The Generation and Mineral Associations of Rock Assemblages at Mud Volcanoes: Southeastern Siberia A

ISSN 0742-0463, Journal of Volcanology and Seismology, 2016, Vol. 10, No. 4, pp. 248–262. © Pleiades Publishing, Ltd., 2016. Original Russian Text © A.V. Tatarinov, L.I. Yalovik, S.V. Kanakin, 2016, published in Vulkanologiya i Seismologiya, 2016, No. 4, pp. 34–49.

The Generation and Mineral Associations of Rock Assemblages at Mud Volcanoes: Southeastern Siberia A. V. Tatarinov, L. I. Yalovik, and S. V. Kanakin Geological Institute, Siberian Branch, Russian Academy of Sciences, ul. Sakh’yanovoi 6a, Ulan-Ude, 670047 Russia e-mail: [email protected] Received January 29, 2014

Abstract—We consider the main features in the formation of rock assemblages in the southern Siberian Meso- zoic–Cenozoic mud volcanism area that the present writers identified. The related mineral associations and mechanism of generation were found. We identified fluid dynamic regimes of mud volcanoes with different mechanisms of mineral generation, viz., root (chamber) structures of fluid generation, as well as the channels for the transmission of the fluid–rock substratum and of hydrothermal fluids.

DOI: 10.1134/S0742046316030052

INTRODUCTION and Cenozoic basins in the Baikal region, as well as for Gas manifestations of mud volcanism in the Baikal soda and salt lakes, and mineral springs (Tatarinov Rift Zone have been known since the 1930s and Abramov, 2001; Tatarinov and Yalovik, 2006). (Ryabukhin, 1933). A gas volcanic feature was identi- Numerous mud-volcanic features have been iden- fied in the Patom Upland and called the Dzhebolda tified in Lake Baikal itself (De Batist et al., 2000; Isaev (Patom) crater. S.V. Obruchev believed that its forma- et al., 2002; Isaev, 2001; Colman et al., 2002), in the tion was related to a breakthrough of gas fluids (Kol- Barguzin basin (Isaev, 2006), and on the Barguzin– pakov, 1951). Chivyrkui isthmus (Dzyuba et al., 2002). Subsequent results from studies of the Patom crater The occurrence of the present-day mud volcanism corroborated the hypothesis of its fluid origin (Antipin has its most intensive form in the Baikal Rift Zone et al., 2011) and gave support to the hypothesis of its (BRZ) during large earthquakes, especially near epi- being one of the gas volcanic (gas–lithoclastic) variet- centers. Catastrophic earthquakes produce numerous ies of mud volcanoes (Isaev et al., 2012). A feature like small gryphon–salse cone-shaped edifices (Solonenko the Patom crater was found in the western Baikal and Treskov, 1960). region (the Levosarminskii crater) (Tatarinov, 1993). This study is concerned with the southern Siberian Occurrences of mud volcanism in the form of salses mud-volcanic region. We show distinctive miner- were discovered in some depressions of the eastern alogic features and indicators of mud volcanoes in Baikal region (Krendelev and Shamsutdinov, 1987; Cenozoic and Mesozoic intraplate riftogenic struc- Krendelev et al., 1988; Frish, 1967). tures and discuss how they came into being. The near-Sayan depression was found to contain basins surrounded by low earth ridges that mark the METHODS OF STUDY craters of mud–volcanic features with spatially and We studied the structural material complexes of the genetically related Fe–Mn mineralization (Tatarinov, Cenozoic, primarily present-day, occurrences of mud 1988). volcanism (Fig. 1). The mud–volcanic origin of the Lower Cretaceous Mineralogic studies were preceded by structural gold-bearing rock sequence in the Balei graben was geological observations to identify structural elements discussed by Gladkov et al. (1989). These authors in mud-volcanic edifices, such as the central hum- established the fact that the Balei ore field is a subver- mock, ring bank, gryphon, salse, compensation trough, tical degassing pipe that was composed of geyserites crater, caldera, and other elements, as well as by a lith- and carbonitized pelite–aleurite–psammite, breccia ologic and petrographic study of ejecta from mud-vol- conglomerate mud–volcanic complexes (Tatarinov canic eruptions. We used heavy concentrate sampling et al., 2011a). of unconsolidated mud-volcanic deposits. Crushed A predominantly mud-volcanic origin has been rock samples of 4–10 kg were used for studying the corroborated for rock assemblages of the Mesozoic mineral composition of travertines, geyserites, and

