ISSN 01458752, Moscow University Geology Bulletin, 2013, Vol. 68, No. 5, pp. 265–281. © Allerton Press, Inc., 2013. Original Russian Text © A.A. Marakushev, L.I. Glazovskaya, S.A. Marakushev, 2013, published in Vestnik Moskovskogo Universiteta. Geologiya, 2013, No. 5, pp. 3–17.

Evolution of the Iron–Silicate and Carbon Material of Carbonaceous A. A. Marakusheva, L. I. Glazovskayab, and S. A. Marakushevc aInstitute of Experimental , Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia email: [email protected] bFaculty of Geology, Moscow State University, Moscow, 119234 Russia email: [email protected] cInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia email: [email protected] Received February 18, 2013

Abstract—The observed consistence of the composition of and the matrix in chondrites is explained by their origin as a result of –matrix splitting of the material of primitive (not layered) planets. According to the composition of chondrites, two main stages in the evolution of chondritic planets (silicate–metallic and olivine) are distinguished. Chondritic planets of the silicate–metallic stage were ana logs of chondritic planets, whose layering resulted in the formation of the terrestrial planets. The iron–silicate evolution of chondritic matter is correlated with the evolution of carbon material in the following sequence: ± moissanite → hydrocarbons → primitive organic compounds.

Keywords: matter, carbonaceous chondrites, hydrocarbons DOI: 10.3103/S0145875213050074

INTRODUCTION 2003) in star–planet systems that are similar to the , in which nearstar giant planets were still The occurrence of diamond in a stable paragenesis preserved and are distinguished under the name rapid with moissanite (SiC) in an ironrich matrix is a char Jupiters. Passage of the protoplanetary stage with the acteristic and the most interesting peculiarity of all formation of the dense cores by chondritic planets is types of chondrites. Diamond grains are overfilled also proven by other discoveries. This was directly con with hydrogen fluid to the extent that their bulk den 3 firmed in 1996, when the Galileo space probe pene sity decreases to 2.2–2.3 g/cm (Brearley and Jones, trated to the fluid envelope of Jupiter. This envelope 1998, p. 278; Besmen, Hoppe, and Ott, 2011) at a 3 was characterized by a high ratio of xenon isotopes density of diamond of 3.5 g/cm . (136Xe/134Xe = 1.04) equal to that in fluid inclusions in The presence of the moissanite–diamond paragen from carbonaceous chondrites (Kissin, esis provides direct evidence for the origin of 2003). In the solar wind this ratio is 0.8. matter in the cores of giant planets, which are the only Paragenesis of diamond with moissanite is typical objects in the solar system in which the huge fluid of the matrix of all types of chondrites, which allows us pressure may be found that is necessary for the forma to assume that all chondritic planets were formed and tion of this paragenesis. Small diamond grains dis developed under the huge pressure of the fluid enve persed in a chondrite matrix demonstrate the original lopes of their parental giant planets on orbits between ity of this process controlled by the extreme compres Mars and Jupiter. They became individual planets sion of hydrogen fluids: only after the complete loss of the fluid envelopes by H2 + CO = H2O + C (diamond) and 4H2 + 2CO their parental giant planets under the influence of the + SiO2 = 4H2O + C (diamond) + SiC (moissanite). Sun, but underwent explosive decomposition into The nearsolar planets that were lost by the solar ; their belt is the source of chondrites that system under the influence of the Sun were the paren compose 87% of all meteorite falls (Vityazev, Pecher tal giant planets for the chondritic planets (which were nikova, and Safronov, 1990). destroyed with the formation of asteroids and chon Destruction was initiated by the accumulation of drites), as well as for the terrestrial planets. Their ana such condensed fluids in the cores of chondritic plan logs were discovered by astronomers (Charbonneau, ets that their expansion with the loss of total pressure

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Fe chondrules (their fragments form CAI in carbon 1 aceous chondrites) were formed; then forsterite chon 2

ix drules originated. The age of CAI has been estimated r 3 0.82Fe + 0.18SiC t a 4 at 4567–4568 Ma (Krot et al., 2009); chondrules were m

ordinary y 5 r formed later by 1–4 m. y. Later, enstatite primary a e m n 6 i s r chondrules were formed (Fig. 1). t p a

t

i 0.66Fe + 0.34SiC t The occurrence of diamonds accompanied by e moissanite in the primary chondrite matrix reflects the reduced character of matrix formation at an extremely high hydrogen pressure. A metallic chondrite matrix HH containing diamond and moissanite is formed under E H C these conditions. It contains native silicon, although c a L r less abundantly than moissanite. The following b LL o n sequence of chondrites (their average compositions a c e o are given in Table 1) occurs by enrichment in moisso u s nite: carbonaceous chondrites (C, enriched in Mg SiO MgSiO3 2 4 moissanite); enstatite chondrites (E); and ordinary Si Mg primary chondrules chondrites (HH, H, L, and LL) with negligible con tents of Si and SiC in the primary metallic matrix. Fig. 1. The systematics of chondrites based on correlations of their average compositions (data from Tables 1–6), the The primary metallic taenite–kamacite matrix of compositions of their primary chondrules (empty circles), carbonaceous chondrites was a unique formation, and the metallic matrix (ful circles). The tie lines connect because of the high concentrations of Ca, Al, and Ti. ing them correspond to the types of chondrites: (1–4) With an increase of the H2O/H2 ratio in fluids, they ordinary (HH–H–L–LL), (5) enstatite (E), and (6) car were oxidized first, which was the basis for the forma bonaceous. tion of relatively large calc–alumina chondrules in the matrix. These were ejected by chondrites with smaller had an explosive character. Indicators of the explosive forsterite chondrules formed later. CAIs consisting of formation of asteroids include the presence of impact calc–alumina (melilite, hibonite, spinel, diopside, plagioclase, and others) are characterized by minerals (ringwoodite and others) in the newly formed 16 superposed glassy phase of the chondrites. Chondrites an extremely light oxygenisotope composition ( O). are heliocentric and their falls from the This peculiarity is also typical of primary forsterite (Si belt occurred during 4 billion years, judging 33.3; Mg 66.7 at %) that forms primary chondrules by the age of the oldest chondrites. Because of this, the (Fig. 1), which is characterized by the presence of modern weight of the asteroid belt is quite far from its inclusions of metallic nickel–iron drops. initial weight. The evolution of chondritic magmas is controlled Consequently, the protoplanetary (in the cores of by the introduction of isotopically heavy oxygen of the parental giant planets) and planetary evolutions of water. With the presence of silicon, this results in the chondrite matter are distinguished. Protoplanetary replacement of forsteritic chondrules by enstatitic evolution occurs during the selective loss of hydrogen ones, according to the reaction: by parental giant planets in the mode of a decrease of Mg2SiO4 + Si + 2H2O = 2MgSiO3+ 2H2. total pressure and an increase of the H2O/H2 ratio in This provides a completely different, primarily fluids. enstatitic type of chondritic magmatism, which is dif ferent from the formation of carbonaceous chondrites with primary forsterite and calc–alumina chondrules. SYSTEMATICS AND STAGES OF THE EVOLUTION OF CHONDRITE The chondrule–matrix interaction under the pres MATTER sure of the hydrogen component of fluids controlled the entire successive evolution of the iron–silicate Chondritic planets (parental in relation to asteroids matter of chondritic planets. The initial stage of the and chondrites) were primarily formed as metallic cores evolution is illustrated in a diagram (Fig. 1) with tie lines of nearsolar giant planets composed of iron, nickel, connecting the compositions of the primary matrix and many other elements (Si, Ca, Al, Mg, and others), and chondrules of the main types of chondrites. The average carbon. Selective loss of hydrogen by their parental compositions of differentiates of carbonaceous and giant planets and corresponding increase of the enstatitic chondrites, as well as the main types of ordi H2O/H2 ratio in their fluid envelopes were accompa nary chondrites (the sequence HH–H–L–LL corre nied by oxidation of metals starting from the most lates with increase of iron content in their silicates) plot refractory ones and the formation of chondrules in the on tie lines. The evolution of the enstatitic type of following sequence of parageneses of typical elements: chondritic magmatism is schematically characterized (Ca + Al + Si + Ti)–(Si + Mg). First, calc–alumina by the reaction:

