Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKhI): Scientific results in 2011–2015

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ISSN 0016-7029, Geochemistry International, 2016, Vol. 54, No. 13, pp. 1096–1135. © Pleiades Publishing, Ltd., 2016.

Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKhI): Scientific Results in 2011–2015 Academician E. M. Galimov Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul. Kosygina 19, Moscow, 119991 Russia e-mail: [email protected] Received February 15, 2016; in final form, February 25, 2016

DOI: 10.1134/S001670291613005X

(Report presented at the Academic Council of GEOKhI on November 30, 2015). This is an overview of the main scientific achievements of the Institute during the last 5 years, submitted to the Scientific Council. The results were obtained in the following fields: —Space research. Moon and planets. Meteoritics and cosmochemistry. —Geology and geochemistry. Crust—mantle— core. Ore elements. Diamonds. Oil and gas. —Arctic. —Origin and evolution of the biosphere. Organic geochemistry. —Biogeochemistry and ecology. —Analytical methods and equipment. —Radiochemistry. SPACE RESEARCH. MOON AND PLANETS. METEORITICS AND COSMOCHEMISTRY Let me start with Space Research. GEOKhI was the initiator of the Luna—Glob and Phobos—Grunt projects (Galimov et al., 1998). The main objectives of the Luna—Glob project were exploration of the Moon’s interior structure and searching evidence for the presence of water in the lunar polar craters. The main objective of the Phobos—Grunt project was the return of soil samples from the surface of Phobos (Fig.1). GEOKhI proposed a proprietary analytical scheme for studying soil samples, which became the basis for the project and involved isotopic, geochemical and mineralogical analyses. The three-oxygen isotope data (16О –17О–18О) from this study could be used to clarify whether Phobos is captured or formed in situ. The study of organic compounds from Phobos was essential for the evaluation of the probability of the origin of life on Mars. The proposed analytical scheme involved isotopic, geo-

chemical and mineralogical analyses. Work on these projects began in 1997. If these projects had been implemented, Russia would have recaptured global leadership in space research. This however did not happen (Galimov, 2015). I will not go into details about many interesting solutions that have been developed under these projects over almost 20 years, yet I will give a brief sketch of the scientific payload mounted on the Phobos—Grunt spacecraft, which failed to complete its mission in 2011. The MAL-1F mass analyzer, which comprised a miniature chromatograph and mass spectrometer for in situ chemical analysis (Fig. 2), was developed at the Laboratory of Planetary Geochemistry (led by L.P. Moskaleva) and Laboratory of Chemical Sensors (led by B.K. Zuev) in cooperation with the Space Research Institute (IKI). Figure 3 show the flight version of the Phobos— Grunt spacecraft at NPO Lavochkin before the delivery to Baikonur and mounting location of MAL-1F. Another instrument is a cosmic dust detector (Fig. 4). Information about the space density of cosmic dust particles is crucial for improving the safety of space f lights. Numerous accidents in past Mars missions can probably be explained by high concentration of dust particles in the vicinity of Mars produced by its two moons, Phobos and Deimos. Despite the loss of Phobos—Grunt, all of the scientific instruments and results of the studies performed do not lose their value because they can be used in case of the renewal of the Phobos—Grunt project mission as well as in other sample return missions. At present, a proposal by GEOKhI to develop a next generation lunar robotic geologist equipped with a drilling device was included in the Federal Space Program for 2020–2030. The development of such rover is an essential element of the concept for the Moon exploration pro-

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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).

Whether Phobos material is cognate to that of Mars and SNC–meteorites. If itis not—which type of meteorite the Phobos material is close to. 1. 16О–17О–18О 2. Kr/Ar/Ne Does Phobos contain debris of Martian material? Looking for such debris and their analysis. Does Phobos contain remnants of presolar material? Isotope anomalies. Researches are feasible: Age of Phobos? light sector– Sm/Nd; Hf/W; U/Pb/Rb/Sr etc. only on delivery soil Presence of organic matter. dark sector– Identiﬁcation of organic compounds. without soil delivery

At contact moment Vvert ≤ 2 m/s; Vhor ≤ 0.7 m/s; ω = 1 deg/s

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gram developed by GEOKhI under the agreement with Roskosmos. *** Scientific substantiation of space missions and the development of spacecraft science payloads represent one area of space activity of GEOKhI, whereas the other equally important area involved the development of planetology. The Laboratory of Thermodynamic Modeling (led by Corresponding Member of the RAS O.L. Kuskov) has developed a software tool that allows us to link the physical parameters (e.g., seismic) to chemical and mineralogical composition of rocks (Kronrod and Kuskov, 2011). The seismic data obtained by the Apollo lunar mission were used for modeling the chemical and mineralogical composition of the lunar lower mantle. Although current interpretations of seismic profiles vary greatly, many researchers agree that the Moon is greatly enriched in refractory elements (e.g., about 6.2–6.4% Al2O3) compared to the silicate Earth (about 4% Al2O3). This conclusion is important for understanding the origin of the Moon. Tentative estimates indicate that the size of the lunar core is about 300–320 km. GEOCHEMISTRY INTERNATIONAL

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A similar thermodynamic calculation was used to estimate the interior structure of Jupiter’s and Saturn’s moons (Kuskov et al., 2009, 2010). It was shown that the Jovian moon, Callisto, may have a liquid ocean beneath its ice cover. The possibility for the presence of the ocean of liquid water or ice cover was also confirmed for Saturn’s moon Titan (Fig. 5). *** GEOKhI has proposed a new concept of the origin of the Moon or, more precisely, the origin of the Earth–Moon system. The giant impact hypothesis of lunar origin proposed by American researchers in the mid-1970s became widely accepted by the western scientific community. According to this hypothesis, the Moon was formed by a catastrophic collision between the Earth and a planetary-sized body (Fig. 6a). However, new facts have been discovered that contradict this lunar origin hypothesis. Calculations show that the Moon was derived from the impactor’s material, whereas the apparent similarity in the isotopic signatures of the Earth and the Moon confirms their genetic link, which contradict the giant impact hypothesis. 2016

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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).

