Sr (2.5), Ti (2.9), U (3.5), Y (3.5), Zn (3.7), Mo (3.8) and Sn (4.9), which could be caused by the geological structure of the basin and the naturally occurring processes of mobilizing the elements. The concentration of Mo, Mn, Cu, Al, Fe, V in the general river station of the Selenga River and the tributaries thereof in some seasons are slightly higher than Russian standards established for fish-industry water basins (in 80 % of cases less than 2 MPC). Within the barrier zone of Lake Baikal there is an excess over the fish industry water standards in Mo registered to be constant (1.22.1 MPC): for Cu in winter (up to 1.8 MPC), in summer (up to 1.9 MPC), in autumn (up to 1.3 MPC); for V in summer (up to 1.6 MPC); for Mn in winter (up to 2.2 MPC).



15.
Analysis and Processing of Heavy Pyrolysis Tar

M. A. LEBEDEVA1,2, V. I. MASHUKOV2 and A. K. GOLOVKO1
1 Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
2 Scientific Centre of SIBUR for Chemical Technologies NIOST Ltd., Kuzovlevskiy Trakt 2, Build. 270, Tomsk 634067 (Russia),
E-mail: lma-niost@mail.ru
Keywords: heavy pyrolysis tar, chromatographic analysis, chemical composition, processing technology, radical polymerization, dark petroleum polymer resin
Pages: 581585

Abstract >>
Chemical composition of the light fraction (boil ≤ 300 C) of heavy pyrolysis tar (HPT) was studied; more than 40 components were identified. The content and nature of the still bottoms of HPT were determined. It was established that the method of HPT processing is determined mainly by the concentrations of naphthalene, unsaturated compounds and still bottoms. The processes of HPT polymerization with the application of radical type initiators dicumyl peroxide and di-tert-butyl peroxide (DTBP) were studied. New grades of petroleum polymer resins (PPR) with high softening temperature were developed; they can be used in rubber-processing industry. A method of HPT processing using the still bottoms of styrene rectification and DTBP, followed by evaporation of volatile components, was proposed for obtaining PPR with required properties and the yield up to 68 %.



16.
Mechanical Activation of the Process of Enzymatic Saccharification of the Carbohydrates of Rice Husk

E. G. SHAPOLOVA1,2, A. L. BYCHKOV1,2 and O. I. LOMOVSKY1
1 Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia),
E-mail: shapolova@solid.nsc.ru
2 Novosibirsk State University, Research and Education Centre for Molecular Design and Ecologically Safe Technologies, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
Keywords: mechanoenzymatic hydrolysis, rice husk, biofuel, carbohydrates
Pages: 587591

Abstract >>
Effect of the mechanical activation of rice husk on the progress of subsequent enzymatic hydrolysis was studied. It was established that mechanical treatment promotes an increase in specific surface area, destruction of the silica shell coating lignocellulose, and substantial amorphization of the crystal regions of cellulose. As a result, the degree of conversion of polymer carbohydrates into soluble saccharides increases practically by a factor of 13. So, mechanoenzymatic treatment of rice husk allows one to obtain carbohydrate-containing intermediate product that may be used for further microbiological processing.