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Table 1. Comparison of the average bulk compositions of chondrites (at %) Elements LL (60) L (166) H (172) HH* C (31) E (7) Si 15.42 15.44 14.75 14.71 13.48 15.36 Ti 0.03 0.03 0.03 0.07 0.05 0.03 Al 1.22 1.15 1.13 0.97 1.48 1.34 Fe 8.65 9.59 12.52 16.61 11.03 14.23 Mn 0.11 0.11 0.10 0.13 0.09 0.10 Mg 14.99 15.06 14.75 13.31 14.69 12.39 Ca 0.76 0.76 0.73 0.80 0.97 0.56 Na 0.70 0.68 0.60 0.67 0.33 0.61 K 0.05 0.05 0.04 0.11 0.03 0.04 P 0.09 0.09 0.08 0.21 0.10 0.12 Cr 0.15 0.15 0.14 0.21 0.17 0.14 Ni 0.38 0.45 0.64 1.16 0.54 0.73 Co 0.01 0.02 0.02 0.05 0.02 0.03 S 1.63 1.76 1.71 1.15 2.34 4.34 O 55.81 54.66 52.75 49.84 54.69 49.99 The bulk compositions of meteorites are given after (Marakushev, Zinov’eva, and Granovsky, 2010). The number of the meteorite anal yses is given in parentheses. *Analysis of the chondrite component of the meteorite Nechaevo.

MgSiO3 + Fe + H2O = MgFeSiO4 + H2. quent autobrecciation of chondrules during a rapid pressure decrease. The series of ordinary chondrites is characterized by a stepwise shift of reactions to the right, synchro nously in chondrules and the metallic matrix. This CARBONACEOUS CHONDRITES results in the formation of olivine parageneses with The process of chondritic magmatism related to pyroxene; their iron contents discretely increase with carbonaceous chondrites is complicated by the partic the formation of the main types of ordinary chon ipation of silicon or moissanite in reactions: drites: 15HH–20H–25L–30LL. This sequence cor responds to the following stages of shift of hydration Mg2SiO4 + (2Fe + SiC) + 4H2O reactions to the right: = 2MgFeSiO4 + C + 4H2, and may be accompanied by the formation of free car (HH): MgSiO3 + 0.176Fe + 0.176H2O = 0.824Mg Fe SiO + 0.176Mg Fe SiO + bon, as well as hydrocarbons: 0.85 0.15 3 1.7 0.3 4 Mg SiO + (2Fe + SiC) + 4H O 0.176H2; 2 4 2 = 2MgFeSiO4 + CH4 + 2H2. (H): MgSiO3 + 0.25Fe + 0.25H2O = 0.75Mg0.8Fe0.2SiO3 + 0.25Mg1.6Fe0.4SiO4 + 0.25H2; Hydrocarbons in carbonaceous chondrites are widely variable (Pizzarello, Cooper, and Flynn, 2006; Meier (L): MgSiO3 + 0.33Fe + 0.33H2O = henrich et al., 2004). 0.67Mg Fe SiO + 0.33Mg Fe SiO + 0.33H ; 0.75 0.25 3 1.5 0.5 4 2 Shifting of reactions to the right results in the (LL): MgSiO3 + 0.43Fe + 0.43H2O = replacement of the primary metallic matrix with a sec 0.57Mg0.7Fe0.3SiO3 + 0.43Mg1.4Fe0.6SiO4 + 0.43H2. ondary olivine matrix with a widely ranging iron con Under deviation from equilibrium, the iron con tent. However forsterite is preserved in abundant frag tent in silicates of the metallic matrix increases more ments of primary chondrules, which characterizes rapidly than that in chondrules, in which the compo carbonaceous chondrites as nonequilibrium. sition of silicates may remain close to the primary Fig. 2a clearly demonstrates the replacement of enstatite. The initial state was preserved in enstatitic primary forsterite chondrules with a matrix melt; the chondrites (E), as well as those consisting of partially compositions of ironrich olivine are given in Table 2. brecciated enstatitic chondrules and a metallic matrix Some chondrules preserve their primarily forsteritic containing an association of moissanite and diamond. composition. Splitting of chondritic melts results in more effective The presence of metallic drops in chondrules pro accumulation of hydrogen fluids in a metallic matrix vides evidence for their separation from the iron phase than in chondrules, which determines the high stabil on the early stage of the evolution of chondritic mag ity of the liquid state of the matrix and causes subse matism, in accordance to the diagram (Fig. 1). This

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100 μm 20 µ (а) (b) m

Fig. 2. A primary forsterite chondrule containing drops of metallic iron and replaced by a secondary olivine matrix in the chon drite Allende, scale bar 100 µm (a), and finegranular olivine matrix of the meteorite Allende composed of ironrich olivine and containing sulfide–metallic inclusions of kamacite, taenite, and troilite (light segregations) (b). The quenched texture of the matrix, which is represented by elongated (laminar, sometimes zoned) olivine laths, proves its primarily melt (magmatic) nature. Carbonic and hydrocarbonic material occurs in the interstitials, scale bar 20 µm. stage corresponds to the left side of the considered Si/Mg in the matrix and bulk composition of carbon reaction. Shifting of this reaction to the right results in aceous chondrites were considered in (Palme and the appearance of carbonaceous chondrites in the Hezel, 2011) in comparison with the composition of sequence CI–CR–CM–CV–CK; their average com the Sun. Figure 3 gives a comparison of the chondrites positions are successively plotted on the tie line (Fig. 1) Allende and Efremovka in this regard. According to connecting the compositions of the matrix 0.66Fe + their position, we may suggest a more primitive state of 0.34SiC and forsterite chondrules (Marakushev et al., the evolution of the Efremovka chondrite in compari 2011). Similar relationships between Fe/Mg and son with Allende; the average composition of the latter is more distant on the tie line from the composition of the primary matrix. Fe The compositions of their secondary matrix and 1 2 chondrules (Tables 2–4) are characterized on the dia 3 gram. These cover the entire compositional range 4 between the primary matrix (0.66Fe + 0.34SiC) and 5 chondrules (Mg2SiO4). The prevailing secondary 6 matrix, which corresponds to an olivine composition 0.66Fe + 0.34SiC 7 8 close to MgFeSiO4, can be named hortonolitic 9 (Fa 51–70%). Its more ironrich composition, which corresponds almost to fayalite (Table 2, analyses 19–12) is explained by the presence of silicon or moissanite in the primary matrix, which is the basis for the forma Kir tion of extremely ironrich fayalite:

SiC + 2Fe + 4H2O = Fe2SiO4 + C + 4H2. In the chondrite Efremovka these form fayalite Prv drops contained in an olivine matrix, which was Si Hb formed as a result of a chondrule–matrix interaction; Cpx Mg2SiO4 Mg + Ca the most magnesiumrich olivines are presented in Table 3. The olivine matrix of chondrites is typical (Table 4); its composition was determined by energy Fig. 3. The carbonaceous chondrites Efremovka and dispersive microanalysis of the areas of the matrix Allende: (1 and 2) their average compositions (at %), material by scanning of an electron beam over an area. respectively; (3) metallic matrix; (4) forsterite chondrules; (5) calc–alumina chondrules (CAIs); (6) secondary oliv Carbonaceous chondrites and the olivine matrix usu ine matrix (Table 4); (7 and 8) olivines from products of its ally contain forsterite chondrules replaced from mar interaction with a metallic matrix ((7) ironrich, Table 2) gins to a variable degree. and products of interaction of the secondary matrix with forsterite chondrules ((8 magnesiumrich, Table 3); (9) We may name carbonaceous chondrites forsterite– some minerals and their symbols: Kir, kirschsteinite; Hb, olivine in order to emphasize the nonequilibrium hibonite; Prv, perovskite; Cpx, clinopyroxene. character of the rocks. In addition to this prevailing