248 THE GENERATION AND MINERAL ASSOCIATIONS 249

P 12 34 5 12 80 160 240 km Bodaibo

56° B 1 8 7 G

L 6 Lake Baikal Irkutsk 5 Chita 52° А 4 11 2 3 9 Zh Ulan-Ude 13 10

102° 108° 114°

Fig. 1. A map showing the occurrences of mud volcanism in southeastern Siberia (the South Siberian mud-volcanic region). (1) Cenozoic and Mesozoic riftogenic troughs with mud-volcanic complexes (1 troughs in the Near-Sayan depression, 2 Tunka, 3 Ust’-Selenga, 4 Uda, 5 Kotokel’, 6 Ust-Barguzin, 7 Barguzin, 8 Baunt, 9 Chita–Ingoda, 10 Torei, 11 Unda–Dai, 12 Bodaibo, 13 Gusinoe Ozero); (2) areas of mud-volcanic features studied by the present authors; (3) craters of gas–explosive origin (L Levaya Sarma, P Patom); (4) mud volcanoes in Lake Baikal; (5) deposits of thermal springs (studied by these authors): A, Arshan; B, Baunt; G, Garga; Zh, Zhemchug. lithified sediments. Special attention was paid to bac- minerals from the crystalline basements of the basins terial organic and mineral aggregates that are widely (see Table 1), which were sometimes transported from abundant in the sand and mud deposits of thermal great depths (7–15 km). springs and crater lakes, travertines, and geyserites. We Rounded and oval-shaped massifs of gryphon used several techniques for detection, the study of sands, which are occasionally as high as 200 m, have mineral and rock compositions; ordinary mineralogic areas as large as 400 km2 and occupy 70–75% of the analysis; microprobe, electron microscopy, and X-ray Tunka, Barguzin, and Chara basins. They also com- structural analysis; various kinds of chemical analysis; pose small cones and ridge-shaped uplifts (Fig. 2). and Ram spectroscopy. Gryphon sands make, apart from ridge-shaped and isometric (in map view) massifs, also dike-like, vein- RESULTS AND DISCUSSION shaped, and tubular bodies. One frequently observes patches of secondary stalagmite- and coral-like, crus- The Main Features of the Structures and Rock tose, sulfate carbonate formations at the vents of cold Assemblages of Mud Volcanoes in Southeastern Siberia gas jets (seeps) on the surface of sand massifs (Fig. 3). The overwhelming majority of mud-volcanic com- Carbonitization involves considerable parts of sec- pensation basins (see Fig. 1) are shallow (less than tions of compensation basins, as far as forming traver- 2 km), and the conduits of mud volcanoes penetrate tines and silicate carbonate marl-like deposits (see deep into the Precambrian basement. Their sources Table 1). While sand massifs (diapirs) usually occur on are estimated to lie at depths of 3.5–15 km (Table 1). the tops of Cenozoic mud-volcanic basins, the sec- The ejecta of mud-volcanic eruptions are largely rock tions of sheet-like cone rock assemblages in the older assemblages of the psammite–gravelite–conglomer- (K1) Unda–Dai basin are crowned with geyserite ate dimension, with abundant gryphon sands, whose domes. massifs (diapirs) were called “kuituns” (Florensov, One remarkable feature of the southern Siberian 1960). They were found to contain clasts of rocks and mud-volcanic area consists in a wide abundance of

