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Chemistry for Sustainable Development

2014 year, number 5

1.
Composition of Atmospheric Suspensions from the Botchinsky State Reserve (Khabarovsk Territory) from the Data on the Pollution of Snow Cover

K. S. GOLOKHVAST1, S. V. KOSTOMAROV2, I. V. KOSTOMAROVA2, P. A. NIKIFOROV1, V. V. CHAIKA1, I. V. SEREDKIN3, I. YU. CHEKRYZHOV4, T. YU. ROMANOVA4 and A. A. KARABTSOV4
1Far East Federal University, Ul. Pushkinskaya, 37, Vladivostok 690990 (Russia)
2Botchinsky State Natural Reserve, Ul. Sovetskaya, 28B, Sovetskaya Gavan, Khabarovsk Territory 682800 (Russia)
3Pacific Institute of Geograph, Far East Branch of the Russian Academy of Sciences, Ul. Radio, 7, Vladivostok 690022 (Russia)
4Far East Geological Institute, Far East Branch of the Russian Academy of Sciences, Prospekt 100 Let Vladivostoku, 159, Vladivostok 690022 (Russia)
Keywords: suspensions, reserve, snow, microparticles, W, Ti

Abstract >>
The first results of the granulometric studies of nano– and microparticles of atmospheric suspensions in snow samples collected in winter 20122013 at the territory of Botchinsky reserve are presented. It is shown that the snow samples from five sampling stations contain nano- and microparticles of metal compounds (W, Ti, Fe, Ba, Sn, Zn, Zr, Ag, Ce, La) of technogenic origin, as well as increased concentrations of water-soluble compounds of some metals (zinc). In the samples from two sampling stations (the valleys of the Mulpa and the Botchi) the fraction of particles with the size 110 mm is 100 %.



2.
Pollution of Snow Cover with Polycyclic Aromatic Hydrocarbons and Toxic Elements for Novokuznetsk as Example

N. V. ZHURAVLEVA1, R. R. POTOKINA1, Z. R. ISMAGILOV2,3 and E. R. KHABIBULINA1
1PC West Siberian Test Centre, Ul. Ordzhonikidze 9, Novokuznetsk 654006 (Russia)
2Institute of Coal Chemistry and Material Science, Siberian Branch of the Russian Academy of Sciences, Sovetskiy Pr.18, Kemerovo 650000 (Russia)
3Gorbachev Kuzbass State Technological University, Ul. Vesennyaya 28, Kemerovo 650000 (Russia)
Keywords: snow cover, polycyclic aromatic hydrocarbons, toxic elements, particle size distribution, high-performance liquid chromatography, atomic emission spectroscopy, laser granulometry

Abstract >>
Qualitative and quantitative composition of polycyclic aromatic hydrocarbons was studied in the samples of snow water in Novokuznetsk. The distribution of these hydrocarbons between the solid and liquid phases was studied by means of high-performance liquid chromatography. The maximal content of carcinogenic and toxic PAH was detected in the samples of snow water from the Kuznetsk region: it exceeds the MPC for benz(a)pyrene by a factor of 72.3. The concentrations of toxic elements in snow water samples were determined b y means of atomic emission spectroscopy with inductively coupled plasma. It was shown that the concentrations of a number of toxic elements (Al, Cu, Mn, Fe) in snow water exceed MPC adopted for surface water. Particle size distribution for the suspended matter of snow water was studied by means of laser granulometry. It was established that 90 % of suspended matter in snow cover is represented by the particles with the size not more than 35.5 mm.



3.
Mechanically Stimulated Low–Temperature Synthesis of LiYO2

M. D. KOVALENKO, G. R. KARAGEDOV and A. L. MYZ
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
Keywords: mechanochemistry, LiYO2, synthesis

Abstract >>
Preliminary mechanical treatment of a mixture of yttrium oxide and lithium carbonate in a planetary mill intensifies subsequent thermal synthesis of LiYO2 and allows reducing the temperature of complete transformation to 850 °C. The synthesized powder can be used as an additive that accelerates sintering of aluminium nitride without additional grinding. Mechanical treatment of the mixture results in the formation of aggregates that are frameworks of Y2O3 filled with lithium carbonate. Due to this, the surface of contact between reagents increases. However, with excess over some limiting acceleration developed in the mill, the framework densifies, and extrusion of the second component is observed. As a consequence, the reactivity of the mixture decreases, especially if lithium carbonate is changed for hydroxide. in this connection, mechanical treatment of the mixture under the same experimental conditions is unreasonable. The mixture obtained by precipitation from solution without mechanical treatment allows carrying out the synthesis even at 700 .