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Table 2. The composition (at %) of secondary ironrich olivine, which metasomatically replaces primary chondrules (anal yses 1–10, 13–20) and the metallic matrix (analyses 11 and 12) Analysis Si Al* Fe Mn Mg Cr 1 33.72 1.70 18.24 0.11 44.88 0.30 2 33.05 0.00 19.18 0.23 47.20 0.00 3 32.64 0.32 19.21 0.28 47.29 0.00 4 33.25 1.60 24.72 0.24 39.01 0.37 5 33.19 0.00 28.11 0.32 37.99 0.00 6 33.03 0.00 31.94 0.30 34.43 0.10 7 32.90 0.00 35.20 0.37 31.21 0.00 8 32.53 0.00 39.70 0.43 26.89 0.00 9 32.56 0.00 47.91 0.48 18.83 0.00 10 33.16 0.00 50.20 0.51 15.95 0.00 11 33.91 0.00 57.00 0.61 7.85 0.12 12 32.8 0.00 57.01 0.54 9.65 0.00 13 31.80 1.25 22.40 0.00 43.93 0.23 14 32.84 0.34 23.5 0.00 42.48 0.56 15 32.55 0.71 25.02 0.19 41.34 0.00 16 33.83 0.45 25.90 0.22 39.01 0.41 17 32.97 0.35 26.19 0.28 39.76 0.21 18 33.27 0.30 28.88 0.00 36.86 0.34 19 33.16 0.28 29.05 0.00 37.21 0.29 20 32.84 0.38 31.99 0.20 34.22 0.24 Analyses (1–12), the meteorite Efremovka; analyses (13–20), the meteorite Allende, Fig. 3. Hereinafter, analyses were performed in the Laboratory of Local Methods of Material Study of the Geological Faculty of Moscow State University on a Jeol JSM6480LV scanning electron microscope equipped with an INCAENERGY350 energydispersive spectrometer. Analyses were performed at an accelerat ing voltage of 15 kv and a current of 15 nA. *The high concentration of Al results from microscopic inclusions of the aluminum phase in olivine analyses from Tables 2, 3, and 5. type, there are varieties in which forsteritic chondrules directly above the core. Their fragments are preserved are almost completely replaced by olivine ones. This in the prevailing forsterite–olivine type of carbon compositional similarity of olivine of chondrules and aceous chondrites (Fig. 2). The sulfide component in the secondary matrix is typical of equilibrium olivine them is represented by troilite, as well as microinter chondrites. They may be named olivine carbonaceous growths of troilite and pentlandite crystals with the chondrites. Their link to forsterite–olivine chondrites composition of Fe 43.5–6.2%, S 33.4–34.5%, and Ni is proven by the presence of CAIs in both of them. Oli 18.2–21.8% (the composition of pure pentlandite is vine chondrites finish the evolutionary series of car Fe 32.56, Ni 34.21, and S 32.23%). The concentration bonaceous chondrites: forsteritic chondrites with a of Ni in taenite from the Efremovka chondrite is 65.2– taenite–kamacite matrix–forsterite–olivine chon 68.2%. The concentration of nickel in taenite and drites–olivine chondrites. kamacite from chondrules and the matrix does not dif The chondrite Hammadah al Hamra (Krot, Mei fer significantly. However, the concentration of cobalt bom, and Russel, 2001) is an example of the very begin in the matrix of the chondrite Efremovka is slightly ning of this series. Magnesiumrich chondrules and higher. Replacement of the sulfide–metallic matrix of their fragments are included in the metallic matrix. Its carbonaceous chondrites with an olivine matrix results finegranular kamacite mass contains larger metallic from an increase of the H2O/H2 ratio in fluids and a zoned grains (5–10 wt % Ni). This chondrite contains decrease of the total fluid pressure. large (~1 cm) metallic drops, which provides data about The magmatic nature of this process is clearly its formation as a result of separation of the metallic 1 core in the corresponding chondritic planet. reflected in the meteorite Allende , in which the matrix melt underwent rapid quenching with the for We may assume the occurrence of chondrites with a metallic matrix and forsteritic chondrules with drops 1 A sample of Allende was provided to the investigation by the of a metallic (sulfide–taenite–kamacite) phase Meteorite Committee, Russian Academy of Sciences.

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Table 3. The composition (at %) of magnesiumrich olivine, which shows the decrease of the magnesium concentration during the interaction of forsterite chondrules with the secondary olivine matrix Analysis Si AI Fe Mn Mg Ca Cr 1 33.22 0.29 0.45 0.00 65.78 0.26 0.00 2 33.37 0.00 0.69 0.00 65.70 0.24 0.00 3 33.21 0.00 0.70 0.00 65.83 0.26 0.00 4 33.07 0.60 0.73 0.00 65.40 0.00 0.19 5 33.27 0.18 0.79 0.00 65.63 0.13 0.00 6 33.38 0.55 1.75 0.17 63.46 0.69 0.00 7 33.42 0.27 1.85 0.00 64.46 0.00 0.00 8 33.09 0.00 2.95 0.00 63.69 0.27 0.00 9 33.10 0.00 3.02 0.00 63.75 0.12 0.00 10 33.25 0.00 3.04 0.20 63.39 0.13 0.00 11 33.24 0.00 3.52 0.00 62.88 0.20 0.17 12 32.99 0.00 4.14 0.00 62.62 0.24 0.00 13 33.21 0.00 5.27 0.73 60.63 0.16 0.00 14 33.18 0.00 5.64 0.00 61.02 0.16 0.00 15 33.12 0.00 6.03 0.00 60.85 0.00 0.00 16 33.19 0.00 6.99 0.37 59.29 0.17 0.00 17 32.97 0.00 9.79 0.61 56.04 0.24 0.00 18 33.07 0.43 11.01 0.23 54.54 0.43 0.29 19 33.42 0.00 12.24 0.00 53.93 0.26 0.15 20 33.07 0.00 4.93 0.00 61.85 0.15 0.00 21 33.16 0.00 5.64 0.00 61.05 0.15 0.00 22 33.25 0.67 7.27 0.20 58.09 0.25 0.00 23 32.94 0.21 7.52 0.00 59.14 0.19 0.00 24 33.47 0.00 9.89 0.00 56.64 0.00 0.00 25 33.69 0.00 13.96 0.09 52.19 0.00 0.06 Analyses (1–19), the meteorite Efremovka; analyses (20–25), the meteorite Allende. mation of a finegranular aggregate of tablular the primary matrix and chondrules. Deviation from (columnar in section) olivine grains with a size of up to this regularity is typical only of calcic–aluminum 20 μm. Its texture (Fig. 2b) is represented by a variety chondrules (CAIs); their minerals (diopside, spinel, of quenched spinifex texture that is typical of ultraba hibbonite, melilite, and others) occupy a random sic rocks. Such a habit of olivine grains resulting from position on the Si–Fe–(Mg + Ca) diagram (Fig. 3) its crystallization from the melt under the conditions are not controlled by the forsterite–kamacite interac of rapid cooling is well correlated with the experimen tion. However, the minerals of these chondrules were tal data (Donaldson, 1976). The interstitials between involved in the formation of the secondary olivine olivine plates contain carbon and hydrocarbon mate matrix of carbonaceous chondrites as well. For exam rials. The compositional variations of the secondary ple, the participation of normative diopside controls matrix are characterized in Table 4. Taenite and the incorporation of kirschsteinite (CaFeSiO4) in the kamacite associate with sulfides, and small (2 μm) secondary matrix of carbonaceous chondrites via the intergrowths of Pd and Sn are found as well. Forster reaction: ite–olivine (prevailing) and olivine carbonaceous CaMgSi2O6 + 2Fe + 2H2O chondrites, which represent successive stages of the = CaFeSiO4 + MgFeSiO4 + 2H2. evolution of primary chondritic melts are character Olivine chondrites contain andraditic garnet; its ized mineralogically on the diagrams (Fig. 3 and 4). main feature that is typical of carbonaceous chondrites These diagrams clearly reflect the specifics of the evo is the incorporation of the koharite endmember lution of matter, the composition of which is con (Mg3Fe2Si3O12). The concentration of koharite in trolled by the tie line connecting the compositions of andraditic garnet from dark inclusions reaches 76%