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 250 TATARINOV et al. = 4 = = 2 2 4 = 0– = 78.99, = 78.99, = 2.41, 4 4 2 = 0–0.41, 2 = 16.06. 2 = 0–0.07 2 = 6.36, N =0.012, CH =0.012, 2 2 ), nitrogen with an 4 = 0.008, CO = 0.8, N N = 0.73–2.47, 2 2 2 composition of gas fluidscomposition 65.50; Nitrogen–methane – He = 0.002, CH Н О CH 35.3–97.50, О (up to 5.9 vol %) in gas gas in %) 5.9 vol (up to Methane and hydrates. of gas jetsnitrogen in holes in the Baikal ice О 26.14, %) (vol Gas compositions in at spontaneous vents – Н lakes crater admixture of CH 60.35, CO Average compositions Average %). Methane and nitro- (vol – gen Н Ethane and methane %), vol 14.9 up to (ethane % of methane (99 vol CH n and Granina, 2002; Kis- 9; Ufimtsev et al., 2008) er, 2004;er, Lomonosov and Lysak, 1967; conditions hydrogeological hydrogeological 0–100 m hydrocarbonate m hydrocarbonate 0–100 groundcalcium–sodium water; Artesian sulfate– groundcalcium–sodium range in the depth water 900100–900 m, below m of the waters are thermal Fis- composition. same hydrocarbon- sure–vein ate–sulfate, sulfate and sulfate–hydrocarbonate waters in the crystalline Concentra- basement. of dissolvedtions oil are 0.01– hydrocarbons 3.46 mg/L Bottom waters chloride– waters Bottom sodium–hydrocarbonate, pore magnesium–calcium, of an underwa- waterWater thermalter spring on Fro- likha mud volcano, hydrocarbonate–sulfate– of sodium. Concentrations dissolved petroleum hydro- mg/L – 0.02–0.67 carbons , 2 , 2 C ° C ° in the Bar- 2 in zones in zones 2 , with up to , with up to 2 geothermal geothermal characteristics in fault zones it is 115– it isin fault zones 155 mW/m 7900 mW/m Tempera- fault zone. guzin ture in source of mud zones 150–200 volcanoes and 119 mW/m and 119 of discharge of thermal of discharge thermal water. Temperatures in chamber zones of mud – 200–500 volcanoes Heat flow mW/m Heat 50–100 Heat flowHeat mW/m 50–100 rn Siberian region based on materials from Bulin, 2005; Grani from rn Siberian region based on materials 86; Pospeev, 1988; Shabynin et al., 2002; Shpeizer et al., 199 et al., 2002; Shpeizer et Shabynin 1988; 86; Pospeev, inferred from from inferred geophysical data geophysical fluid-charged layers, 98; Krylov et al., 2008; Kulikova, 1961; Lishnevskii and Distl 1961; al., 2008; Kulikova, et 98; Krylov Baikal–Sukhoi-Log crustalupper seismic of thick- zone waveguide km. Wave- ness 2.5–10 5 km thick layer guide depths at with the top km. Electri- of 12–18 cally conductive layers in ranges (km): 6–10, depth 18–28, 12–18, 10–20, 10–36 In the northwestern part In the northwestern of the basin the 10-km Baikal–Sukhoi- thick Log crustal upper seismic occurs, zone waveguide out crops at the which surface rock assemblages assemblages rock of mud volcanoes Upper parts of sections sections of parts Upper mud volca- of underwater 100 about to down noes m gas contained that depth oil. occasionally hydra-tes, mudSand aleurolites, with carbon- clay breccia, rhodochrosite– the of ates with and family siderite xeno- Contain dolomite. of crystal- minerals genic (pyroxene, line basement garnet, pla- olivine, gioclase, and fuchsite). sedi- of bottom thickness km 7.5–8 reaches ments A 1400-m thick section. section. thick A 1400-m section, the of part Upper gryphonviz., quartz–feld- spar sand (diapirs, “kuituns”, down to sand- m depth), 150–200 with clay alternating stone section Lower interbeds. sandstonescontains with and carbo- of clay interbeds schist,naceous and inclu- Crater sions coal. of brown and sulfate mud-volcanic sand contain lakes chloride and mud deposits with mira- Oil bitumen and halite. bilite abundantis through- widely out the including the section, crystalline basement Geological peculiaritiesGeological system Fluid-dynamic volcanoes) crystalline basement (parentheses enclose (parentheses enclose the age or hypothetical the hypothetical age or 4–15 км – sedimentary 4–15 rock metamorphic and granitoids sequence and(Precambrian Paleo- км – “basaltic 15–28 zoic); ortho- Precambrian layer”: amphibolites, gneisses, dio- 28 andrites, gabbro diorites; ultra- км – Moho interface: assemblages basite–basite of Riphean (?) stratified massifs: 7–32 км – a frag- of Early of a block ment metamor- Precambrian phosed ultrabasites and km) l (5.4–15 basites 3.5–15 km – Early Pre- km – Early 3.5–15 gneiss, crystal-cambrian amphibo- and loschist, and Riphean Paleo- lites, gabbroids, granites, zoic km – and ultrabasites; 15 Precambrian Moho: Early ultrabasite–basite com- km) (5–10 plex depth to chambers of mud mud of chambers to depth The main characteristics of mud-volcanic depressions in the southe of mud-volcanic The main characteristics (age) Structures Baikal basinBaikal (age) Barguzin basinBarguzin (Kz) Table 1. sin, 2001; Krendelev and Shamsutdinov, 1987; Krendelev et al., 19 Lunina, 2009; Mineral’nye vody …, 1961; Moiseenko and Smyslov, 19 and Smyslov, Moiseenko …, 1961; vody Lunina, 2009; Mineral’nye