We have demonstrated that the Earth and the Moon may have identical isotopic compositions if they were formed via fragmentation of the collapsing dust cloud. The proposed numerical model illustrates the dynamics of the fragmentation process (Fig. 6b, 6c) and explains the depletion of iron and the enrichment of refractory elements (Al, Ca, and Ti) in the Moon (Fig. 7a, 7b). Our analysis of the isotopic systems Hf–W, Rb–Sr, J–Pu–Xe, and U–Pb allowed evaluation of some quantitative characteristics of the model (Fig. 7c). The analysis of the 182Hf/184W systems shows that the Moon could have formed between 50 and 70 Myr after the formation of the solar system because rocks of the same age were found in the Moon (Galimov, 2013). These results are consistent with Rb/Sr data, indicating that before the final accretion of the Moon the protolunar material has evolved for about 50 Myr in a medium with a relatively high Rb/Sr ratio. The deficiency of radiogenic 206Pb and 207Pb in the Earth could be explained by losses of initial Pb. The

simultaneous solution of the equations for the 238U– 206Pb and 231U–207Pb systems shows that the Earth’s embryo would remain dispersed for the first ~120 Myr. A similar conclusion can be reached from the analysis of 129J–244Pu–129Хе–134Хе systems. Therefore, all known isotopic systems indicate that the fragmentation of the collapsing cloud and the formation of the main mass of the Moon took place by ~50–70 Ma while the condensation of the protoplanetary cloud completed by ~120 Ma when the Earth was finally accreted as a consolidated body. This concept and its geological implications were discussed in detail in our previous book “Origin of the Moon. New concept: Geochemistry and Dynamics” (Galimov and Krivtsov, 2012). The proposed model works well but it implies that planets form out of a cloud of dust particles, as opposed to the widely accepted model of planet formation by the collision of solid bodies. This indicates the need to elaborate a new accumulation model for the growth of the protoplanetary nebula. Such studies are underway. Two research groups under the leader-

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ship of Prof. A.M. Krivtsov in St. Petersburg and Academician M.Ya. Marov at GEOKhI have already presented some ideas and achievements. If the theory would prove successful, we could come to a new understanding of the formation mechanism of the solar system’s planets. The numerical model was developed to evaluate migration of small bodies (asteroids and comets) to the Earth from different regions of the solar system at the various stages of its formation and to estimate water and volatile fluxes at the expense of bombardment during the early evolution of the Earth and terrestrial planets (Ipatov and Marov, 2014). A theory of fractal accretion of dust clouds is developed by Academician M.Ya. Marov on the basis of his earlier theory of turbulent multicomponent continuum media (Kolesnichenko and Marov, 1999). GEOCHEMISTRY INTERNATIONAL

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*** Our specialists who work for a long time in the USA, have access to the original materials of American space missions that enable them to make important discoveries, which are recognized as of broad international and domestic scientific significance. The results of joint efforts of GEOKhI and Brown University, USA, were published as a global geological map of Venus, which was compiled using Magellan radar image data (Ivanov and Head, 2011). Figure 8 shows the results of another joint Russia– USA project. Images show that the hotspots indicating active thermal anomalies were found to flash and fade over the course of a few days. The observation of hotspots makes a strong case for a volcanically active Venus (Shalygin et al., 2015). 2016

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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.

*** On February 15, 2013, an event that attracted public attention was the fall of a meteorite near the town of Chelyabinsk (Fig. 9). On February 19, 2013, an expedition was sent by GEOKhI to the region of the fall for the collection of meteorite fragments. The results of the petrographic, elemental and isotopic analysis were used to study the

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cosmic history of the Chelyabinsk meteorite and to assign it to LL-group chondrites. These results of the study were submitted to the International Meteorite Nomenclature Committee (Galimov et al., 2013). The analysis of meteorites performed at the Laboratory of Cosmochemistry (led by V.A. Alekseev) revealed a distinct trend in the variations of galactic cosmic rays in the heliosphere (Alexeev and Ustinova, 2006). A total of 39 meteorites with different fall dates (the last one dated 2013) were analyzed for short-lived radionuclides 54Mn, 22Na, and 26Al produced in meteorites by galactic cosmic ray intensity (Fig. 10). The galactic radiation is constant and isotropic and becomes modulated in the heliosphere by solar activity. Most of the galactic cosmic rays (GCR) are swept out of the solar system by the solar wind. The maxima in the GCR flux density coincide with the maxima of solar activity based on a ~11-year periodicity. This unique trend, which was first recognized at GEOKhI, is crucial for risk assessment and the development of schedule options for long-term manned space flights, e.g., missions to Mars. PROBLEMS OF GEOLOGY AND GEOCHEMISTRY In accord with Vernadsky’s principles, GEOKhI strives to adopt the broader planetary approach to investigating many geological and geochemical problems. In the last 50 years, there seems to be an increasing understanding of the fact that part of the subducting GEOCHEMISTRY INTERNATIONAL

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oceanic plate sinks deep into the mantle where it is ultimately recycled as a result of planetary convection. However, the quantitative aspects of this process remain poorly constrained. A research group of M.V. Portnyagin developed a novel experimental approach, allowing deciphering initial H2O and CO2 content in parental arc magmas. Their pilot study of melt inclusions in olivine from Klyuchevskoy volcano on Kamchatka showed that parental magmas contained up to 4–5% H2O and 0.4 wt % of CO2 and that up to 80% CO2 in magmas was derived from subducting oceanic plate (Mironov et al., 2015). Sobolev et al. (2011) demonstrated the presence of a young crust of Phanerozoic age in the mantle source of Hawaiian lavas. These data were used to conclude that the rate of recycling of crustal material in the deep mantle was 1–3 cm yr–1. Therefore, the results of these studies provide important quantitative constraints on crust-mantle interaction. Studies of melt inclusions in Archaean komatiites confirmed a plume origin for these ultramafic lavas and high Archaean mantle temperatures, and also revealed a hydrous reservoir in the transition zone between the upper and lower mantle existing early in Earth’s history (Sobolev et al., 2016). *** It is widely accepted that the Earth has a chondritic composition. Kostitsyn (2014) demonstrated using his own Sm/Nd data and data from the literature that the ini2016

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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.

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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).

The oxidation state of the present-day mantle determined in log units of oxygen fugacity (logfO2) corresponds to the QFM (quartz—fayalite—magnetite) buffer. As fO2 decreases by four orders of magnitude, approximately to the IW (iron—wüstite Fe-FeO) buffer, CH4 and reduced nitrogen species become the dominant volatiles instead of CO2 molecular nitrogen. The hydroxyl ion and water become stable. The work of the laboratory of A.A. Kadik (Fig. 16a) made an important contribution to the discovery of this evolutionary trend. Further experimental work was conducted at GEOKhI under the leadership of Prof. A.A. Kadik (Kadik et al., 2014, 2015) to study the behavior of volatiles at oxygen fugacity about 5–8 orders of magnitude lower than that of the present-day mantle (Fig. 16b). This fO2 value physically corresponds to a melt: silicates plus metallic Fe. Experiments show that such conditions lead to a decrease in CH4 and an increase in NH3. It was found, surprisingly, that volatiles still contain water, although in much smaller quantities. This can account for the unexpected presence of water in the lunar mantle (Saal, 2008), which is seemingly contradictory to the prevailing ideas that the bulk Moon is almost entirely depleted in highly

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volatile elements and that it was formed during hightemperature impact. *** Chlorine is geochemically important volatile element. Its ability to form stable bonds with essentially all the other elements, including trace elements, under magmatic Р–T conditions, defines its role in ore element migration and precipitation. Lukanin (2015, 2016) have analyzed experimental and theoretical data on Cl partitioning in the fluid—melt system during sequential decompression and crystallization. It was shown that Cl exhibits a nonlinear behavior (Fig. 17). An important implication from this study was that the same initial melt at various degassing pressures (depths) can act as a source of magmatic fluids with different initial element contents. Fluid inclusions formed at different stages of crystal growth may have different REE abundances (Lukanin and DernovPegarev, 2010). This fact is essential for the correct GEOCHEMISTRY INTERNATIONAL