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Table 4. The composition (at %) of the secondary olivine matrix Analysis Si Ti Al Fe Mn Mg Ca Na Cr 1 32.14 0.00 2.68 25.9 0.00 38.84 0.22 0.00 0.22 2 30.73 0.00 2.92 30.36 0.00 34.99 0.60 0.00 0.40 3 33.11 0.00 2.69 30.60 0.00 31.46 1.42 0.71 0.00 4 33.52 0.00 2.78 30.87 0.00 29.65 2.11 0.81 0.00 5 35.78 0.00 3.18 32.87 0.00 26.32 1.16 0.00 0.29 6 33.25 0.00 2.20 32.91 0.00 30.06 1.24 0.00 0.35 7 32.21 0.00 2.72 33.39 0.00 28.81 2.04 0.59 0.00 8 33.91 0.29 2.89 33.43 0.00 26.69 2.64 0.00 0.44 9 32.3 0.00 2.53 34.78 0.00 28.74 1.23 0.43 0.00 10 30.89 0.00 2.19 35.08 0.00 30.95 0.39 0.00 0.44 11 31.39 0.18 2.30 35.25 0.00 28.56 1.43 0.59 0.00 12 33.81 0.00 3.85 37.52 0.38 23.77 0.47 0.00 0.22 13 32.66 0.00 3.44 37.86 0.24 23.7 1.16 0.93 0.00 14 34.1 0.00 2.73 38.31 0.31 23.26 1.09 0.00 0.19 15 33.47 0.00 3.08 39.08 0.38 23.27 0.50 0.00 0.23 16 32.26 0.00 2.00 39.66 0.29 25.57 0.22 0.00 0.00 17 33.05 0.00 2.88 40.16 0.36 21.86 0.60 1.10 0.00 18 33.61 0.00 2.13 40.80 0.49 22.26 0.70 0.00 0.00 19 33.13 0.00 2.37 31.05 0.00 30.75 2.23 0.47 0.00 20 33.02 0.00 3.31 31.43 0.00 27.19 4.73 0.00 0.33 21 32.44 0.00 3.37 32.61 0.00 27.71 3.52 0.00 0.35 22 31.41 0.00 2.77 33.43 0.24 28.51 2.46 0.64 0.54 23 31.86 0.00 2.18 33.54 0.00 30.62 1.54 0.00 0.25 Analyses (1–18), the meteorite Efremovka; analyses (19–23), the meteorite Allende. The compositions were analyzed over an area of 200 × 200 µm2.

(Biryukov, 1998). Rims around dark inclusions are (Fig. 5b), which provides evidence for a plastic state of composed of hedenbergite, wollastonite, and andra a fragment that occurs in the matrix. dite (Fig. 5a). The formation of andradite occurred The main characteristics of olivines from chon under an oxidized environment produced by drules; the main constituents of olivine chondrites are extremely high partial pressure of water in fluids: the following: (1) Chondrules crystallized from an ironrich melt 1.5Mg2SiO4 + 2Fe + 1.5SiC + 6H2O = Mg Fe Si O + 1.5C + 6H . and composed of large phenocrysts of ironrich olivine 3 2 3 12 2 and a matrix represented by small elongated laths of Olivine chondrites are observed only as ironrich olivine (Figs. 6a and 6b) predominate. The (dark inclusions) with sizes smaller than 3 cm (Fig. 5). composition of ironrich olivine is given in Table 5 The compositions of matrix in olivine–forsterite (analysis 30); according to the concentration of iron, it is chondrite (Table 5, analyses 7–19) are similar to those quite consistent with the matrix (Table 5, analyses 15– of ironrich olivine from chondrules (Table 5, analyses 30 18) and corresponds to equilibrium olivine chondrites. and 31) plotted on the diagram (Fig. 4). The average Such olivines are often characterized by a high alumi size of chondrules in them is smaller than that in host num concentration (up to 2 at %, Table 5). Maps of chondrites (Fig. 5a); the bulk concentration of chon the AlKα and NaKα distribution in olivine grains drules is lower as well. Matrix recrystallization results show that the high concentrations of these elements in the formation of a block texture in dark inclusions are controlled by microinclusions of phases enriched (Fig. 5d). The boundaries of dark inclusions often have in aluminum, as well as both aluminum and sodium clastic contours (Fig. 5c). However, in other cases (relics of highalumina phases); there are “injections” of the matter of an inclusion (2) Chondrules containing relics of magnesium matrix to the matrix of the host meteorite and “pres rich olivine in the center (Table 5, analyses 21–23) sure” of the host meteorite chondrule in an inclusion replaced by ironrich olivine (Table 5, analyses 24–

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Fe 1 Some olivine chondrites (both chondrule and the 2 matrix in them) are crossed with veins of pyroxenes, 3 Fe and Ni sulfides, and fayalite, and are surrounded by 4 5 rims (Fig. 5a) consisting of hedenbergite, wollastonite, 6 and andradite (Buchanan, Zolensky, and Ried, 1997). Fa 7 These minerals are observed in the matrix of the mete 8 orite Allende as well. Using intergrowths of heden 9 bergite and salite, the temperature of the formation of pyroxenes in the matrix (1320 K), as well as the rate of melt cooling (>10°C/h) were determined. The tem perature of the formation of rims around dark inclu sions estimated by intergrowths of wollastonite and hedenbergite is 1000°C (Brenker and Krot, 2002). The oxygen isotope characteristics of carbon aceous chondrites and their dark inclusions were Si reported in (Clayton and Mayeda, 1999); the data on Di Fo Mg + Ca dark inclusions are given in parentheses: the chondrite Efremovka: δ18O = –3.42‰ (+9.79‰); δ17O = Fig. 4. The material of dark inclusions in the chondrite ⎯6.86‰ (+4.87‰); and the chondrite Allende: δ18O = Efremovka (at %) (Table 5, Fig. 5): (1) ironrich olivine of δ17 chondrules; (2) relict magnesiumrich olivine of chon +1.51‰ (+5.75‰); O = –2.73‰ (+1.08‰). The drules; (3) matrix (average compositions analyzed over an heavier oxygenisotope composition of olivine chon area of 200–400 µm; (4) CAIs; (5) dark inclusions; (6–9) drites from dark inclusions results from their strong compositions of host matter of the chondrite Efremovka: oxidation as a result of the introduction of heavy oxy (6) matrix, (7) magnesiumrich chondrules, (8) ironrich gen isotopes from water of carbonaceous chondrites chondrules, (9) bulk composition of the meteorite Efre 18 17 movka. Some minerals and their symbols: Fa, fayalite; Fo, (δ O = +28.10‰; δ O = +17.70‰). Olivine chon forsterite; Di, diopside. drites represent the highest stage of the regressive evo lution of chondritic matter, which reflects a complete shift of the reactions considered above to the right. 29) to a variable degree. Replacement at the final stage Most likely, they were formed in peripheral parts on starts from a rim around chondrules (Fig. 2a); the surfaces of chondritic planets and underwent fluid (3) Chondrules with primary forsterite forming influence to a higher degree than forsterite chondrites, phenocrysts and elongated laminar microlites of which is evident from the heavier oxygenisotope groundmass with aluminumrich diopside in intersti composition in them. By contrast, forsterite and for tials. Replacement of forsterite phenocrysts by iron sterite–olivine chondrites composed the internal parts rich olivine could occur with preservation of the pri of planets. They preserved a liquid state for a longer mary matter of forsterite as relics in the central parts time, and during the removal of the outer limiting (Fig. 5d), whereas microlites of groundmass were pressure they were expansively intruded in the chon completely replaced by olivine; dritic crust of planets capturing olivine chondrites (dark inclusions) as xenoliths (Fig. 5) with progressive (4) chondrules of a specific type with the barred (hightemperature) influence. texture of ironrich olivine and relics of forsterite or magnesiumrich olivine (Figs. 6c and 6d). Such chon Weighting of oxygen in the sequence of the forma drules are surrounded by thin rims with extremely tion of forsterite–olivine and then olivine chondrites ironrich olivine (Fig. 6c); is controlled by hydration with the introduction of heavy oxygen with water. In contrast to this process, (5) Chondrules with radial structures represented metasomatic replacement of forsterite with ironrich by ironrich olivine and lowcalcium pyroxene. olivine (Mg2SiO4 + FeO = MgFeSiO4 + MgO) takes The compositions of the secondary matrix of oliv place without being accompanied by the observed ine chondrites, as well as their magnesium and iron effective weighting of oxygen. However, metasomatic rich olivines, are given in Table 5. The matrix of dark replacement similarly results in the equilibration of inclusions (Table 5, analysis 31) composed of second the olivine composition in the matrix and chondrules ary olivine is peculiar by its heterogeneous texture with the formation of olivine chondrites, although it is (Figs. 5b and 5d) and enrichment of olivine in alumi not significantly different from the host forsterite–oli num. Replacing minerals of chondrules, ironrich oli vine chondrites by the oxygen composition. An exam vine of olivine chondrites (dark inclusions) preserves ple is provided by the chondrite Murchinson with dark the primary texture of chondrules. The similarity of its inclusions containing lighter oxygen (δ18O = composition to the composition of the matrix mostly +4.12‰; δ17O = –1.42‰) in comparison with the results in the disappearance of boundaries between host chondrite (δ18O = +7.30‰; δ17O = +1.20‰) chondrules and the matrix (Fig. 5b–d). (Clayton and Mayeda, 1999).