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 THE GENERATION AND MINERAL ASSOCIATIONS 251 = 0.003, = 22.12. = 0.02, = 5.21, = 5.21, 2 4 4 2 = 0.02, = 9.3. At 4 2 = 2.04, О = 85.6 = 53.5, О 2 2 2 = 12.2, CH = 12.2, = 68.59, CH = 36.8, CH 2 2 2 composition of gas fluidscomposition N CO N In 400–580 m depth range: In 400–580 m depth N CO 750 m depth – Н m depth 750 Average gas composition = 0.004, %): Нe (vol CO Mostly nitro- methane, a lesser degree. to gen A of cadrocar- lens small bon gases has been m at 250–270 detected schist black the in depths basement conditions hydrogeological hydrogeological Hydrocarbonate. hydro- Hydrocarbonate. carbonate–chloride– sodium, sulfate–hydrocarbonate, and sulfate– sodium. Concentrations of dissolved oil hydrocar- mg/L bons– 1.7–3.93 Ground water in mud- Ground water complexes— volcanic hydrocarbonate–magne- Thermal sium–calcium. waters in crystalline base- are hydrocarbonate ment sulfate–cal- calcium, cium, chloride–sodium, brinesand calcium . , 2 2 C ° in Tunka in Tunka 2 C ° geothermal geothermal characteristics C. Temperature in C. Temperature ° source zone of mud volca- mud of zone source noes ≥400 fault zone. Temperature of fault zone. Temperature of the at depth ground water 200– top the basement 300 Heat flowHeat 40–50 mW/m Temperature in source zones Temperature ≤400 of mud volcanoes mW/m and 146 Heat flowHeat 60–80 mW/m inferred from from inferred geophysical data geophysical fluid-charged layers, Baikal–Sukhoi-Log crustalupper seismic with top zone waveguide and km depth at 1.3–5 7.5 km thickness. Subho- layer conductive rizontal km, of 4–10 at depths branches with vertical the near to come that ground (2000– surface as crop- m), as well 150 ping out High conductivity layer layer High conductivity range 0.3–5.6 km in depth rock assemblages assemblages rock of mud volcanoes 20–180 m thickness. Boul- m thickness. 20–180 and comglomer- pebble der including breccias, ate-like orienta- those with vertical of peb- axes of longer tions gravel containing ble psammite and carbonitized chippings mud interbeds; car- and psammite, heavily con- that deposits bonitized Oil- sands. gryphon tain has been bitumen family One notes charac- detected. gry- “rollers,” clay teristic phon siderite–dolomite– ankerite and pyrite–marcasite as clasts nodules, as well Pre- Early of Riphean to (gneiss, rocks cambrian amphibolite, pyrox- granite, enite, and serpentinite) and (olivine, minerals xenogenic hypersthene, and awaruite) Gryphon sands in “kuituns” (0–200 m), are in individ- encountered 1900 m to down ual layers sand- clay, sandy depth; argil- stone, aleurolite, and conglomerate- lite, breccias. gravelite-like range 200–450 m depth almost con- everywhere material carbonate tains and calcite, (siderite, in the pelite dolomite) fraction Geological peculiaritiesGeological system Fluid-dynamic volcanoes) crystalline basement (parentheses enclose (parentheses enclose the age or hypothetical the hypothetical age or 0.2–7 km – rocks of Ven- 0.2–7 km – rocks black- Riphean dian to km 7–12 schist formation; metamorphosed interval: of the ultrabasite–rocks Riphean complex, basite Precambrian Early to km) (≤10 granitoids (1700–3000 m) interval – m) interval (1700–3000 Kz; gran- rocks volcanic amphibolites, crys-ites, talloschist, marble, rocks of the ultra- Precambrian basite–basite complex depth to chambers of mud mud of chambers to depth (Contd.) (age) Structures Bodaibo basin (Kz) Tunka basin Tunka (Kz) Table 1. Table

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 252 TATARINOV et al. = + 2 2 = 4 = 39– 2 = 12–22; 2 = 25–38, CO 2 =0.18 vol %, heavy heavy %, vol =0.18 jets. Data from gas from jets. Data %, = 52.8 vol 4 2 2 = %, 46.98 vol = 24–75 to 97, H 97, to = 24–75 S = 19–27, CH S = 19–27, 2 2 2 composition of gas fluidscomposition There are vents of dry are vents There CO 47, H 100–300 m – N 100–300 1.3–4.3 CO HC – 0.04 % vol H CH log graben in the Balei m – %): 0–100 (vol section N 11–52, CO N conditions hydrogeological hydrogeological Hydrocarbonate–chloride calcium–magnesium, fissure–formation hydro- cal- carbonate–sulfate cium–magnesium– pore–formation sodium ground Waters water. springs mineral of cold Hydrocarbonate–sodium and chloride–sodium of an artesian waters basin. Gryphon effusions the onto water of thermal lakes crater of bottom . 2 . 2 C C ° ° geothermal geothermal characteristics Heat flow–Heat 60 mWt/m in source Temperatures zones 100–120 Temperatures in source Temperatures zones 150–600 Heat flowHeat – 70–80 mWt/m inferred from from inferred geophysical data geophysical fluid-charged layers, No data No data rock assemblages assemblages rock of mud volcanoes Geyserites, pelite–aleur- Geyserites, ite–psammite and breccia deposits of dome section, (upper structures m m); at 180–400 0–180 (siderite- are carbonized psammite–dominated), andpsephite breccia– deposits of conglomerate with facies the crater clasts of basement rocks gneiss,(granite, crystal- and quartzite, loschist, ore quartz). Xenogenic serpentine, minerals: and actinolite, talc, chrome-spinelide Upper section (0–100 m): (0–100 section Upper mostly Quaternary, crater-lake unconsolidated and grypho–salse carbon- and ate-bearing (dolomite deposits (mud, calcite) sand, and aleuropelite, sand–gravel– psammite), deposits, pebble breccia containing occasionally drop–liquid oil and oil bitumen Geological peculiaritiesGeological system Fluid-dynamic volcanoes) ) with numerous relics ) with numerous relics 3 crystalline basement (parentheses enclose (parentheses enclose the age or hypothetical the hypothetical age or and xenoliths of Precam- and xenoliths metamorphosed brian (crystalloschist, rocks gneiss, metabasites and meta-ultrabasites, and schists); carbonaceous km 1.1–6 section Lower of the Pre- rocks contains belt greenstone cambrian subjected been have that metamor- dynamic to phism (6–7 km) Upper section (400–1100 m) (400–1100 section Upper Jurassic gran- contains granitoids Paleozoic ites, (C Triassic to Jurassic volca- Jurassic to Triassic and sedimentarynic rocks gran- deposits; Paleozoic metavolcanites, itoids, metapelites, and shales; metamorphosed dynamic complex on Precambrian rock sedimentary volcanic km) (5–10 sequence depth to chambers of mud mud of chambers to depth (Contd.) (age) Structures Umda–Dai Umda–Dai basin(Mz) Torei basin (Kz and Mz) Table 1. Table