4.
Syntheiss of the Derivatives of Hydrotropic Cellulose

A. A. KORCHAGINA, M. N. DENISOVA, V. V. BUDAEVA and V. N. ZOLOTUKHIN
Institute of the Problems of Chemical and Power Technologies, Siberian Branch of the Russian Academy of Sciences, Ul. Sotsialisticheskaya 1, Biysk 659322 (Russia)
Keywords: miscanthus, hydrotropic cellulose, nitration, cellulose nitrates, stabilization, IR spectroscopy, scanning electron microscopy

Abstract >>
The properties of refined hydrotropic cellulose and cellulose nitrates synthesized using the commercial sulphuric-nitric mixture were studied. In spite of the high content of non-cellulose components, the obtained cellulose nitrate samples are close in their characteristics to highly viscous colloxilin. It was established by means of IR spectroscopy that hydrotropic cellulose is identical to classical cellulose in characteristic frequencies, while the products of its synthesis are cellulose nitrates. The morphology of hydrotropic cellulose and its nitrates was characterized by means of scanning electron microscopy.



5.
Experimental Analysis of Response Resource of Motor Oil of Diesel Engines by Means of High-Resolution NMR Spectroscopy

V. V. KORYAKINA1, E. YU. SHITS1 and I. I. SEDALISHCHEV2
1Institute for Petroleum and Gas Problems, Siberian Branch of the Russian Academy of Sciences, Ul. Oktyabrskaya 1, Yakutsk 677891 (Russia)
2PC Almazy Anabara OJSC, Ul Chernyshevskogo 6, Yakutsk 677000 (Russia)
Keywords: motor oil, NMR spectroscopy, phosphoruscontaining additives, zinc diorganodithiophosphate

Abstract >>
Results of integrated high-resolution NMR studies of operating changes of motor oil of Texaso Company (the USA) for diesel engines of automobiles are presented. It is shown that a number of the chemical characteristics of oil change during operation: the degree of aromaticity, the ratio of methyl to methylene group content, content of phosphorus–containing additives. Qualitative and quantitative analysis of phosphoruscontaining additives was carried out, the adaptation mechanism of the response of oil additive was revealed. The promising character of the use of NMR spectroscopy in monitoring-based analysis of motor oil was demonstrated.



6.
Utilization of the Wastes of Fibrous and Film Polyethylene and Polypropylene Materials by Means of Surface Oxidation

E. I. KULISH, M. V. BAZUNOVA, S. V. KOLESOV and A. N. ZHUKOVA
Bashkiria State University, Ul. Zaki-Validi 32, Ufa 450076 (Russia)
Keywords: wastes of polyolefin products, hydroperoxide groups, modification

Abstract >>
Physicochemical regularities of the surface oxidation of materials made of polypropylene, polyethylene and their wastes were studied as the method to make secondary polymer materials. The properties of the obtained samples were studied. A comparative analysis of the results of modification of the wastes of fibrous and film materials of polyolefins using different methods (oxidation with atmospheric oxygen in the aqueous medium, in the gas phase, ozonation) shows that the simplest and the most efficient method is non-initiated solid-phase thermal oxidation with atmospheric oxygen.



7.
Biochemical Features of Soil of Industrial City under the Conditions of Eastern Siberia

E. V. NAPRASNIKOVA
Sochava Institute of Geography, Siberian Branch of the Russian Academy of Sciences, Ul. Ulan-Batorskaya 1, Irkutsk 664033 (Russia)
Keywords: city, soil, heavy metals, pollution, biochemical activity, sanitary state

Abstract >>
The features of the modern state of soil in Cheremkhovo city (Irkutsk Region) and adjacent territories are demonstrated. The high level of soil pollution with heavy metals was revealed. The results of sanitary microbiological analysis provide evidence of soil pollution with communal and household organic substances and allow evaluating the state of soil as close to epidemically dangerous one.