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CAI

rim

1 μm (а) (b)

Fo groundmass

500 μm 100 μm (c) (d)

Fig. 5. Dark inclusions (olivine chondrites) in the chondrites Allende (a) and Efremovka (b–d): (a) dark inclusion NWa 3118 (CV3) (url: http://www.meteorites.com.au/odds&ends/DarkInclusions.html) characterized by the smaller size of chondrules in comparison with the host ; CAIs (light) occur in the dark inclusion, as well as in the host chondrite; arrow indicates the surrounding rim composed of hedenbergite, wollastonite, and andradite, scale bar 1000 µm; (b) dark inclusion E53 from the meteorite Efremovka represented by ironrich chondrules in an ironrich matrix; “pressed” chondrules of the host meteorite are observed in the marginal parts of the inclusion, which provides evidence for a plastic state of the inclusion at the moment of its capture by the host meteorite, scale bar 1000 µm; (c) dark inclusion E80 (1) from the meteorite Efremovka char acterized by angular boundaries, which provides evidence for its appearance in the host meteorite as an already cooled fragment, scale bar 500 µm; (d) chondrule from dark inclusion E80 (1) from the meteorite Efremovka replaced by ironrich olivine with a forsterite (Fo) relic in the center; relict areas of crystallized groundmass with microlites of olivine and alumodiopside in intersti tials are observed; the groundmass is identical to that demonstrated in Fig. 6a according to the composition and texture, scale bar 100 µm.

These data are compared with the data on the determine the evolutionary sequences of the main chondrites Efremovka and Allende on the diagram types of ordinary (HH–H–L–LL), as well as carbon (Fig. 7). The average composition of the meteorite aceous (CI–CR–CM–CO–CV–CR) chondrites. Efremovka differs from that of the meteorite Allende The iron–silicate evolution of chondrites correlates by the light oxygenisotope composition, which pro with the evolution of carbon materials, which was in vides additional evidence for its more primitive char part considered in (Marakushev et al., 2003; Maraku acter. Thus, the evolution of the iron–silicate matter shev, Glazovskaya, and Marakushev, 2010). of carbonaceous chondrites is a complex multifaceted The carbonic matter of carbonaceous chondrites process, which nevertheless has a general direction contains widely variable hydrocarbons and organic controlled by the oxidation of metallic iron under the compounds: aliphatic and aromatic hydrocarbons, influence of the water component of fluids and fullerenes, amino acids, diamino acids, carboxylic involvement of its oxides in the composition of sili acids, dicarboxylic acids, hydroxy acids, phosphonic cates. The process starts from the formation of iron– acids, sulfonic acids, purines, pyrimidines, Nhetero silicate chondrites, which represent the initial stage of cycles, amides, amines, alcohols, and carbonyl com the evolution of carbonaceous, as well as other types of pounds (Meierhenrich et al., 2004; Irvine, 1998; Pizza chondrites. The chondrule–matrix tie lines in Fig. 1 rello and Holmes, 2009; Shimoyama and Ogasawara,

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Table 5. The composition (at %) of the matrix of the chondrite Allende (analyses 1–6) around the dark inclusion, the matrix of its dark inclusion (analyses 7–19), magnesium (analyses 20–23) and ironrich (analyses 24–32) olivines from chondrules of the dark inclusion Analysis Si Al Fe Mn Mg Ca Ni Cr 1 37.09 4.32 22.55 0.3 35.12 0.03 0.00 0.59 2 33.66 2.73 29.53 0.26 31.95 0.02 1.38 0.47 3 33.52 2.45 29.85 0.31 32.33 0.01 1.09 0.44 4 33.66 3.26 30.46 0.00 30.80 0.03 1.40 0.40 5 33.87 3.18 33.78 0.29 28.41 0.01 0.47 0.00 6 32.69 2.92 35.16 0.00 27.82 0.02 0.92 0.47 7 35.45 2.85 24.52 0.00 35.91 0.04 0.95 0.29 8 34.46 3.6 25.36 0.00 35.58 0.01 0.53 0.46 9 32.95 3.18 26.54 0.00 35.57 0.02 1.30 0.45 10 33.29 3.47 26.92 0.21 34.64 0.01 1.13 0.33 11 33.69 3.00 27.25 0.28 34.58 0.01 0.86 0.32 12 33.40 2.89 27.54 0.24 34.71 0.01 0.84 0.37 13 33.25 3.39 27.67 0.31 34.08 0.02 1.03 0.27 14 33.50 3.50 27.78 0.24 33.21 0.01 1.38 0.39 15 32.93 2.64 28.29 0.00 34.05 0.00 1.79 0.29 16 33.09 3.13 28.82 0.00 33.91 0.01 0.67 0.37 17 33.30 2.68 28.59 0.21 34.29 0.01 0.67 0.24 18 33.09 2.68 28.87 0.00 33.85 0.01 1.21 0.29 19 32.42 3.50 29.42 0.24 32.91 0.01 1.13 0.37 20 33.15 0.00 0.31 0.00 66.54 0.00 0.00 0.00 21 33.34 0.61 0.34 0.00 65.70 0.00 0.00 0.00 22 33.28 0.19 0.59 0.00 65.93 0.00 0.00 0.00 23 33.27 0.23 1.48 0.00 65.02 0.00 0.00 0.00 24 33.29 1.43 20.12 0.20 44.52 0.00 0.00 0.43 25 32.58 1.96 20.57 0.00. 44.71 0.00 0.00 0.18 26 32.79 1.58 20.64 0.00 44.67 0.01 0.00 0.31 27 31.82 1.46 21.48 0.00 44.75 0.00 0.00 0.49 28 32.48 1.42 22.42 0.00 43.28 0.00 0.00 0.39 29 32.45 1.33 27.50 0.00 38.40 0.00 0.00 0.32 30 32.71 1.46 28.14 0.21 37.10 0.00 0.00 0.38 31 32.69 1.50 29.16 0.16 35.75 0.35 0.00 0.30 32 31.55 1.07 31.63 0.24 35.50 0.00 0.00 0.00 The compositions of the matrix were analyzed over an area of 200 × 200 μm2.

