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ISSN 0016-7029, Geochemistry International, 2016, Vol. 54, No. 13, pp. 1096–1135. © Pleiades Publishing, Ltd., 2016.
Fig. 1. Luna–Glob and Phobos–Grunt projects.
Structure of the surface layer. TV–image, granulometry, layering of regolith column.
Internal structure of Phobos. Seismic sounding.
Whether Phobos contain differentiated material? Trace elements analysis including REE pattern, petrological studies (texture, mineral assemblages).
Fig. 2. MAL-1F mass analyzer mounted on the Phobos–Grunt spacecraft.
Fig. 4. Cosmic dust detector.
Fig. 5. Thermodynamic calculation of the interior structure of Callisto and Titan. (a)—a model of partially differentiated Callisto’s interior with an internal ocean. The maximum total thickness of the outer water–ice shell is estimated as 270–315 km. The thickness of the ice-I crust is 135–150 km, and the thickness of the underlying internal ocean is about 120–180 km. (b)—internal structure of Titan with a subsurface water ocean (~300 km thick) and an outer conductive crust of I h ice 80 km thick. The maximum thickness of the outer water–ice shell is ~450 km. Dotted lines are phase transition boundaries for ices in the ice–rock mantle. Hatching indicates the permissible range of the size of the central rock–iron core (Dunaeva et al., 2016).
Fig. 6. Formation of the Earth–Moon system. (a) giant-impact hypothesis, widely accepted in the Western literature (Hartman, 1975; Canap, 2004 and others); (b) model invoking formation of Moon by fragmentation of the original dust cloud (Galimov, 2011); (c) computer modeling of fragmentation process (Galimov and Krivtsov, 2012).
Fig. 7. Quantitative parameters of the Earth–Moon system formation, as suggested by our models. (a) the composition of the Moon corresponds to the chondrite composition after 40% evaporation, (b) asymmetric growth of the Moon and the Earth, (c) a timeline of the Moon’s and Earth’s formation based on the results of isotope analysis.
Fig. 9. Identification the Chelyabinsk meteorite. Originally published in Geochemistry International in July 2013.
These works provide a strong support to the national school of space research, despite the absence of any long-term space projects in Russia.
At difficult times, GEOKhI was able to save a priceless collection of meteorites of lunar samples. Moreover, about 750 additional meteorites were added to the collection over the past 15 years.
*** The national meteorite collection at GEOKhI consisting of a diverse array of extraterrestrial material is one of the major meteorite collections in the world. This collection also comprises lunar samples delivered by the Soviet probes Luna-16, Luna-20, and Luna-24. The Meteorite Committee of the Russian Academy of Sciences and the Laboratory of Meteoritics are also located at GEOKhI.
Fig. 10. Variations in the galactic cosmic ray intensity in the heliosphere.
Fig. 11. Revision of Sm/Nd and initial Nd isotopic ratios of terrestrial materials.
tial Sm/Nd ratio of the Earth is slightly different from the chondritic value. This conclusion is of fundamental importance because global geochemical models are based on the concept of mantle enrichment or depletion relative to the chondritic composition (Fig. 11). The observed correlations between element ratios require a substantial revision of the existing models and isotope ratios (Kostitsyn, 2014). For example, the Rb/Sr value should be taken to be 0.0205 instead of 0.0286, the Th/U ratio would become equal to 4.0, etc. (Fig. 12). These data can substantially change our understanding of the composition of the primitive Earth. *** The laboratory of Academician L.N. Kogarko has collected a vast database on carbonatites of the world. Global distribution of carbonatite massifs was shown to be spatially related to zones of weakness in the mantle that have been identified by seismic tomography. Moreover, the distribution of carbonatites and their geological evolution are global in character (Fig. 13).
Alkaline magmatism apparently commenced and became more extensive at 2.8 Ga. This period is also marked by the carbonatite magmatism and the widespread emplacement of kimberlitic rocks with low diamond potential, probably reflecting the redox evolution of the mantle toward more oxidized conditions (Kogarko, 2007). Kogarko et al. (2002) suggested that large-scale release of Н2О-bearing СО2-rich fluid may result in the migration of incompatible elements, leading to the formation of economically significant REE deposits. A detailed study of the Lovozero alkaline massif revealed the presence of distinct trends of trace element concentrations in ore minerals (Fig. 14). The lower part of the intrusion is characterized by high REE and Ti contents, while its upper part has high contents of Nb, Ta, and radioactive metals (Kogarko et al., 2002). From a mineralogical point of view, the main ore-bearing zones are those containing early euhedral loparite and eudialyte. Zones containing late interstitial segregations of loparite and eudialyte proved to be of low economic potential. These results can serve as a new geochemical criterion for an exploration model of REE deposits.
Fig. 12. Revision of some element ratios of terrestrial materials.