8.
Biodestruction of Hydrocarbons of Highly Viscous Petroleum with Soil Microorganisms

V. S. OVSYANNIKOVA, D. A. FILATOV, L. K. ALTUNINA and L. I. SVAROVSKAYA
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
Keywords: indigenous soil microflora, enzymatic activity, biodestruction, highly viscous petroleum, hydrocarbon-oxidizing microorganisms, petroleum hydrocarbons, naphthenes, arenes

Abstract >>
The effect of highly viscous petroleum from the Tzagaan Els deposit (Mongolia) on the oxygenase activity of indigenous soil microflora was studied. It was shown that after the adaptation of microorganisms to hydrocarbons their number increases by two orders of magnitude, while the enzymatic activity increases by a factor of 2–3. Utilization of viscous petroleum during 180 days of experiment is 78 %. Analysis of petroleum after biodegradation showed that it contains a large number of oxygen-containing compounds — intermediate products of oxidation during microbiological assimilation of petroleum hydrocarbons. In the composition of highly viscous petroleum, all hydrocarbons are affected by the biochemical oxidation by soil microorganisms.



9.
Migration of Petroleum Products from Polluted Soil into the Bulk Insulating Layer of Pure Sand

E. N. FEDOSEEVA, A. D. ZORIN, V. F. ZANOZINA and L. E. SAMSONOVA
Lobachevsky Nizhniy Novgorod State University, Prospekt Gagarina, 23, build. 5, Nizhniy Novgorod 603950 (Russia)
Keywords: soil, contamination, oil products, capillary rise, wetting

Abstract >>
It is shown that insulation of masout soil pollution with a bulk layer of pure sand may cause its contamination. The migration of the pollutant against the force of gravity occurs through the mechanism of capillary rise in the case of low moisture content in the pore space, and in water–saturated horizons this occurs also due to the difference in the densities of masout and water.



10.
Synthesis of Biopolymers with Improved Performance Characteristics

O. N. VINOGRADOVA1,2 and D. A. SYRVACHEVA2
1Institute of Biophysics, Siberian Branch of the Russian Academy of Sciences, Akademgorodok 50, build. 50, Krasnoyarsk 660036 (Russia)
2Siberian Federal University, Prospekt Svobodny 79, Krasnoyarsk 660041 (Russia)
Keywords: degradable biopolymers, polyhydroxyalkanoates, PHA, copolymers, 3–hydroxybutyrate, 4–hydroxybutyrate, 3–hydroxyhexanoate, chemical composition, properties

Abstract >>
Urgency of the studies aimed at the development of ecologically safe, naturally biodegradable polymer materials including biopolymers of natural origin — polyhydroxyalkanoates is demonstrated. Short– and mediumchain samples of polyhydroxyalkanoates of the new chemical structure with different combinations of the fractions of 3 and 4hydroxybutyrate or 3hydroxyhexanoate were obtained. The physicochemical and mechanical properties of copolymer samples of polyhydroxyalkanoates were studies.



11.
Sorption Capacity of the Alloys of (TiCr1.8)1–xVx System under the Conditions of Electrolytic Saturation with Hydrogen

A. L. GABOV1, N. A. MEDVEDEVA1, N. E. SKRYABINA1 and DANIEL FRUCHART2
1Perm State National Research University, Ul. Bukireva 15, Perm 614990 (Russia)
2Institut L. Nel, CNRS, 166, 38042, Grenoble (France)
Keywords: alloys of Ti–Cr–V system, reaction of hydrogen evolution, electrochemical extraction, impedance, sorption of electrolytic hydrogen

Abstract >>
Electrocatalytic activity of the alloys of (TiCr1.8)1–xVx system in the reaction of hydrogen evolution was studied by means of polarization curves, electrochemical extraction and impedance spectroscopy. Parameters characterizing sorption properties of alloys under the conditions of electrochemical saturation were determined: the amount of absorbed hydrogen, effective diffusion coefficient, thickness of diffusion zone.