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interpretation of fluid inclusion data and may give us a powerful clue for the evaluation of ore potential. It should be noted that GEOKhI is renowned for its studies of fluid and melt inclusions in minerals, which provide unique insights into the composition of fluids and the history of magmatic differentiation. V.B. Naumov has compiled the largest and probably most representative database for fluid and melt inclusions (Naumov et al., 2009, 2017). The first discoveries of hydrocarbon inclusions in olivine and pyrope from kimerlites and minerals from alkaline rocks were made by GEOKhI (Galimov and Petersil’e, 1967; Galimov et al., 1989). It was shown that the isotopic composition of endogenous methane is markedly different from that of methane in sedimentary rock, whereas the partitioning of isotopes between endogenous hydrocarbons is reversed as compared to oil and gas fields. Some of our recent studies (Sevastianov et al., 2012, 2014; Buikin and Nevinny, 2012) have developed 2016

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(Mg, Fe)2SiO4 olivine

Upper mantle

(Mg, Fe)2SiO4 + O2

400 km (Mg, Fe)2SiO4 ringwoodite

Transition zone 670 km

Lower mantle

( Mg,Fe)O + (Mg, Fe)SiO3 perovskite ferropericlase magnesiowustite (Mg1–XFeX)SiO3

+3 yFe° + (Mg1–XFe+2 X–3yFe2y )SiO3 Fe3+-perovskite

MgO + FeO

(Fe + Fe3O4)

Mg-reach Fe-reach phase phase

High-pressure phase

3Fe2+O = Fe° + Fe3+ 2 O3

D"-layer FeO°

Core

FeO

Outer core

Fig. 15. Evolution of the primitive mantle from reduced to oxidized compositions, accompanied by core accretion (Galimov, 2015).

a new and more refined sample preparation procedure for fluid inclusion isotope analysis. It is also worth noting another important work, which is concerned with the fluid dynamics. I would like to mention diamonds produced by the cavitation synthesis. Many years ago, I published a theoretical study in Nature (Galimov, 1973) justifying the possibility of

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.

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1111

(b)

FW –1 0

–2

1

2

3

QFM 4

3320

OH–

H2O

0 2800

3000

Moon

3800

ΔlogfO2(IW) = –3.5 NH–2, NH+4

30 3289

NH3, NH+2

3185

20 CH4

2917

H2O, CO2, N2

Raman intensity, a.u.

40 Basalts

OH ,

3200 3400 3600 Raman shift, cm–1 3290 3321

Present Earth Upper mantle

CH4, NH+4

3367

CH4

5

5 logfO2

Initial Earth

–

NH–2, NH+4

3400

–3

ΔlogfO2(IW) = –2.1

3184

(a)

10

2918

Raman intensity, a.u.

NH3, NH+2

3287

15

10

H2 O

0 2800

3000

3200 3400 3600 Raman shift, cm–1

3800

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).

More recent studies showed that synthesized nanodiamonds can be doped with other elements and that not only diamonds but other carbon nanostructures can be produced during cavitation (Dnestrovskii et al., 2011, Voropaev et al., 2012). The process dynamics was investigated in details. For example, it was shown that an external pressure of about 200 atm must be applied to the collapsing bubbles to ensure the thermodynamic stability of diamonds. GEOKhI began to develop a larger experimental pilot system for the cavitation synthesis of diamonds using a specified set of process. This setup will give a much higher product yield than the previous versions. GEOCHEMISTRY INTERNATIONAL

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0.25

CI in melt, wt %

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).

800°C

7.25 wt % Н2О 0.25 wt % Cl

0.20 Close 0.15

0.10 Open 0.05 0

1

2

3

P, kbar Fig. 17. The behavior of CI during decompression degassing of magmas (Lukanin, 2015a). 2016

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(a)

(b)

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.

More recently, nanodiamond-based drug delivery to an organ or tissue has received significant medical attention. GEOKhI has started research in this area together with specialists in medicine. A set of diamonds has been recently discovered in the lava eruption of the Tolbachik volcano on the Kamchatka Peninsula. This finding has puzzled scientists because the mineralogy of their host rocks bears no evidence for the high pressure that is required for diamond synthesis. However, some indications were found to support a link between the formation of the Tolbachik diamonds and f luid dynamics. Diamond crystals occur only in pyroclastics and lavas, the products of an early explosive phase, and are absent from the products of a quiet effusive lava phase. We interpreted these diamonds as being produced by cavitation (Fig. 20). If this interpretation is correct, it will allow us to revise the conditions of diamond formation and occurrence in nature. Many geological processes are associated with the fast movement of a f luid in rocks through fractures as a result of tectonic movements. Diamonds may be found under conditions, which do not involve ultra-

high pressures required to synthesize diamonds in nature. It should be emphasized that the cavitation synthesis of diamonds from idea to practice is entirely a domestic product. *** Our institute is also renowned for its studies on geochemistry of platinum-group elements and gold. N.A. Krivolutskaya proposed a new model for the formation of Pt–Cu–Ni deposits of the Noril’sk region. This model does not imply a genetic relationship between ores and their host magmas. Sulfide ores were formed in the lower crust and were then transported by magmas to upper crustal levels (Krivolutskaya, 2015). The above study is based on the model invoking a mantle plume source for the Siberian Traps eruption. It was proposed that the Siberian plume was a major source of toxic gases, and that release of these gases caused the well-known Permian—Triassic mass extinction, i.e., these toxic gases are likely to have had

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1.25 1.16 1.07 –

2.08

Diamond phase

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220 – 311 331

111 1.26 – 1.08 0.82

2.06

dhkl 0 500

100

200

300

Microscopic view of the cavitation particles Reﬂected light

1.25 1.16 1.08 –

2.08

HKL

Diamond

Reference data

Diamond phase

400

P, kb

1500

Ti

Transmitted light

1000

ΔP, bar 800 400 200 100 50

Fig. 19. Cavitation diamonds, their identification and P—T conditions during experiments.