Fig. 13. Evolution of alkaline magmatism over geologic time.
The estimate of potential rare-metal resources at Gremyakha—Vyrmes deposit, Kola Peninsula, showed that the rare-metal ores have a top-cut grade of niobium (up to 3% Nb) and up to 0.4% Zr. The above results confirm a direct link between the current understanding of differentiation trends in the Earth’s mantle, the formation of alkaline-peridotite complexes, and the prediction of economic rare-metal mineralization. *** The evolution of mantle redox state is one of the most crucial areas of research interest at GEOKhI, which covers a variety of research topics from the problems of ore formation to the origin of the biosphere. GEOKhI has developed a core accretion model to explain changes in the redox state of the mantle (Galimov, 2005). It implies that iron in the mantle (in form of FeO) descends to the core boundary by mantle convection where FeO disproportionates to produce Fe metal Fe2O3. Loss of disporportionated Fe metal to the core would raise the Fe2O3 content of the mantle and mantle oxygen fugacity to its presentday levels (Fig. 15).
Fig. 14. Vertical variations in the concentration of ore elements across the Lovozero complex (Kogarko et al., 2002).
Fig. 15. Evolution of the primitive mantle from reduced to oxidized compositions, accompanied by core accretion (Galimov, 2015).
synthesizing diamonds in a cavitating fast fluid flow. This study showed that the fast flow of a fluid through a fracture of a variable section—a case of kimberlite pipe formation—can be accompanied by cavitation in the fluid. The collapse of cavitation bubbles may create very high pressures on the order of tens and even hundreds of atmospheres, which could be sufficient for diamond synthesis.
Fig. 16. (a) Oxygen fugacity and dominant volatiles in Earth and Moon (initial and present). (b) Experimental study of Fe–Si system under 4 GPa, 1550°C and low oxygen fugacity (–2.1 and –3.5 units below IW buffer) (Kadik et al., 2014, 2015).
In 2004, using the experimental setup developed in collaboration with the Bauman Moscow State Technical University, we obtained for first time diamonds during cavitation in benzene (Galimov et al., 2004). The synthesized diamonds were thoroughly identified (Figs. 18 and 19).
Fig. 18. (a) Experimental setup, which was first used for the cavitation synthesis of diamonds in benzene (Galimov et al., 2004); (b) Pilot setup at GEOKhI, which was used for the cavitation synthesis of diamonds.
Fig. 19. Cavitation diamonds, their identification and P—T conditions during experiments.
Fig. 20. Diamonds discovered in Tolbachik lavas as natural examples of cavitation diamonds.
Fig. 21. Simulation results obtained using the COMAGMAT-5 program.
variations in the parameters of sedimentation during the Mesozoic—Cenozoic (Mz–Kz) (Fig. 23). The results show that terrigenous sedimentation prevailed over carbonate deposition in the Artic basin, which is characterized by intervals with high accumulation rates of organic matter (black shales). It was also shown that the sedimentation history in the Arctic basin was mainly controlled by global tectonic trends (Levitan et al., 2015). The lithofacies maps compiled at GEOKhI to reconstruct the sedimentary cover of the Arctic basin can be used as a basis for predicting the hydrocarbon potential of the Arctic. It is also worth noting a study conducted by a research group led by A.S. Nemchenko, which was largely focused on a comparative assessment of petroleum potential of the Russian Artic and petroleumproductive areas of Alaska.
Fig. 23. Lithological maps of the Arctic basin (Levitan et al., 2015). 1—erosion area; 2—facies zone of terrestrial sedimentation; 3—facies zone of shallow marine sedimentation (<200 m); 4—facies zone of deep marine sedimentation (>200 м); 5—facies zone of ocean sedimentation ; 6—sands; 7—gravel; 8—clays; 9—silts; 10—carbonates; 11—cherts; 12—black shales; 13—coals; 14—basalts; 15—andesites; 16—flysh; 17—isopachytes (m).
BIOCHEMISTRY AND GEOECOLOGY Biogeochemistry as a new scientific discipline was first established by V.I. Vernadsky. The main research focus of the Laboratory of Biogeochemistry led by V.V. Ermakov is the problem of the diseases associated with endemic deficiencies or excesses of essential elements. Several Se-deficient areas identified in previous studies gave an impetus to further research on selenium biochemistry, thus providing the basis for pharmaceutical application of selenium for protection against cancer and cardiovascular diseases (Ermakov, 1974). A significant amount of analytical data was accumulated in thousands of analyses of soil and plant samples to determine risk factors for Kashin-Bek disease in some regions. It was shown that soils in these regions are characterized by relatively high contents of Р, Ва, and Sr, whereas the influence of other factors cannot be ruled out (Ermakov et al., 2012).