12.
Features of the Chemical Composition of Interstitial Water of the Holocene Section of Sapropel in Lake Dukhovoye (Southern Pribaikalia)

A. E. MALTSEV1, A. A. BOGUSH1,2 and G. A. LEONOVA1
1Sobolev Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia)
2Lomonosov Moscow State University, Leninskiye Gory 1, Moscow GSP-2, 119991 (Russia)
Keywords: interstitial water, sapropel, phytoplankton, element occurrence forms

Abstract >>
Comparative analysis of interstitial water in organic sapropel (0–167 cm) formed during middle Holocene for 5100 years, and the surface water of Lake Dukhovoye (Southern Pribaikalia) was carried out. Transformation of hydrocarbonate calciumsodiummagnesium lake water into hydrocarbonatesulphate interstitial water of sapropel is observed. It is established that mineralization of interstitial water increases with depth, that is, the transition from ultrafresh surface water to fresh interstitial water of organic sapropel occurs. Interstitial water is enriched with almost all the studied ions (Ca2+, Mg2+, Na+, K+, HCO3 and Cl) and elements (Al, Fe, Mn, Pb, Cd, Zn, Cu, Ni and Co) in comparison with surface water. The series of element mobility show that the mobility of some elements changes substantially in the section of sapropel of Lake Dukhovoye. In surface water Na, K, Ca, Mg, Mn, Cd and Zn dominate in aqua ion forms, Al and Fe in hydroxide complexes, Pb and Ni in carbonate complexes, Cu in fulvate, hydroxide and carbonate complexes. The fraction of aqua ion forms of Na, K, Ca, Mg, Mn, Cd and Zn in interstitial water of sapropel decreases with depth, while the fraction of sulphate complexes increases. Redistribution of forms in comparison with surface water occurs.



13.
Zr–LaPromoted Zeolites for Obtaining Synthetic Fuel — Dimethyl Ether

P. G. MUSICH1, L. N. KURINA1 and A. V. VOSMERIKOV2
1Tomsk State University, Prospekt Lenina 36, Tomsk 634050 (Russia)
2Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
Keywords: zeolite, ZSM–5, catalysts, modification, synthesis gas, dimethyl ether

Abstract >>
Catalysts containing lanthanum and zirconium oxides were prepared on the basis of zeolite of ZSM–5 type using different preparation procedures. The effect of promoting additive and the method of zeolite modification on their catalytic and physicochemical properties in the process of obtaining dimethyl ether from synthesis gas was studied. It is demonstrated that the introduction of the modifying agent by impregnation causes an increase in the yield of target product in comparison with nonmodified sample by a factor of 1.7 and 1.8 for zirconium and lanthanumcontaining catalysts, respectively. The optimal conditions of the process were determined.



14.
Volcano Erebus as the Key Factor of Enhancement of the Antarctic Ozone Hole

E. S. SAVELYEVA, V. V. ZUEV and N. E. ZUEVA
Institute of Monitoring of Climatic and Ecological Systems, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 10/3, Tomsk 634055 (Russia)
Keywords: Antarctic ozone hole, circumpolar eddy, polar stratospheric clouds, volcano Erebus, degassing, chlorine cycle

Abstract >>
Estimation of the amount of stratospheric hydrogen chloride HCl necessary for the formation of the spring ozone hole was carried out during the period of its existence above McMurdo station in 1992 on the basis of the maximal concentration of ClO in lower Antarctic stratosphere. The height of gas plume emitted by the Antarctic volcano Erebus during active degassing was calculated, as well as the trajectories of further cyclonal elevation of these emissions inside high cyclones to the height of more than 18 km, obtained using the NOAA HYSPLIT model. It is demonstrated that the fraction of volcanic emissions reaching the height of the stratosphere averaged per year is 41.5 %. It is established that the amount of volcanogenic HCl entering the Antarctic stratosphere every year is sufficient for the formation of the ozone hole of modern scale. It is shown that anomalous enhancement of the activity of Erebus in early 1980es became the key factor for the substantial increase of the Antarctic ozone anomaly. A decrease of the size of the spring ozone hole above Antarctica is possible only in the case of sharp decrease or complete termination of the activity of this volcano.