Crossed nicols

1.25 1.16 1.07 –

2.08

With diamond phase

Experimental data dhkl

Electron diffraction

e

5 μm

2000

m

2500 T, K

Graphite

Diamond

VERNADSKY INSTITUTE OF GEOCHEMISTRY AND ANALYTICAL CHEMISTRY 1113

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Diamonds of Tolbachik

To l b a c h i k Vo l c a n o

500 μm

Diamond (–25.5…–24.6‰)

Carbon (–25.3…–28.9‰)

Fig. 20. Diamonds discovered in Tolbachik lavas as natural examples of cavitation diamonds.

a significant impact on the biosphere (Sobolev et al., 2015). The COMAGMAT-5 model was developed by A.A. Ariskin research group to simulate crystallization of ultramafic magmas in sulfide-saturated systems and continues COMAGMAT family line (Ariskin and Barmina, 2004). This model was designed to calculate the evolutionary trends in the contents of highly chalcophile elements, PGE and gold in sulfides at various stages of magma crystallization (Fig. 21) (Ariskin et al., 2016). The study of the behavior of gold and PGE in the near-surface environment carried out in the Laboratory of I.V. Kubrakova revealed a significant role played by organic matter (humic substances) in the migration of these elements. Experiments showed that the sorption of the platinum-group elements on humic substances is largely controlled by the solution pH (Fig. 22). For example, the highly acidic media demonstrated 100% adsorption of Au and Pd. The alkaline media are characterized by 50% adsorption of Rh and Pt, whereas Pd and Au almost completely remain in the solution. Therefore, the platinum-

group elements may be found in different concentrations and may exhibit markedly different behavior in different geochemical environments (e.g., Pt and Pd), although they belong to the same group of elements and have almost identical crustal abundances (Kubrakova et al., 2012) ARTIC Special emphasis should be placed on the Arctic research, as it attracts considerable attention from the scientific and economic community. GEOKhI’s school of sedimentary geochemistry of Academician A.B. Ronov became internationally renowned in the past decades. A set of lithofacies maps compiled by A.B. Ronov provided the basis for a revision of the chemical composition and lithology of sedimentary rocks. The laboratory of Prof. M.A. Levitan (formerly led by Ronov) uses the same approach to study the Arctic basin. Lithofacies maps compiled so far for the Lower Triassic, Upper Jurassic, Upper Cretaceous, and Pliocene were used to provide the quantitative estimate of

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VERNADSKY INSTITUTE OF GEOCHEMISTRY AND ANALYTICAL CHEMISTRY

Cu/Pd in sulﬁde

106

Pd

Cu

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Pt D (Sf-Melt) Min Max

105 104 103 102 C & N (1979) 10

Cu/Pd in sulﬁde

10

100

6

10000 Cd

0.01 0.1

1

10 Ag

100 1000

0.0001

0.01

1 Au

100

100 0.01 0.1 1 10 100 1000 0.0001 0.01 Observed and modelled concentration in sulﬁde, ppm

1

100

105 104 103 102 10 0.01 0.1

1

10

Fig. 21. Simulation results obtained using the COMAGMAT-5 program.

*** One of the main radioecological problems of the Russian Artic is that the Kara Sea receives large amounts of riverine freshwater from the Ob’ and Yenisei Rivers, whose drainage areas are affected by runoff from the following Russian radiochemical plants (Mayak PA and Krasnoyarsk mining and chemical plant). Moreover, Novaya Zemlya was the site of nuclear weapon tests, its bays serves as storage sites for aged submarine nuclear reactors. Geochemical mapGEOCHEMISTRY INTERNATIONAL

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ping of the Kara Sea was performed by GEOKhI during the expedition onboard the R/V Akademik Boris Petrov. The results were compiled as the distribution of 137Cs, 239,240Pu, 90Sr concentrations in sediments of the Kara Sea (Fig. 24). The most distinctive feature of our research activities in this area was that we combined simultaneously environmental radiological monitoring with biogeochemical study (Galimov et al., 1996; Galimov et al., 100 Rh % of extraction from solution

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.

4 80 2

3

60

Pt 1

40 Au

20 Pd 0 1

2

3

4

5 pH

6

7

8

9

Fig. 22. Sorption of hydroxychloride complexes of Pt, Pd, Au, and Rh by humic acids. 2016

60°

T1

60°

0° 16

60 °

80°

500

80°

5 11 17

100°

100°

6 12

80°

120°

80 °

80°

70°

0 14

°

60°

70°

60°

60°

60°

60°

K2

0°

20

N2

°

°

0°

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40

40

°

70°

70°

60°

60 °

80°

80°

80°

80°

100°

100°

80°

80°

° 120

120°

0 14

70°

°

0° 14

70° 60°

60°

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).

°

80°

120°

4 10 16

20

J3

40

70°

140 °

70°

3 9 15

° 40

180°

2 8 14

°

16 0°

180° 180°

1 7 13

16

0° 16

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0°

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70°00′

71°00′

Yamal Peninsula

y Techeniy Bay

80°00′

72°00′ 72°00′

Bk/kg <10 10–20 20–40 >40

Lithology 30–55 >65

64°00′ 56°00′ 68°00′ 48°00′

Kolguev Isl. Vaigach Isl.

Chernaya Harbor

Stepovoi Bay Abrosimov Bay

72°00′

74°00′

70°00′

Sedova Bay Oga Bay Tsivol’ki Bay

Blagopoluchiya m Bay

E

A

S

Cs

R

T

76°00′

B

A

N

E

137

a

l

a

<30 60–65

72°00′

73°00′ 73°00′

70°00′

74°00′ 74°00′

71°00′

75°00′ 75°00′

<1 Bk/kg 1–3 Bk/kg >3 Bk/kg

76°00′

Pu 239, 240

78°00′ N 55–60 >70

N o v a y

S

78°00′

e

No. 13

Z

Vol. 54

Ob R.

GEOCHEMISTRY INTERNATIONAL

Yenisei R.

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).

76°00′

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.

77°00′

78°00′ N

***

77°00′

90

Sr

<2 Bk/m3 2–4 Bk/m3 >4 Bk/m3

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.

1117

69°00′ 69°00′ 55°00′ 60°00′ 65°00′ 70°00′ 75°00′ 80°00′ E 55°00′ 60°00′ 65°00′ 70°00′ 75°00′ 80°00′ E

VERNADSKY INSTITUTE OF GEOCHEMISTRY AND ANALYTICAL CHEMISTRY

Fig. 24. Radionuclide distribution in the Kara Sea. 2016

GEOCHEMISTRY INTERNATIONAL

66°00′ 51°00′

69°00′

72°00′

1.30

<1.0 60°00′

1.0–2.0

Vol. 54

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0.25 0.57 1.64 1.65 0.80 0.78

70°00′

0.66

0.88

1.20

1.26

0.49 1.73 0.94 0.93

0.41 0.33

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2 1.85 1.751.81

1.87

0.92 1.74

1.11 1.92

0.52

80°00′

Gydanskii Pen.

1.22

0.12

SEA

0.63

0.98 0.39 0.54

KARA

0.96

–23.2

–23.2 –24.0 –24.0

KARA

–23.4

–24.5 –24.4

–22.6

Techeniy Bay –24.3 –23.9 –23.2 –24.7 S EA –23.3 –23.3 –23.5 –24.7

–22.4

–23.6

66°00′ 51°00′

69°00′

Oga Bay Tsivol’ki Bay

>–22.0

–26.0, –26.9

–23.0, –23.9

60°00′

–25.0, –25.9

Yugorskii Pen.