2002), as well as insoluble macromolecular matter with with strongly predominant hydrocarbons (Pizzarello, compositions from C100H77N3O12S2 to C100H46N10O15S45 Cooper, and Flynn, 2006; Irvine, 1998), which are the (Pizzarello, Cooper, and Flynn, 2006). Carbonaceous basis of the development of organic matter (Maraku chondrites contain nitric hydrocarbons, namely alky shev and Marakushev, 2008; 2010). lamines (e. g., CH5N), alkylamides (CH3N), nitrogen Polycyclic aromatic hydrocarbons (naphthalene, bearing aromatic hydrocarbons (C5H5N) and nitryls diphenyl, chrysene, and pyrene) in the chondrite (C2H3N) including cyanic acid and its polymer, ade Efremovka were studied by thermoluminescent analy nine (CHN)5. sis (Glazovskaya and Ul’yanov, 2010). The study of The iron–silicate evolution of carbonaceous chon hydrocarbons was carried out on a Fluorat 02 Pan drites over the entire range of protoplanetary evolution orama spectrofluorimetric apparatus (equipped with a was correlated with the formation of carbonic matter cryogenic device) in the Laboratory of Carbon at the

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Ol

groundmass

Cpx

20 μm 100 μm (а) (b)

rim

Ol

Fo

100 μm μ (c) (d) 200 m

Fig. 6. Chondrules from dark inclusions in the meteorite Efremovka (b and d) and their details: (a, b) olivine (Ol) phenocrysts crystallized from the ironrich melt in the groundmass with a quenched texture composed of small elongated crystals of ironrich olivine and alumodiopside in interstitials, scale bar 20 µm; (b) 100 µm; (c, d) chondrules with a barred texture of ironrich olivine, relics of forsterite, and a rim of extremely ironrich olivine in the marginal part of the chondrule, which reflects the aggressive influence of an ironrich matrix; scale bars 100 µm (c), 200 µm (d).

Geographic Faculty of Moscow State University. and represents a set of structural and stereo isomers. In Diphenyl (C12H10, 0.0082 ppm), naphthalene (C10H8, the C–H–O–N system they are represented by only 0.0265 ppm), chrysene (C18H12), and pyrene (C16H10) 10 compositions (in contrast to 18 compositions of were registered in a chondrite matrix. Spectra were 20 biological amino acids), whereas the C–H–N sys obtained in a solution of normal hexane at T = 77 K tem has only 7 compositions (Fig. 8) (Marakushev and ( ⎯196°C). All registered aromatic hydrocarbons were Marakushev, 2010). represented by crystalline materials that are insoluble The final stage in the evolution of chondritic plan in water. ets before their explosive decomposition with the for The meteorite Efremovka (with a weight of 21 kg) mation of asteroids is reflected in the strengthening of was found in Kazakhstan; it spent a long period of time intense hydration of carbonaceous chondrite material on a plowed field and was possibly polluted by organic (C3), in which, first of all, the secondary olivine materials. However, polycyclic aromatic and unsatu matrix is replaced by serpentine (chondrites C2) and rated aliphatic hydrocarbons with a prevalence of car then chondrules with only small relics (chondrites C1) bon over hydrogen are typical of the insoluble macro are hydrated. Carbon is introduced in the sequence of molecular matter of almost all carbonaceous chondrites this hydrothermal transformation of carbonaceous (Murchinson, Murray, Nogoya, Orgueil, Allende, and chondrites (C3–C2–C1); its concentration directly others) (Pizzarello, Cooper, and Flynn, 2006). correlates with water content (wt %): C3 (H O 1.0, C 0.46)–C2 (H O 13.23, Numerous investigations of organic matter in car 2 2 bonaceous chondrites have demonstrated the presence C 2.44)–C1 (H2O 20.54, C 3.62). of more than 70 amino acids, but their composition is Introduced carbon is represented by finegranular primitive in comparison with biological amino acids graphite and carbonic matter, which determined the

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δ17O, ‰ differ from chondrites of other types by the high con centration of carbon in their primary matrix. This was reflected in the average compositions of chondrites: 4 C3 (H2O 1.0, C 0.46)–E (H2O 0.62, C 0.29)–H (H2O 0.27, C 0.01). The negligible concentration of carbon in ordinary chondrites reflects the almost com 1 plete absence of carbon in their primary and secondary 2 matrices. Thus, only the most primitive organic mate 0 3 rials are formed in meterorites as a result of regressive 4 5 processes (hydration) of carbon and hydrocarbons. 6 Carbonaceous chondrites do not contain amino –4 acids (such as tryptophan, phenylalanine, histidine, or arginine) that are important for the function of active centers of enzymes. The impossibility of the formation of key enzyme macromolecules from a limited set of amino acids (mostly, the absence of the main amino –8 –4 0 4 8 12 acids, such as lysine and arginine) was demonstrated in (Trifonov, 2008; McDonald, 2010). δ18O, ‰ The compositions of amino acids and their dimers Fig. 7. Dark inclusions (full symbols) in the carbonaceous (dipeptides) of carbonaceous chondrites on the dia chondrites (empty circles) Allende (1, 2), Efremovka (3, gram (Fig. 8) correlate with hydrocarbons of the CH2 4), and Murchison (5, 6) on the diagram of oxygen iso series and nitrogen compounds, and are regularly topes, data from (Pizzarello, Cooper, and Flynn, 2006). located on the CH2–NH, CH2–N2, and CH2–HCN tie lines. Consequently, their formation may be related N to the reactions with the influence of the fluids H2O– N 0 2 NH, H2O–N2, and H2O–HCN on hydrocarbons and 100 carbon (Table 6). As is evident from the relationships 11 between their compositions, amino acids may be 20 22 80 33 formed as a result of dipeptide hydration, whereas dipeptides may be the products of amino acid dehy 40 60 dration. However, the latter process is not thermody NH namically favorable, because, for example, the

60 enthalpy of condensation of alanine (Ala) and glycine 40 HCN N2 (Gly) with the formation of dipeptide alanylglycine H2O + N2 G ly (AlaGly) in water has a positive value of 17.26 kJ at 80 Gly NH 20 Le 37°C and pH 7 (Galimov, 2001). The first variant H2O + NH u 1 2 C (diamond, (Table 6), which corresponds to the general evolution 73 6 Pro moissanite) 100 4 5 0 of carbonaceous chondrites with universal regressive H O H 0 2 20 40 C3H4 60 C4H2 80 100 C CH2 C4H4 hydration as a driving force is preferable. The discov HCN H2O + HCN ery of the dipeptides characterized in (Pizarello and Holmes, 2009) and the observed correlation of their Fig. 8. The series of organic materials from carbonaceous compositions with hydrocarbons largely determine the chondrites ((1) dipeptides, (2) amino acids) in comparison genesis of organic matter in carbonaceous chondrites. with the composition of unsaturated hydrocarbons (3). Dashed lines denote the reactions of their formation as a Monosaccharides, such as ribose (Rib, C5 + 5H2O = result of hydrocarbon dehydration (Table 6) under the C5H10O5) and deoxiribose (dRib, C5H2 + 4H2O = influence of aqueous solutions N /H O + N , NH/H O + 2 2 2 2 C5H10O4), which played the key role in the evolution NH, and HCN/H2O + HCN. Numerals: (1) glycine C H NO ; (2) alanine C H NO , serine C H NO ; (3) of organic matter on the Earth, were not found in the 2 5 2 3 7 2 3 7 3 organic matter in carbonaceous chondrites. They valine, norvaline C5H11NO2; (4) leucine, isoleucine, and norleucine C6H13NO2; (5) proline C5H9NO2, glutamate react with the organic compounds (nitrogen bases) C5H9NO4; (6) aspartate C4H7NO4; (7) treonine with the formation of nucleosides and nucleotides C4H9NO3, aminobutyrate, aminoisobutyrate C4H9NO2. (Table 7), which are absent in meteorites and represent the highest stage of geochemical (abiogenic) evolution formation of this type of chondrites, “the carbon of the organic world. In contrast to primitive organic compounds that formed during regressive processes of aceous chondrites.” However, such secondary enrich hydration, they are formed as a result of progressive ment has deep roots in the protoplanetary primary processes of dehydration that require significant evolution of chondritic magmatism. As was demon energy. Such energy is only created on Earth due to the strated above (Figs. 1 and 3) carbonaceous chondrites presence of a hydrosphere enriched in oxygen, when