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Fig. 2. A fragment of a ridge-like uplift of gryphon sands (Baunt trough).

Late Cenozoic mud volcanism in zones of tectonic as well as of unusual linear psammite–pelite stock- discontinuities among older crystalline features. The work zones (Lobanov et al., 1991). result is the generation of gas volcanic crater morpho- structures (the Levaya Sarma and the Patom craters), It was found that a latent form of mud volcanism occurs widely today. These occurrences characterize not only repose periods between earthquakes in the seismic BRZ, but were also found to occur both in areas of low seismicity and in the southeastern side of the Unda basin (Medvedchikov Spring). We observed tongues of fire above several small funnels, which resulted from discharges and spontaneous ignition of hydrocarbon gases. Patches of mud–sand gryphon deposits affected by pyrometamorphism were found at these patches. A small dome-shaped feature was found in the Uletovskii area of the Chita–Ingoda basin. This feature consists of heated (T ≈ 50°C) deposits of mud- volcanic cone-shaped breccia with clasts of granite and other rocks that were partially subjected to pyrometamorphism. Small crater features that were observed to periodically spout water and mud charged Fig. 3. Secondary stalagmite-like sand–carbonate features in a massif of gryphon sand (Barguzin basin). SC stands with sand were observed in the Barguzin basin (Fig. 4) for sulfate carbonate crust. and at the Khamar–Daban Range.

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Mineral Associations of Rock Assemblages during (а)(а) (b) Different Phases in the Formation of Mud Volcanoes The gas explosive phase in the activity of mud volcanoes can manifest itself as explosive fiery eruptions, burning gas jets, jet–fumarole “injections” of hot steam–gas or gas fluid, as well as cold seeps. The burning of hydrocarbon gases causes partial melting and pyrometamorphism of cement and clasts of previously precipitated sediments of vent and crater facies from mud volcanoes, resulting in the generation Fig. 4. Small (within 1 m across) mud-volcanic craters that of paralavas, glasses, cinders, and pyrometamorphic are erupting clay–sand pulp. Upper reaches of Barguzin R.: minerals. Fluid pyrometamorphism gives rise to melt Barguzin basin, Margasan Mt. in Hamar-Daban Range. microportions, which then produce microspherules of native metals, their alloys, carbides, silicides, and oxides by crystallization (Table 2). Oxides also form, apart from autonomous spherical particles, as well as inclusions (in a glass matrix) of cinders, and baked fragments of the rocks that compose mud-volcanic edifices. The mineral indicators of fluid pyrometamorphism are primarily aluminiferous minerals (Fig. 5): disthene, sillimanite, staurolite, mullite, topaz, corundum, and others, as well as modifications of SiO2 that consist of cristobalite and opal-like quartz, which is usually blue. There may be different mechanisms for the generation of spheroidal, drop-like forms Т of particles of microcinder, glass, and oxides, including microliquation, cavitation, and foam flotation (Adushkin et al., 2004; Ovchinnikov, 1988). D Fluid pyrometamorphism is especially abundant in mud-volcanic complexes in the coal-bearing Lake Gusinoe basin (Tugovik, 1979). There is a peculiar association of fumarole minerals (see Table 2) that are localized in voids and empty fis- Fig. 5. Fluid pyrometamorphic disthene (D) and topaz (T) sures that were produced by steam–gas fluids in lith- in hydromica–smectite–kaolinite cement of psammite ified gas–water deposits of mud volcanoes. rock assemblages in the Balei graben of the Unda–Dai mud-volcanic basin (polished section in transmitted light, The gas–water–lithoclast phase The multicompo- magnification 201). nent composition of the fluid that produces the mud- volcanic rock assemblages during this phase deter- mines a wider range of PT conditions for mineral gen- during this phase of activity of mud volcanoes in eration; hence, a greater diversity of mineral classes southeastern Siberia, contain various modifications of and groups compared with the composition of the crystalline carbon (graphite, nanocrystalline graphite, fluid that existed during the explosive gas phase (see and sooty carbon with a high concentration of ali- Table 2). The distinctive genetic feature of high-tem- phatic bonds) that are important components in these perature spherical microparticles of alumosilicate associations, as well as various bitumen-like com- glass and oxides, primarily native metals and interme- pounds. tallics, consists in the fact that they crystallized from a solution, most probably from one that was due to cav- Carbon pyrolysis produces a kind of empty micro- itation (Adushkin et al., 2004), that is, due to interac- spherules of crystalline carbon with gold nanoparticles tion between “collapsing” gas bubbles with grains of (Fig. 6), micro- and nano-particles of other oxides minerals and the minerals from mud-volcanic pulp. (Fig. 7). The overwhelming majority of the minerals These bubbles in turn obviously occurred during the from rock assemblages include a low-temperature heterogenization of hydrothermal fluids, resulting in association of typical hydrothermal minerals (carbon- the isolation of aqueous, gaseous, and possibly oil ates, sulfates, aqueous silicates, oxides, and sulfides). components. One can also hypothesize that the wide The gas–water phase is seen in the form of above- generation of water–oil emulsions occurred, as well as ground (mineral springs) and underwater (crater their pyrolytic decomposition. The mineral associa- lakes) gryphon discharge of thermal or cold waters, tions that we studied, viz., associations that occurred resulting in deposition of salts, travertines and geyse-