70°00′

<–27.0

–24.0, –24.9

–24.3

80°00′

–23.7 –23.2 –25.2 Sedova Bay –23.6 –25.3 –25.4 –25.6 –26.4 –23.5 –25.2 –25.6 –23.4 –23.4 –25.7 –23.1 –26.4 –25.6 –26.6 –26.5 –26.3 –23.11 –23.0 –26.3 –23.9 –26.3 –26.2 –22.5 –23.1 –26.6 –26.6 –23.3 –26.8 –23.9 –27.1 –23.4 –26.7 –27.1 –24.1 –22.7 –28.9 –27.7 –23.8 Stepovoi Bay –23.2 –23.2 –22.5 –28.7 –26.6 –26.7 –23.1 72°00′ –21.9 Abrosimov Bay –24.4 –24.1 –23.4 –24.3 –23.6 –23.8 –23.2 Vaigach Isl. –24.2 Gydanskii Pen. –22.6 –22.47 –24.2 –24.8 –23.9 –22.37 –23.4 –24.5 –24.2

75°00′

a hiy aB y l ay

luc

gop o

Bla

Fig. 25. Content and isotopic composition of organic matter in sediments of the Kara Sea.

Yugorskii Pen.

1.12 1.17 1.19 1.41 1.23 0.66 1.26 0.36 1.20 Stepovoi Bay 0.60 1.58 1.10 0.99 1.18 1.40 1.15 0.81 Abrosimov Bay 1.50 1.321.64 0.08 0.60 1.63 1.88 1.49 Vaigach Isl. 1.07 1.25 0.53 0 0.94

1.44 0.99 1.31 1.72

Sedova Bay

1.58

1.20 0.62 Techeniy Bay

0.63 1.12 1.20 1.18 0.57 1.32 1.17

hiy a aB y a l y

gop olu c

Oga Bay Tsivol’ki Bay

Bla

Z

m

e

m

2.12

N o v a y a

75°00′

N o v a y a

e

77°00′

Yamal Pen.

Z

δ13Corg in sediments

Yamal Pen.

77°00′

Ob R.

Organic matter in sediments

Ob R.

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VERNADSKY INSTITUTE OF GEOCHEMISTRY AND ANALYTICAL CHEMISTRY

11:19:17

280 ~01

1119

31.07.10

P + 01 R + 00 51.Bm

P + 01 R + 00 Fig. 26. Radiation monitoring buoy.

Soon after the nuclear plant accident at Chernobyl, GEOKhI began and still continues to conduct radiation monitoring of contaminated areas. Iodine-13, a dangerous product of the Chernobyl radioactive fallout, concentrates in the thyroid gland. An increased risk of thyroid due to fallout exists in iodine-deficient areas. A map of the highest thyroid cancer risk was compiled by E.M. Korobova based on the data for stable iodine distribution in the Bryansk region and the results of radiation fallout mapping (Fig. 27). This map was used by medical workers as a basis for preventing thyroid diseases (Korobova et al., 2014). It was also shown that a variety of factors were responsible for a complex pattern of 137Cs distribution, which was reconstructed at different scales using GIStechnologies (Linnik et al., 2015). Indeed, anthropogenic radionuclides are now used as tracers to infer geochemical pathways for element migration, i.e., for solving the main problem of biogeochemistry. *** An extensive series of studies on the water chemistry in small lakes of Russia has been recently completed by a research group led by Corresponding Member of the RAS T.I. Moiseenko. Small lakes are sensitive indicators of regional environmental GEOCHEMISTRY INTERNATIONAL

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change. A comparison of data collected from different geographical, landscape and climatic zones revealed several important trends (Fig. 28), ref lecting variation in the water chemistry in lakes of European Russia and West Siberia. The composition of lake waters in European Russia is more enriched in sulfates, which ref lect the inf luence of anthropogenic (industrial and agricultural) factors, whereas the chemistry of lake waters in West Siberia is more Cl-rich (Moiseenko et al., 2013, 2015). A computer program used in modeling the thermodynamic behavior in water—rock systems was developed in the laboratory of B.N. Ryzhenko. The following parameters should be derived experimentally: —relationship between the interacting masses of water and rock; —rock mineralogy; —temperature and pressure in the medium; —degree of system openness with respect to certain components (volatiles), i.e., the presence of a buffer. Assuming these parameters are known, we can determine the composition of water in any medium: formation waters, hydraulic structures, oceans in the geological past. This program was successfully used to solve the problem of excess F in the Moscow artesian basin. 2016

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(a) Ku/km2 <20

I-131

20–50 50–100 100–150 150–200 >200

50

25

0

50

100 km (b)

1 (min) 2 3 4 5 6 (max)

50

25

0

50

100 km

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.

The results of observations are used to develop methods for efficient localization of anomaly sources. PROBLEMS OF THE ORIGIN AND EVOLUTION OF THE BIOSPHERE These studies coordinated by GEOKhI (coordinator E.M. Galimov) are conducted within the framework of the program of the Presidium of the Russian Academy of Sciences, which embraces the

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2000

4000

6000

8000

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12000

14000

Σions, μeq/L

Vol. 54 Donetsk Volgograd

Moscow Kazan’

90 80 70 60 50 40 30 20 10 0

RU

KZ

Chelyabinsk

Tyumen’

Bishkek KI

Astana

Tundra Taiga Forest Subarid ecoregion ecoregion ecoregion ecoregion

UZ

Ufa

Perm’

Khanty-Mansiysk

Novyy Urengoy

0

100 90 80 70 60 50 40 30 20 10

0

100 90 80 70 60 50 40 30 20 10

40

100

4.5

20

Fig. 28. Geochemistry of small lakes in Russia (Moiseenko et al., 2013).

Forest Subarid Tundra Taiga ecoregion ecoregion ecoregion ecoregion

Observed data Predicted value (under warming on 0.5°C) Predicted value (under warming on 1.0°C) Predicted value (under warming on 1.5°C) Predicted value (under warming on 2.0°C)

UA

Kiev

BY

LV LT Vilnius Minsk

EE Riga

EE

Tallinn

Helsinki

FI

Saint Petersburg

500 km

1 : 12000000

0 125 250

100 90 80 70 60 50 40 30 20 10 0 3.5

Cumulative, % Cumulative, %

NO

TP, μg/L

GEOCHEMISTRY INTERNATIONAL

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N

pH

6.5

60 80 SO4, μeq/L

200 Cl, μeq/L

5.5

SO4

100

300

Cl

7.5

120

140

400

8.5

European part of Russia West Siberian

Ph VERNADSKY INSTITUTE OF GEOCHEMISTRY AND ANALYTICAL CHEMISTRY 1121

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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.