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Table 6. The formation of dipeptides and amino acids in carbonaceous chondrites by reactions of hydration Series (Fig. 8) Name, formula, and symbol (in parentheses) Reaction

Glycyl–glycine, C4H8N2O3 (GlyGly) C4H2 + (N2 + 3H2O) = C4H8N2O3

Glycyl–alanine, C5H10N2O3 (GlyAla) C5H4 + (N2 + 3H2O) = C5H10N2O3

Alanyl–alanine, glycyl–aminobutyrate, C6H12N2O3 C6H6 + (N2 + 3H2O) = C6H12N2O2 CH2–N2 (AlaAla, GlyAba)

Glycyl–valine; alanyl–aminobutyrate, C7H14N2O3 C7H8 + (N2 + 3H2O) = C7H14N2O3 (GlyVal, AlaAba)

Glycyl–leucine, C8H16N2O3 (GlyLeu) C8H10 + (N2 + 3H2O) = C8H16N2O3

Glycyl–proline, C7H12N2O3 (GlyPro) C7H5 + (HCN + 3H2O) = C7H12N2O3

Proline, C5H9NO2 (Pro) C4H4 + (HCN + 2H2O) = C5H9NO2 C H N O + H O = C H NO + C H NO CH2–HCN 7 12 2 3 2 5 9 2 2 5 2

Glutamate, C5H9NO4 (Glu) C5 + (HCN + 4H2O) = C5H9NO4

Aspartate, C4H7NO4 (Asp) C4 + (HCN +3H2O) + 0.5O2 = C4H7NO4

Glycine, C2H5NO2 (Gly) C2 + (NH + 2H2O) = C2H5NO2 C4H8N2O3 + H2O = 2C2H5NO2

Alanine, C3H7NO2 (Ala) C3H2 + (NH + 2H2O) = C3H7NO2 C6H12N2O3 + H2O = 2C3H7NO2

Valine, C 5H11NO2 (Val) C5H6 + ( NH + 2H2O) = C5H11NO2 CH2–NH C7H14N2O3 + H2O = C5H11NO2 + C2H5NO2

Leucine, isoleucine, C6H13NO2 (Leu, Ile) C6H8 + (NH + 2H2O) = C6H13NO2 C8H16N2O3 + H2O = C6H13NO2 + C2H5NO2

Aminobutyrate, C4H9NO2 (Aba, AIB) C4H4 + (NH + 2H2O) = C4H9NO2 C6H12N2O3 + H2O = C4H9NO2 + C2H5NO2 deep fluids containing reduced compounds are intro may be assumed that chondritic planets, which later duced in it. were the source of asteroids and meteorites, were sep The formation of nucleotides proceeds with the arated similarly. Iron–silicate chondritic planets, in introduction of phosphorus and is limited by the dis contrast to essentially olivine ones, were the predeces tribution of phosphorite facies that are abundant in sors of terrestrial planets. Their layering with the for oceanic environments. The key role in the origin of life on mation of metallic cores and hard silicate envelopes the Earth is played by nucleosidphosphates (nucleotides), prevented explosive destruction. The fluid supply in including adenosinetriphosphate (ATP, Table 7), which their metallic cores, which generated magnetic fields, was called material no. 1 by E.M. Galimov (2001) in provided the stress state of planets and was realized in the sense that it finishes the geochemical (abiogenic) endogenic activity until their complete consolidation. evolution of organic matter and mainly controls the The terrestrial planets are in the nearest environ energetics of life. This level of abiogenic evolution of ment of the Sun. In contrast to them, more distant carbonic matter was far from obtainment being limited chondritic planets evolved with the development of the by the primitive development, which, however, regu chondrule–matrix interaction and the replacement of larly correlates with the iron–silicate evolution a metallic matrix by a silicate one, which prevented throughout. layering of these planets similarly to the terrestrial planets. As a result, chondritic planets underwent THE FORMATION OF CHONDRITES explosive decomposition with the formation of the AND THE PLANETARY EVOLUTION asteroid belt that is the source of chondrites. OF THE SOLAR SYSTEM Chondrite matter was formed at high temperatures We should emphasize the importance of the evolu and pressures as well, which could be gained only in tionary separation of chondrate material to iron–sili giant planets. cate (Fig. 1) and essentially olivine (Fig. 3) substances The temperature of their formation significantly in the planetary development of the solar system. It exceeded 1000°C. The high fluid pressure is evident

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Table 7. Nucleosides and corresponding nucleotides (only triphosphates (TP) are given) and their geochemical formation in the redox facies of ribose (Rib) and deoxyribose (dRib) Facies Name and symbol Reaction of dehydration

Uridine (U) C4H4NO2(Ura) +C5H10O5 = C9H12N2O6 + H2O

Phosphate (UTP) C9H12N2O6(U) + 3H3PO4 = C9H15N2O15P3 + 3H2O

Guanosine (G) C5H5N5O(Gua) + C5H10O5 = C10H13N5O5 + H2O

Phosphate (GTP) C10H13N5O5(G) + 3H3PO4 = C10H16N5O14P3 + 3H2O Ribose (Rib) C5H10O5 Adenosine (A) C5H5N5(Ade) + C5H10O5 = C10H13N5O4 + H2O

Phosphate (ATP) C10H13N5O4(A) + 3H3PO4 = C10H16N5O13P3 + 3H2O

Cytidine (C) C4H5N3O(Cyt) + C5H10O5 = C9H13N3O5 + H2O

Phosphate (dG) C9H13N3O5(C) +3H3PO4 = C9H16N3O14P3 + 3H2O

Deoxyguanosine (dG) C5H5N5O(Gua) + C5H10O4 = C10H13N5O4 + H2O

Phosphate (dGTP) C10H13N5O4(dG) + 3H3PO4 = C10H16N5O13P3 + 3H2O

Deoxyadenosine (dA) C5H5N5(Ade) + C5H10O4 = C10H13N5O3 + H2O

Phosphate (dATP) C10H13N5O3(dA) + 3H3PO4 = C10H16N5O12P3 + 3H2O Deoxyribose (dRib) C5H10O4 Deoxytimidine (dT) C5H6N2O2(Thy) + C5H10O4 = C10H14N2O5 + H2O