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 THE GENERATION AND MINERAL ASSOCIATIONS 255 utheastern Siberia utheastern silomelane, Ni-cuprite, Ni-cuprite, silomelane, Cr–Ni and Ni–Cu alloys, moissanite, alloys, and Ni–Cu Cr–Ni cohenite, Minerals in the generation of Cenozoic and mud Mesozoic volcanoes in so of Cenozoic in the generation Olivine, rhombic and monoclinic pyroxenes, zircon, sphene, garnet of the pyrope–almandine zircon, and monoclinic rhombic pyroxenes, Olivine, chrome-spinelide, fuchsite, plagioclase, quartz, amphiboles, tourmaline, serpentine, family, magnetite ilmenite, Cu, and Fe–Mn– Si, graphite Au, Pb, Fe, Native plagioclase, quartz, opal, chal- cinnabar, galenite, marcasite, pyrite, hematite, mangan-ilmenite, cerus- ankerite, dolomite, siderite, boehmite, kaolinite, calcite, smectite, hydromica, chlorite, cedony, aqueous jarosite, sulfates, phosphates, smithsonite, apatite, site, barite, and anglesite, Fe gypsum armalcolite, chrome-spinelide, spinel, chrome-magnetite, ilmenite, maghemite, hematite, rutile, hematite, maghemite, ilmenite, chrome-magnetite, spinel, chrome-spinelide, armalcolite, disthene, melillite, mullite, massicot, andalusite, sillimanite, galenite, staurolite, iocite, chloritoid, corun- diopside, topaz, plagioclase, zircon, garnet,hornblende, epidote, tourmaline, mayenite, dum, lime, cristobalite, quartz and opal-like and analcime sooty opal, carbon, chalcedony, rutile, hematite, sulfur, Fe–La–Ce–Si, and Ce–La–Nd–Pr Ni–Cu, Zn, Cu, Au, Ag, electrum, Cr–Fe, Pb, Ni, Native sphalerite, pyrite, scheelite, powellite, maghemite, hematite, magnetite, cohenite, intermetallics, quartz, opal, altaite, massicot, uraninite, montroydite, b-meta-cinnabarite, cinnabar, argentite, thermona- cutinite, lanthanite, dolomite, aragonite, calcite, hydromica, smectite, chlorite, zeolite, bismoclite, barite, glauberite, jarosite, gypsum, carnallite, thenardite, schaire- halite, sylvite, trite, and fluorite phosphosiderite,rite, gorceixite, apatite, lanarkite, associations Genetic groups of mineral groups of mineral Genetic line basement in mud-volcanic in mud-volcanic line basement basins). and of the Fluid pyrometamorphic pyrogenous melt. Fumarole gaseousFumarole bischofite, Na and ammonium Ca chlorides, chloride, aragonite, Gypsum, anhydrite, laurencite, with microorganisms involved genic Stages Mineral associations in rock assemblages during different phases assemblages during in rock different associations Mineral gas–explosive of the (minerals crystal- Xenogenic Gas–aqueous Hydrothermal–sedimentary–chemo- Gas–water–lithoclastic p hydrogeothite, goethite, Au, Ag, Pb, Cu–Zn intermetallics, Fe, Native Hydrothermal–sedimentary–clastogen Table 2.