*** The problem of K/Na paradox has been solved as part of the program (Galimov et al., 2012a). Proteins are known to be synthesized in the medium showing the predominance of K over Na. It is also known that the composition of seawater through geologic time was characterized by the predominance of Na over K (K/Na = 0.03). The cell membranes of present-day organisms contain the Na-K exchange pump, which maintains the intracellular K/Na ratio above 1. However, the cell membrane and the Na–K exchange pump emerged at a certain evolutionary stage. And how, then, peptide synthesis can proceed at the earliest stage? The numerical thermodynamic model of water— rock interaction developed at the laboratory of B.N. Ryzhenko demonstrated that in the medium with a predominance of methane over carbon dioxide (CH4/CO2 > 1), the K/Na ratio will be greater than 1 (K/Na > 1) (Fig. 30). Therefore, these results provide additional evidence that a reduced atmosphere was likely on the early Earth. *** Some interesting results were obtained from a series of experiments on the physiological effects of the isotopic composition. In this experiment, the organisms were grown under conditions when carbon has a monoisotopic composition (Fig. 31). The recent study by A. Ivanov (Laboratory of Carbon Geochemistry) revealed that insects that were fed carbon monoisotopes lost their capacity to breed. It can be thus concluded that the effect of isotopy may occur at the genetic level. This can be associated with an isotope spin effect in the DNA methylation reaction. The spin effect is found to operate in radical reactions. Our current study aims to identify the character of the methylation reaction. If we succeed in explaining the mechanism of this phenomenon, we will possess a powerful tool for further investigation. OIL AND GAS It should be noted that the notion of recharging oil accumulations from deep sources in the Earth’s crust and mantle has recently received increased attention. For example, in Tatarstan, this view is now widely accepted by many leading scientists and administrative officials. Arguments supporting this conclusion are based on the long empirical record of the Romashkino oilfield exploration and development. Romashkino is a super-giant field, which stands out among the world’s ten largest oilfields with proven reserves of more than 5 billion tons of oil. Oil accumu-

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Evolution of life

Prebiotic evolution

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Organic compounds background

Sugars HCN, HCHO, HPO3

Synthesis of ATP

Adenosine triphosphate

Stationary system of irreversible reactions supported by inﬂow of energy through ATP

t-RNA

C

HC N

C

N

C

NH2

CH

OH

HC

CH

N

N

Adenin

O

O

O

P

OH O

O

Phosphate

OH

P

O

O

P

OH

ATP

Nucleotides → Polynucleotide

Amino acids → Peptide

ATP + H2O → ADP + Pi ΔS > 0 M + N → H2O + MN ΔS < 0

OH

C C H H CH

H

Ribose

“World of ATP” → peptides → biosynthesis (selective catalysis) (nucleotides)

The concept of ATP—dependent ordering

Fig. 29. Origin and evolution of life.

Lipids

Films

Amino acids

hν, minerals, H2O, CO2, CO, CH4, NH3 Primary medium on Earth

Cellular wall No-coded peptides

Synthesis of chemical precursors

Comets, interstellar particles metheorites HCN, HCHO, CH3OH, NH2CHO, CH3NH etc

Nucleotides

Non-coding RNA

Coded peptides

Cell Organism

Establishing of code

Gene Encoding RNA

Virus

Eucariots Procariots

Multicellular organisms

Higher organisms

Intellect

Technology

OH

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–8 When CH4/CO2 < 1 then K/Na < 1 Present Earth (ocean)

logPCH4

–6

–4

When CH4/CO2 > 1 then K/Na > 1

–9

–8

–7 logPCO2

Early Earth

–6

–2 –5

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).

*** Previous work of the Laboratory of Carbon Geochemistry laid the foundation for the study of organic isotope geochemistry and biological fractionation of carbon isotopes, the results of which were presented in a series of monographs published in Russia and abroad. These results provided the basis for the interpretation of many of the trends revealed in recent geological observations (Galimov, 2006). The study of gases from the En-Yakha upltradeep well in West Siberia revealed that variations in the isotopic composition of gases occur to a certain depth and that radical transformation at depths greater than 6000 m can be explained by a change in the mechanism of gas generation (Galimov et al., 2012b). It is noteworthy that the trend in the isotopic composition of gases measured in one borehole is identical to variations observed across the entire petroleum area. The available literature data indicate that methane carbon isotopic composition varies considerably between pools within the Nepa–Botuoba anteclise of East Siberia. It was shown that the methane fraction of gases is slightly depleted in 13С relative to crude oil, which is typical of gases produced by oil cracking. The isotopically heavier methane, like that from the ultradeep well, was found in the northeastern part of

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−OOC + NH3

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O N

N N

N + O

N H

DNA

Cytosine

N

NH2

DNA MTase

Enzyme

O

N H

NH2

DNA

CH3 +

5-Methylcytosine

N

Fig. 31. Effects of the isotopic composition on organisms.

CH3-SAM

OHOH

CH3 S+

NH2

The monoisotope plant louse has died out

SAM

The ordinary plant louse gives posterity

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Corg(D3sm)

caldera of Uzon volcano. Samples of microbial mats and plant remains collected from the surface were analyzed in the laboratory by thermal hydrolysis.

Normal borehole (H-5)

RBM

The results show that hydrocarbons from this volcanic area are mainly products of the hydrothermal transformation of biota.

Anomalous borehole

RB RHB

Therefore, none of the studied examples provides compelling evidence for the existence of a deep inorganic source for the hydrocarbons in these accumulations.

HC δ13C, ‰

ANALYTICAL METHODS AND INSTRUMENTATION

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.

It is worth noting one more study concerning the genesis of hydrocarbons from a volcanic area (Galimov et al., 2015). Oil seeps in the caldera of Uzon volcano, Kamchatka, have long been considered to be of inorganic origin. Oil samples were collected from the

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).

West Siberia SG-7 borehole

5700 m 7163 m

Mirninsk Upper Vilyui

4950 m

Taas-Yuryakh Iktekh

–30

Gas Central Botuoba

δ23C

Oil

U. Chon

(1360–2116 m)

Preobrazhen

(2350–2360 m)

NE

Gas

Danilov

(1970–2774 m)

–40

Nepa-Botuoba anteclise

SW –42 –40 –38 –36 –34 –32 –30 Yaraktin

δ23C

Ayansk

A

–20 CH4

C2H6

C3H8

i-C4H10

Fig. 33. Isotope composition of gases as a function of their formation mechanisms. GEOCHEMISTRY INTERNATIONAL

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The device for uniform irradiation of the large samples has been developed

SEM

Autoradiography

(a) Pd zones

(d) T½ = 16.4 ± 1.3 h

(b) Cu zones

(e) T½ = 15.0 ± 3.5 h

(c) Ni zones

(f) T½ = 24.0 ± 6.0 h

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The essence of the method consists in computer’s processing of time series of autoradiography images obtained while the sample is cooling (deconvolution of the decay curves)

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.

A technology for the separation and concentration of substances by applying a combination of different physical fields is developed under the guidance of Corresponding Member of the RAS B.Ya. Spivakov. IT

*** The general principles of a theory of molecular structure formulated in the Laboratory of Molecular

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).