Phosphate (dTTP) C10H14N2O5 + 3H3PO4 = C10H17N2O14P3 + 3H2O

Deoxycytidine (dC) C4H5N3O + C5H10O4 = C9H13N3O4 + H2O

Phosphate (dCTP) C9H13O4 + 3H3PO4 = C9H16N3O13P3 + 3H2O from presence of diamonds with a low bulk density with the formation of the asteroid belt (the source of (2.32–2.33 g/cm3) in all types of chondrites (Brealey chondrites). and Jones, 1998, p. 278; Besmen, Hoppe, and Ott, Thus, chondrites finish the planetary evolution of 2011), which results from the presence of numerous the solar system (Marakushev, 2005). This idea differs fluid inclusions in diamonds. These parameters reflect from the traditional concept on the formation of the features of the formation of chondritic planets chondrites at the very beginning of the planetary evo (Marakushev, 2005; Marakushev, Zinov’eva, and Gra lution of the solar system, directly in the protosolar novsky, 2010). nebula (Krot et al., 2009; 2010; Gilmour, 2010). The Sun (a yellow dwarf) produces only light ele According to the nebular hypothesis, chondrites do ments, which remain in its interior and cannot be not finish, but start the formation of iron–silicate studied directly. The observed chemical composition planets. From this point of view, chondrites are con of the solar system was inherited from its predecessor, sidered as samples of planetesimals (ElkinsTanton namely a giant star, which exploded as a Supernova and Zuber, 2011), the accretion of which resulted in and formed a gaseous disc that was rapidly cooled with the formation of iron–silicate planets. the formation of space dust and icy planetesimals. Due Accretion of such a type cannot explain the forma to rapid rotation of the disk, hydrous planetesimals tion of fluid magmatic cores that are responsible for were removed to its periphery, where their accretion magnetic fields and the endogenic activity of terres resulted in the formation of protocomet masses and trial planets. They determine the evolution of the peripheral giant planets (Neptune and Uranus). Earth during 4.6 billion years, whereas the activity of Accumulation of hydrogen icy masses resulted in other terrestrial planets proceeded until their com the formation of the Sun and giant planets in the inter plete consolidation. The endogenic activity of terres nal part of the disc. Reaching the stellar state, the Sun trial planets, which is clearly reflected in volcanism, is caused the dissipation of the disc to space, so that the evidence for the evolution and layering of parental rapidly rotating giant planets were in a vacuum. By giant planets under the pressure of their fluid enve contrast to the distant planets of the Jupiter group, the lopes. Fluid nickel–iron cores were typical of primi nearsolar giant planets lost their hydrogen envelopes, tive chondritic planets as well, as may be judged from and iron–silicate cores were transformed into individ their explosive destruction with the formation of aster ual planets, namely terrestrial planets and chondritic oids (fragments of planets) and the residual magneti planets, which underwent explosive decomposition zation of chondrites. All these peculiarities are

MOSCOW UNIVERSITY GEOLOGY BULLETIN Vol. 68 No. 5 2013 EVOLUTION OF THE IRON–SILICATE AND CARBON MATERIAL 279 explained by the hypothesis that is described in this researchers (Russel et al., 2005, p. 317): “melting of paper and are not substantiated by the nebular model silicates, metal, CAIs mixed in various proportions.” (hypothesis). The magmatic chondrule–matrix interaction lies at According to the nebular hypothesis, the origin of the base of the formation of the main types of chon chondrites is the natural continuation of the formation drites. of iron–silicate space dust. According to some points of view, chondrules and the matrix are considered as CONCLUSIONS independent formations (Brearly and Jones, 1998), whereas other models (Hezel and Palme, 2008; Palme Chondrites are heliocentric meteorites with an and Hezel, 2011) demonstrate the correlation of their asteroid belt as their source. Asteroids are the frag compositions thus providing evidence for synchro ments of iron–silicate primitive (chondritic) planets nous formation and a close genetic relationship. For that developed as molten iron–silicate cores of their example, Brearly and Jones (1998) considered that parental giant planets, which occurred in the solar sys chondrites were formed as conglomerates of particles, tem between the orbits of Mars and Jupiter. They lost which recorded various individual nebular histories. hydrogen selectively under the influence of the Sun, Chondrites are the refuge of interstellar particles, which resulted in an increase of the H2O/H2 ratio in which determined the formation of the solar system their fluid envelopes; their pressure controlled the evo and survived in the environment of protoplanetary lution of the chondritic planets. This controls the uni disc (solar nebula). This model excludes the synchro versal direction of the evolution of the iron–silicate nous, mutually related formation of chondrules and material of chondritic planets resulting from the oxi the matrix of chondrites, which is a significant short dation of metals under the influence of the hydrous coming, since the regular evolution of the composi component of fluids. First, this resulted in the forma tions of chondrules and the matrix is not explained by tion of chondrules in a nickel–iron metallic matrix; this model. then, it was the basis for the water–matrix interaction, Based on the analysis of the Ca–Al distribution in which provided all of the observed diversity of chon carbonaceous chondrites, the authors of much more drites. progressive studies (Hezel and Palme, 2008; Palme Chondritic planets were formed as metallic cores of and Hezel, 2011) demonstrated that chondrules and hydrogen giant planets composed of iron, nickel, and the matrix were not formed independently, but were many other metals that contained finely dispersed dia separated together from the same chemical reservoir mond and moissanite. (Hezel and Palme, 2008, p. 716). In essence, these The influence of the hydrous component of fluids conclusions are close to our ideas, according to which controlled the oxidation of metals and the separation “the chemical reservoirs” were represented by prima of primary chondrules, first calc–alumina (their frag rily homogeneous primitive planets that separated into ments in carbonaceous chondrites are named CAI), chondrules and the matrix (Fig. 1). The main types of and then forsteritic ones. Further strengthening of the chondrites were produced by further chondrule– role of the hydrous component in the fluid envelopes matrix interaction with the introduction of heavy oxy of the parental planets resulted in interactions between gen isotopes. All these facts provide evidence for the primary chondrules and the primary metallic matrix, formation of the chondritic structure on the basis of a which was replaced by the secondary olivine matrix homogeneous substance. Most likely this was the melt, (Mg2SiO4 + (2Fe + SiC) + 4H2O = 2MgFeSiO4 + judging from the high (magmatic) temperature of C+4H2). Its primarily molten state is proven by the chondrite formation. A hightemperature state of the quenched texture in the chondrite Allende. The sec internal parts of the nebular disc with a decrease in ondary matrix of carbonaceous chondrites contains temperature to its periphery was suggested in order to the fragments of primary forsteritic chondrules, which explain hightemperature chondrite formation via the determines them as nonequilibrium forsterite–oliv nebular hypothesis (Wood, 1999). ine chondrites. At a complete shifting of the reaction However, in such variant it is not clear how the to the right, the composition of olivine from the sec huge mass of hydrogen that formed the Sun and sur ondary matrix and chondrules is equilibrated and rounding giant planets was accumulated in this disc. equilibrium olivine carbonaceous chondrites are Judging from their hydrogen composition, they were formed. Their formation is typical of the peripheral formed at a temperature close to absolute zero from parts of chondritic planets, where they were subjected icy planetesimals with iron–silicate material that to a longer fluid influence than forsterite–olivine occurred in a dispersed state (as space dust), whereas chondrites, which were isolated in the internal parts of the hightemperature state was reached later due to chondritic planets. With a decrease of the total pres gravitational compression. The formation of asteroids sure, they were expansively intruded to the outer enve and chondrites required a stage of evolution in the lopes of chondritic planets and captured olivine chon interiors of parental nearsolar giant planets. This drites as xenoliths (dark inclusions). stage includes clearly reflected signs of the magmatic The stepwise shifting of the reaction to the right is evolution of chondrites, which attracts the interest of characterized by an increase of the iron content in sil

MOSCOW UNIVERSITY GEOLOGY BULLETIN Vol. 68 No. 5 2013 280 MARAKUSHEV et al. icates, which determines the main types of carbon ElkinsTanton, L.T. and Zuber, M., Chondrite as samples aceous chondrites: CK–CV–CO–CM–CR–CI. of differentiated planetesimals, Earth Planet. Sci. Lett., This evolution of the iron–silicate material of chon 2011, vol. 305, pp. 1–10. drites correlates with the evolution of carbonic matter: Galimov, E.M., Fenomen zhizni. Mezhdu ravnovesiem i neli a decrease in temperature results in the formation of neinost’yu. Proiskhozhdenie i printsipy evolyutsii (Life hydrocarbons and primitive organic compounds. phenomenon: Between equilibrium and nonlinearity However, monosaccharides, which complete the abio (origin and evolution principles)), Moscow: URSS, genic formation of organic materials on the Earth, 2001. have not been observed among the latter. 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