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(а)

6 2 1 1

7 µ 2 3 4 20 m 5

10 8 9 500 µm

(b) C Au Ca

O Fe 40 µm

0.9 1.8 2.7 3.6 4.5 5.4 6.3 7.2 8.1 9.0 Fig. 7. Mineral aggregate from bitumen-bearing clay–sand deposits in Lake Kotokel’ (Kotokel’ basin). (1–3, 9) native Fig. 6. Fragments of a crushed hollow carbonaceous Pb; (4) arsenides of Cu, Pb, and Sb; (5) native Pb with an microspherule from sand–mud deposits of the Zmeinyi admixture of Sb; (6–8) native Si (?); (10) galenite with an thermal spring (shore of the Chivyrkui Bay, Lake Baikal). admixture of Sb. a structure: (1) fragments of the crushed spherule; (2) microtextures of the spherule fragment (reticulate on inner wall, columnar in cross section); b composition (carbon the formation of pelitomorphous bacterial contains gold nanoparticles). organic–clay–carbonate aggregates that serve as centers of crystallization for various minerals in hydrocar- rites, as well as carbonate, clay–marl, ferrous, ferro- bonate solutions; manganese, and sulfide nodules. The generation of the bacteria (filaments, bacilli, cocci) in such minerals during this phase mostly occurs through the aggregates are almost completely lithified (fossilized); chemogenic and biogenic (bacterial) genetic mechanisms, as well as by cavitation with accompanying along with carbonaceous substance of gas-and-oil combustion and pyrolysis. origin (solid residual bitumen, bulbous dust-like car- The minerals of chemogenic origin (mirabilite, bon, nanocrystallic graphite), numerous minerals are glauberite, carnallite, and thermonatrite) are the most crystallized in travertines, mostly ore minerals. The abundant in mud-volcanic deposits of hydrocarbonate carbon ore formations consist of rounded and circular microaggregates up to 60 μm across with the rings up and sulfate–sodium crater lakes in the Barguzin μ depression and in the Onon–Torei–Borzu group of to 0.3–0.4 m thick (Fig. 8) that occur on fine-brec- basins. The species diversity of minerals in the associ- ciated carbonate substratum or in the form of micro- ations of the biogenic and chemogenic genesis is breccia cement with travertine fragments. greater. Some of these are rock-forming minerals for travertines (carbonates) and for geyserites (siliceous minerals). The Fluid Dynamic System of Mud Volcanoes in Southeastern Siberia The effects of microorganisms on mineral generation and petrogenesis (in crater lakes, discharges of The mud volcanism in southeastern Siberia is due gryphon waters, and vents of gas jets on mud volca- to fluid dynamic processes of plume origin, which noes) are considerable and occur as follows (Tatarinov accompanied the Mesozoic and Cenozoic rifting epi- et al., 2011b): sodes. Kissin (2004) proposed a model of a fluid con- differentiation and alteration of original chemical solidated crust of type II for such regions, which are compositions of gas-charged hydrothermal fluids by classified as ones of Mesozoic–Cenozoic folding and cyanobacteria, iron bacteria, and sulfur bacteria; tectonomagmatic activation.