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5 15

6

2 15

4

3 7

14 8 9 1

10

11

12

13

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.

+

Optical ﬁber to a spectrometer

–

DSD—source of atomization and excitation 6

5

2 Electrolyte 1

Sample drop 4

Fig. 36. Drop-spark discharge-based device. GEOCHEMISTRY INTERNATIONAL

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remarkable theoretical studies that were performed by Corresponding Member of the RAS L.A. Gribov and his colleagues. *** New atomization and excitation sources using a drop-spark discharge on boiling in a channel were developed in the Laboratory of Chemical Sensors (Zuyev et al., 2014). With low power consumption, the miniaturization allows such devices to be used in a variety of field application. The portable device was manufactured for medical diagnostics application. The method was tested in the Central Clinical Hospital of the Russian Academy of Sciences. The other version of the microplasma analyzer on the basis of drop-spark discharge was used to control the composition of processing solutions. One more invention includes a luminescent analyzer for uranium determination in environmental samples (Patent no. 2488808 of February 28, 2012). The portable design of this device enables analysis in field applications (Fig. 37). ***

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.

Modeling (led by Corresponding Member of the RAS L.A. Gribov) were used as the basis for developing a methodology of the calculation of molecular spectra. The standardless method developed in the laboratory includes the determination of the concentrations of mixture components (Gribov and Baranov, 2006). According to the general principles, the earliest stages of the appearance of the molecular world were marked by optimization of the isomeric structure and formation of straight-chain acyclic molecules (Gribov and Baranov, 2007). Other examples of the application of the general principles of the theory of molecular structure include theoretically derived empirical dependences, e.g., the Arrhenius equation, or the quantum efficiency of reaction, which show a good agreement between the calculated and measured values. These are the GEOCHEMISTRY INTERNATIONAL

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A high-sensitivity luminescent analyzer for actinide determination developed in the laboratory of A.P. Novikov (Mogilevskii et al., 2013) is used for the analysis of trace neptunium (Fig. 38). This actinide with a high potential for bioaccumulation and a long half-life would present the most serious hazard to human health. *** It is well known that the main difficulty encountered in organic trace analysis using a mass spectrometer is that organic compounds require soft ionization energy. Hard ionization with an electron beam will destroy organic compounds. For example, the conventional MALDI methodology uses a suitable matrix material as a mediator, which is thought to transfer protons to the analyte molecules, thus ionizing the analyte in a relatively soft way. However, organic compounds are not susceptible to protonation using the MALDI technique. The LETDI (laser-induced electron transfer desorption ionization) method which uses semiconductor material as an electron-transfer mediator for the soft ionization was developed in the Laboratory of Instrumental Methods (Grechnikov et al., 2010). This method proved to be highly sensitive in most cases (Fig. 39). 2016

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Fig. 38. Luminescent analyzer of actinide determination. Detection limit: 10–13g for Pu.

522.993

100 Relative abundance

Mass-analyzer Orbitrap

Pulse laser

80

N

S 520.991

60

Re

N

S

O

40 521.994

20

523.997 524.989 525.99

0 518 Substrate– the emitter of ions

520

522 524 m/z

526

528

MALDI (Orbitrap)

10 pg

LETDI (Orbitrap)

0.005 pg

Fig. 39. A new high-sensitive technique for determination of organic compounds.

*** A theoretical basis for selective gas-liquid chromatography was developed in the Laboratory of Sorption Methods (laboratory head R.Kh.Khamizov) (Dolgonosov et al., 2013, 2015). As seen in Fig. 40, the results demonstrate a good agreement between theoretical and experimental retention times. A new method was proposed for the purification of industrial phosphoric acid and simultaneous sorption

of rare-earth elements (Fig. 41). This method was patented and is applied at the Belorechensk fertilizer plant (Khamizov et al., 2012, 2015). RADIOCHEMISTRY Special attention should be given to radiochemistry in our institute, which can even be traced to the participation of GEOKhI in the atomic project. In Soviet times, the institute played a decisive role in analytical

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Save Print Load Eluent Base line Curve

A.M. Dolgonosov

H2SO4 t = 5.489 H = 7.998 c = 0.312 τ = 0.1218 R = 1.98 x = 0.1443

9

1—F 2—HCOO 3—Cl 4—HPO4 5—NO2 6—PO3F 7—SO4 8—Br 9—NO3

8

Conductivity

7 6 5 4 3 2

Resolution OK R/R0 = 1.615

1

3 9 6 4

5

7

2

NONSPECIFIC SELECTIVITY in the Problem of Modeling of High-performance CHROMATOGRAPHY

8

1 0 0

0.5

1.0

1.5

2.0

2.5

3.0 3.5 4.0 Time, min

4.5

5.0

5.5

6.0

6.5

7.0

Fig. 40. Evolution of the theory of adsorption and chromatography.

(a)

(b)

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).

monitoring of the production of weapons-grade plutonium. In subsequent years, the institute became a leader in studies of the chemistry of transuranium elements in Russia. Some interesting results have been achieved in the laboratory, formerly headed by Academician B.F. Myasoedov, a leader of national radiochemistry, and now headed by Doctor of Sciences Yu.M. Kulyako (Myasoedov and Kalmykov, 2015, Myasoedov et al., 2013). The most recent studies established the existence of Pu (VIII) in the highest oxidation state, in the form of PuO4. The important achievement of GEOKhI in GEOCHEMISTRY INTERNATIONAL

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the field of radiochemistry is the development of a new technology for reprocessing spent nuclear fuel (SNF) in weakly acidic Fe nitrate solutions (Trofimov et al., 2014). The use of concentrated nitric acid process solutions (6–8 М HNO3) and other toxic materials are eliminated in the suggested technology. The method allows efficient separation of U, Pu, and Np from residues of fission products. Some of the sintered pellets that can be rejected due to defects need to be reprocessed. Crushing of rejected ceramic pellets is a labor-intensive and time-consuming operation, involving the use of strong reagents. The use 2016

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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.

(a)

***

(b)

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.