The main objective of radioecologists is the identification of physicochemical forms of radionuclides supplied to the Russian Arctic seas. Work is being done in this area. A new method for identification of radionuclide-carrying colloidal particles was developed in the Laboratory of Radioecology (Alenina et al., 2014). An automatic radiation control buoy developed in the same laboratory (Fig. 26) was designed to be installed in the vicinity of potentially hazardous submarine sites, e.g., in the bays of the Novaya Zemlya Archipelago acting as storage sites for aged submarine nuclear reactors. The buoy makes routine measurements and transmits its data in real-time through satellites. A non-hygroscopic scintillator developed in cooperation with the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences was designed to ensure continuous operation of the above submarine buoy.
2006) for mapping the distribution of δ13C, organic matter content (Fig. 25), and redox potential of the sediments. Thus, these results were used as a basis for our current understanding of the radiological state of the environment in the Russian Arctic seas. It should be emphasized that our previous investigations demonstrated that the concentrations of radionuclides in seawater did not exceed permissible levels. This conclusion was very important in view of publicly raising concerns about severe pollution hazard in the Russian Arctic. However, radioecological control and monitoring in Arctic seas should be continued.
Fig. 25. Content and isotopic composition of organic matter in sediments of the Kara Sea.
P + 01 R + 00 Fig. 26. Radiation monitoring buoy.
Fig. 27. Map showing the distribution of radioactive iodine-131 in the Bryansk region (a) and environmental risk (b) compiled by E.M. Korobova from a comparison of maps for Chernobyl iodine-131 fallout and natural iodine deficiency.
*** Another focus of research (laboratory of V.N. Nosov) lies in the development of methods for detecting local anomalies observed on the sea surface as a result of natural phenomena, such as submarine volcano eruption, tsunami, tectonic dislocation, as well as those of anthropogenic origin. In 2013–2015, GEOKhI conducted photographic mapping of trace anomalies in the sea surface from the International Space Station.
Fig. 28. Geochemistry of small lakes in Russia (Moiseenko et al., 2013).
cooperative efforts of several institutions. Last year, these studies received support from the Russian Science Foundation. We define the phenomenon of life as the evolution of ordering. It was shown that in steady state systems the processes of entropy production, or disordering, coupled with negentropy production, or ordering, are possible. These conjugated processes are governed by the second law of thermodynamics (Galimov, 2004). At the molecular level, this mechanism is manifested by the reaction with the participation of adenosine— triphosphate (ATP) (Galimov, 2009). This concept was further developed as part of the academic program “The Origin and Evolution of the Biosphere” (Fig. 29). The hypothesis that current life on Earth descends from an RNA world (ribonucleic acids) is widely accepted in biology. The RNA world hypothesis implies that nucleic acids were the first ones to emerge and dominate under prebiotic conditions, which gave rise to other processes of biosynthesis. Our model turns to the other logic. Synthesis of RNA was the first step in the evolution of life. The ordering process with the participation of ATP is limited to molecular selection. Peptides and amino acid chains are very efficient organic catalysts. Therefore, the next step after the emergence of the RNA world was a synthesis of peptides, precursor proteins, rather than nucleic acids. Nucleic bases played a secondary role in the evolution of life. They assured indirect replication of amino acid sequences by agency of nucleotide sequences. Through the millions of years and billions of trials it would take to translate amino acid sequences into the language of nucleic bases, which are now known under the name of genetic code. According to our understanding, the carriers of the genetic code, DNA and RNA, are not a primary substance, acting as agent of ordering of life, but they originated as a certain form of indirect replication of peptides. These postulates were discussed in a series of papers published in the framework of the academic program (Fig. 29). The proposed concept has several important implications. First, one can assume considerable differences in isotope distributions in biogenic and abiogenic compounds. Experimental studies on this issue are being conducted by GEOKhI in cooperation with the Bakh Institute of Biochemistry of the Russian Academy of Sciences. The development of a tool for discrimination of biogenic and abiogenic forms of organic compounds is one of the most urgent tasks of a vigorous program, which would search life within the solar system.
Fig. 29. Origin and evolution of life.
Fig. 30. Solution of the K/Na paradox.
lations in this field occur close to the crystalline basement. Some long producing wells are characterized by an increase in their production rate. This evidence was taken as confirmation of the recharge of oil accumulation from deep basement rocks. This phenomenon excited our interest. We have developed the method that can be used to infer a genetic link between oils and their source rocks based on the distribution pattern of carbon isotopes in the fractions of crude oils. The results of isotope analysis revealed a genetic link between oils from producing beds at the Romashkino oilfield and organic matter from the Devonian Domanik facies beds (Fig. 32). For a measure of genetic affinity, we used the correlation coefficient calculated using an appropriate procedure. The anomalous performance of high-flow-rate wells can be attributed to the hydrodynamic conditions of the oildfield disturbed by the long-term peripheral and pattern water flooding operations. We came to the conclusion that oil migrated into the reservoirs of the Romashkino field from the depressions adjacent to the Tatar arch, where the rocks have already passed through the oil generation window (Galimov and Kamaleeva, 2015).