It should be noted, in summary, that over the report period, the institute continued to publish the following scientific journals: Geokhimiya (or in English Geochemistry International) and Zhurnal Analiticheskoi Khimii (Journal of Analytical Chemistry). Unfortunately, the research vessel Akademik Boris Petrov that has made many successful cruises until 2010 was not used in the last years for the reasons known to all of us. In 2013, we celebrated the 150th anniversary of the birth of V.I. Vernadsky. His collected works, in 24 volumes, were published to commemorate this date (Fig. 43). Our institute houses the V.I. Vernadsky’s office-museum, A.P. Vinogradov’s office-museum, Museum and Committee of

Fig. 43. The Collected Works of V.I. Vernadsky. Compiled and edited by E.M. Galimov, 2013. GEOCHEMISTRY INTERNATIONAL

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Meteorites, and a number of other Interdepartmental and Academic Commissions and Councils. REFERENCES M. V. Alenina, V. P. Kolotov, and Yu. M. Platov, “Lithium carbide is prospective material for breeder of fusion reactor,” Inorg. Mater. Appl. Res. 5 (2),149–153 (2014). V. A. Alexeev and G. K. Ustinova, “Solar modulation of galactic cosmic rays in the three-dimensional heliosphere according to meteorite data,” Geochem Int. 44 (5), 423–438 (2006). A. A. Ariskin, and G. S. Barmina, “COMAGMAT: Development of a magma crystallization model and its petrologic applications,” Geochem. Int. 42 (Supplementary 1), S1S157 (2004). A. A. Ariskin, E. V. Kislov, L. V. Danyushevsky, G. S. Nikolaev, M. L. Fiorentini, S. Gilbert, K. Goemann, A. Malyshev, “Cu-Ni-PGE fertility of the YokoDovyren layered massif (Northern Transbaikalia, Russia): thermodynamic modeling of sulfide compositions in low mineralized dunite based on quantitative sulfide mineralogy,” Mineralium Deposita, Springer Verlag, (2016) doi:10.1007/s00126-016-0666-8 A. I. Buikin and Yu. A. Nevinny, “Sample Preparation Line for Gases from fluid inclusions in rocks and minerals,” Patent no. RU 2449270 (2012). A. Yu. Dnestrovskij, A. M. Dolgonosov, N. K. Kolotilina, and M. S. Yadykov, “A way of preparation of high-performance columns for ion chromatography,” Patent RF No. 2499628. Byul. Izobret. No. 23 (2013). A. M. Dolgonosov, O. B. Rudakov, and A. G. Prudkovskii, Column Analytical Chromatography: Practice, Theory, and Simulation (Lan’, St. Petersburg, 2015) [in Russian]. A. N. Dunaeva, V. A. Kronrod, and O. L. Kuskov, “Physico–chemical models of the internal structure of partially differentiated Titan,” Geochem. Int. 54 (1), 27– 47 (2016). V. L. Ermakov, Jovanovic, V. Berezkin, S. Tjutikov, A. Danilogorskaya, V. Danilova, E. Krechetova, A. Degtyarev, and S. Khushvakhtova, “Chemical assessment of soil and water of Urov biogeochemical provinces of Eastern Transbaikalia,” Ecologica 19 (69), 5–9 (2012). V. V. Ermakov, Biological Significance of Selenium (Nauka, 1974) [in Russian]. P. S. Fedotov, M. S. Ermolin, A. I. Ivaneev, N. N. Fedyunina, and Yu. G. Tatsy, “Continuous—flow leaching in a rotating coiled column for studies on the mobility of toxic elements in dust samples collected near a metallurgic plant,” Chemosphere 146, 371–378 (2016). E. M. Galimov, “Possibility of natural diamond synthesis under conditions of cavitation, occurring in a fast– moving magmatic melt,” Nature 243, 389–391 (1973). E. M. Galimov, “Phenomenon of life: Equilibrium and non–linearity,” Origin of life and evolution of the biosphere 34 (6), 599–613 (2004). E. M. Galimov, “Analysis of isotope systems (Hf–W, Rb– SR, J–Pu–Xe, U–Pb) with reference to the problem of planet origin by the Earth—Moon system, in Origin of GEOCHEMISTRY INTERNATIONAL

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Life and Evolution of the Biosphere, Ed. by E. M. Galimov (Krasand, Moscow, 2013), V. 2, pp. 47–59. E. M. Galimov, “Concept of sustained ordering and ATP– related mechanism of life’s origin,” Int. J. Mol. Sci. 10, 2019–2030 (2009). E. M. Galimov, “Formation of the Moon and the Earth from a common supraplanetary gas–dust cloud,” Geochem. Int. 49 (6), 537–554 (2011). E. M. Galimov, “Intentions and failures. Fundamental space investigations in Russia of the last twenty years. Twenty years of fruitless efforts,” Geochem. Int. 53 (13), 1151–1248 (2015). E. M. Galimov, “Isotope organic geochemistry,” Org. Geochem. 37, 1200–1262 (2006). E. M. Galimov, “Redox evolution of the Earth caused by multistage formation of its core,” Earth Planet. Sci. Lett. 233, 263–276 (2005). E. M. Galimov and A. I. Kamaleeva, “Source of hydrocarbons in the supergiant Romashkino Oilfield (Tatarstan): recharge from the crystalline basement or source sediments?” Geochem. Int. 53 (2), 95–112 (2015). E. M. Galimov and A. M. Krivtsov, Origin of the Moon. New Concept. Geochemistry and Dynamics (De Gruyter, 2012). E. M. Galimov and I. A. Petersilie, “Carbon isotopic composition of hydrocarbon gases and CO2 in alkaline igneous rocks of the Khibiny, Lovozero, and Ilimaussaq massifs,” Dokl. Akad. Nauk SSSR 176 (4), 914–917 (1967). E. M. Galimov, A. I. Botkunov, V. K. Garanin, M. Yu. Spasennykh, L. A. Bannikova, I. V. Nikulina, L. E. Shishmareva, and A. V. Belomestnykh, “Carbonbearing fluid inclusions in olivine and garnet from kimberlites of the Udachnaya pipe,” Geokhimiya 27 (7), 1011–1015 (1989). E. M. Galimov, N. P. Laverov, O. V. Stepanets, and L. A. Kodina, “Preliminary results of ecological and geochemical investigations of the Russian Arctic Seas (data obtained from cruise 22 of the R/V “Akademik Boris Petrov”,” Geochem. Int. 34 (7), 521–538 (1996). E. M. Galimov, S. D. Kulikov, R. S. Kremnev, Yu. A. Surkov, and O. B. Khavroshkin, “The Russian Lunar Project,” in: Proc. The 3rd Intern Conf. On the Exploration and Utilization of the Moon, Ed. by E. M. Galimov et al. (1998), p. 54. E. M. Galimov, A. M. Kudin, V. N. Skorobogatskii, V. G. Plotnichenko, O. L. Bondarev, B. G. Zarubin, V. V. Strazdovskii, A. S. Aronin, A. V. Fisenko, I. V. Bykov, and A. Yu. Barinov, “Experimental corroboration of the synthesis of diamond in the cavitation process,” Dokl. Phys. 49 (3), 150–153 (2004). E. M. Galimov, L. A. Kodina, O. V. Stepanets, and G. S. Korobeinik, “Biogeochemistry of the Russian Arctic. Kara Sea: research results under the SIRRO Project, 1995–2003,” Geochem. Int. 44 (11), 1053– 1104 (2006). E. M. Galimov, Yu. V. Natochin, B. N. Ryzhenko, and E. V. Cherkasova, “Chemical composition of the primary aqueous phase of the Earth and origin of life,” Geochem. Int. 50 (13), 1048–1068 (2012a). 2016

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Translated by N. Kravets

2016

Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKhI): Scientific results in 2011–2015

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