Fig. 31. Effects of the isotopic composition on organisms.
caldera of Uzon volcano. Samples of microbial mats and plant remains collected from the surface were analyzed in the laboratory by thermal hydrolysis.
The results show that hydrocarbons from this volcanic area are mainly products of the hydrothermal transformation of biota.
Therefore, none of the studied examples provides compelling evidence for the existence of a deep inorganic source for the hydrocarbons in these accumulations.
Fig. 32. Isotopic data suggest a genetic link between the Romashkino oils and organic matter from the Devonian Domanik-facies bed. Oils from the anomalous boreholes are similar to those from normal boreholes.
The Laboratory of Prof. V.P. Kolotov, who is also in charge of the Analytical Department, is involved in many GEOKhI’s projects.
the area. These results and previously studied mechanisms suggest that the Precambrian gases of East Siberia Восточной Сибири were generated by cracking of preexisting oil and that the Precambrian oils were derived from organic matter of mostly bacterial origin.
The development of in-situ analytical technique is the primary goal of this laboratory. Microanalysis is the main geochemical research tool. However, most studies require screening analysis of samples larger than those routinely used in microanalyzer.
In connection with this, we developed a method of computerized digital gamma-activation autoradiography equipped with a uniform irradiation device, which was effective for registration of the decay dynamics of different induced activity (Kolotov et al., 2011).
Fig. 34. New method based on digital gamma-activation autoradiography for screening analysis of element distributions over the large-sized thin sections (tens cm2).
The observed distributions of Pd, Cu, and Ni coincide with the distribution maps for the same area of the thin section surface obtained by SEM (Fig. 34).
was shown that the combined use of acoustic and magnetic fields can substantially improve extraction of the organic molecules (including DNA) from water and aqueous solutions (Fig. 35). Continuous-flow leading in a rotating coiled column has been applied to studies on the mobility of toxic elements in relation to environmental monitoring (Fedotov et al., 2016). This laboratory is well renowned for its inventions, typically a combination of separation techniques such as liquid chromatography and centrifugation. For example, the paper by Shkinev et al. published in this issue illustrates some of the approaches developed in the laboratory.
The other area of research in the lab is the search for materials resistant to neutron radiation in nuclear reactors. Radiation-resistant structural materials can be used to minimize long-lived radiation waste forms. The most recent results show that lithium carbide is a prospective tritium-breeding material for thermonuclear reactors (Alenina et al., 2014).
Fig. 35. Suspension-based ultrasound system. 1—thermostatic control; 2—eluent and eluate collector; 3, 4—pumps; 5—outer cooling jacket; 6—ultrasound column; 7—ultrasound exciter; 8—piezoelectric transducer; 9—Bluetooth USB adapter; 10—computer; 11—sample; 12—eluate; 13—effluent; 14—valve; 15—magnet.
Fig. 37. Analyzer for uranium determination in the concentration range of 3(10–6–10–3) g/L in natural, drinking, and waste waters. Pogonin, V.I., Romanovskaya, G.I., Zevakin, E.A., Zuev, B.K., Patent no. 2488808, priority date February 28, 2012.
Fig. 38. Luminescent analyzer of actinide determination. Detection limit: 10–13g for Pu.
Fig. 39. A new high-sensitive technique for determination of organic compounds.
Fig. 40. Evolution of the theory of adsorption and chromatography.
Fig. 41. A new technique proposed for the purification of industrial phosphoric acid and simultaneous sorption of rare-earth elements. (a) Bench tests at the Institute of Fertilizers and Insectofungicides (2011—2012); (b) Pilot tests at the Belorechensk fertilizer plant (2013—2014).
of microwave radiation allows an easier and faster solution to this problem (Kulyako et al., 2011). The industrial application of this method is scheduled for 2016 at the mining and chemical plant. The magnesium potassium phosphate matrices developed at GEOKhI can be used for immobilization of actinides and other components of solutions containing radioactive waste (Fig. 42). The advantages of this new method, which was tested at the Mayak PA and Siberian Chemical Plant, are as follows (Vinokurov et al., 2009): —low-temperature immobilization, —up to 60% compound accumulation, —mechanical strength and radiation resistance. The proposed radiochemical methods are discussed in more detail in the papers by Academician B.F. Myasoedov et al. in this issue.
Fig. 42. Testing of a magnesium potassium phosphate matrix for immobilization of components of radioactive waste at: (a) Mayak PA and (b) Siberian chemical plant.
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