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trievskii, 2008). These anomalous low-velocity and high-conductivity zones are called crustal waveguides 1 (Dmitrievskii et al., 2007). The Baikal–Sukhoi-Log upper crustal seismic waveguide zone was identified (Bulin, 2005) for the Baikal and Barguzin basins, as 2 well as for the Bodaibo basin, which is part of the 3 northeastern extension of the Baikal basin; the top of this zone is within the depth range 0–5 km and its 4 thickness varies between 2.5 and 10 km. The top of the 6 5 second waveguide layer 5 km thick is much deeper (12–18 km) (Kissin, 2001). Subhorizontal conductive layers saturate the entire crustal section beneath the 8 Baikal basins (Pospeev, 1988). The depth range 0.3– 9 10 36 km contains at least five layers of this kind, as inferred by several investigators, with the layer thick- 7 nesses varying between 4 and 17 km. The crust of the 11 Bodaibo basin has anomalous conductivity, containing a “relict” (conductive according to V.I. Pospeev) layer in the upper part (2.5–15 km), to be followed by an intermediate one, and a lower (12–30 km), so- 40 µm called “lithospheric,” conductive layer. Deep electromagnetic studies (MTS) on four lines Fig. 8. Rounded carbon-ore microaggregate from traver- in the Bodaibo basin conducted by the VostSibNIIG- tines of Garga thermal spring. (1) calcite grain in a brec- GiMS (V.I Pospeev, Yu.A. Karavaeva, and others) ciated travertine; (2) HC + calcite; (3) and (5) hypotheti- revealed the existence of 14 nearly vertical zones of cal nanoparticles of Ti-Cr alloy in HC matrix; (4) same, Ti–Cr–Fe; (6) hypothetical nanoparticles of pyrite and high conductivity 1.5–10 km long. These zones have rutile in hydromica; (7) HC with an admixture of calcite; their tops near the ground surface (2000–150 m), (8) hypothetical nanoparticles of rutile and native Cr in a occasionally extending as far as the ground surface. It partially oxidized HC; (9) hypothetical nanoparticles of may be hypothesized that these are “degassing pipes” pyrite and rutile in hydromica; (10) barite; (11) black bitu- that mark the vents of mud volcanoes. menoids with graphite. Geothermal characteristics. Most of the southern Siberian region of mud volcanism is character- The main parameters of this model are as follows: ized by anomalous values of heat-flow density (40– heat flow, 80 ± 20 mW m2; temperature at the Moho, ≥ 100 mW/m2) (Tatarinov and Abramov, 2001), sim- 1000 ± 200°C; the quantity 3He/4He × 108 is 5.0— ilarly to classical areas of mud volcanism such as the 994; and the presence of electric conductive layers at Crimea–Caucasus region or the Caspian Sea. The several depths in the crust. highest heat flow occurs at tectonic discontinuities (see Table 1). There is a unique geothermal anomaly However, these data are average ones in the first 2 place and do not characterize their ranges of variation (1050–37000 mW/m ) at the location of the Frolikha for the region of study; secondly, they do not include underwater thermal spring in the northern Baikal very important parameters of the fluid system of mud basin (Golubev, 2007), which is by all accounts a gry- volcanoes, such as the phase composition and the phon in an underwater mud-volcanic crater edifice concentrations of fluid components. For this reason (1.6 by 1.0 km). we provide a fuller description of the fluid dynamic An analysis of geothermal sections for the mud- system below based on an analysis of published infor- volcanic basins in the Baikal region based on the mation for the best studied mud-volcanic basins (see materials from (Moiseenko and Smyslov, 1986) Table 1). showed that the highest heating occurs in the crust of Fluid-charged layers in the upper crust as inferred the Baikal and Torei basins. All mud-volcanic basins from geophysical observations It is well known that are also different in the distribution of temperature at fluid-charged layers or volumes in the crust and upper depth and in the accordingly wide range of tempera- ° mantle are generally treated as zones and volumes of tures (100–600 C) in the source zones of mud volca- rock destruction and density deficit that are filled with noes (see Table 1). fluids, which were produced by developing tectonic Hydrogeological conditions. The parameters of stratification in the lithosphere. They are commonly aqueous fluids that take part in the formation and identified from several geophysical characteristics, activity of mud volcanoes in southeastern Siberia are with those carrying more weight being considered to largely determined by the region of underground min- be layers of anomalously low velocity (Dmitrievskii et eral waters that these volcanoes belong to or their arte- al., 2000) and of high electrical conductivity (Dmi- sian basin. One part of the Cenozoic mud-volcanic

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 258 TATARINOV et al. features resides in the Baikal area of hot waters that are While the latter are usually dominated by CH4 and rich in N2 and CH4 (the Baikal, Barguzin, and occasionally by CO2, the gases of the southern Sibe- Bodaibo basins), while the rest are in the Daurian area rian zone contain, apart from CH4 and CO2, N2 and of cold acidulous and radon waters (the Unda–Dai H2 as the leading gases. and Torei basins). The Tunka basin occupies a special The materials presented above in our interpretation position. Its north part belongs to the eastern Sayan are consistent with the following main tenets of the area of hot and cold acidulous waters, while the south fluid dynamic model of intracontinental mud volca- flank is in the Baikal region. It can be gathered from nism (Karakin and Karakin, 2000): published sources that the prevailing water types in the artesian basins of mud-volcanic depressions (see Table 1) The mud volcanoes, oil and gas fields, and anoma- are variously mineralized (from fresh to salt brine) lously high reservoir pressure (AHRP) have one com- waters dominated by hydrocarbonates and sulfates. mon origin and similar mechanisms of generation; Sulfate chloride and chloride sodium waters are less Mud volcanoes are formed, like hydrocarbon fields abundant. The waters of many thermal mineral springs in an AHRP zone, through self-excited vibrations in have compositions that are similar to those of under- crustal waveguides at depths of 10–15 km. ground fissure and formation waters in artesian basins. The fluid system (water, gas, and oil) is formed in Those most frequent among these are hydrocarbon- crustal waveguides at depths of 10–20 km (Dmi- ate–sulfate–sodium, hydrocarbonate–calcium, trievskii et al., 2000). The waveguides form both in sodium–sulfate, chloride–hydrocarbonate–sodium, sedimentary rocks of oil–gas basins and in crystalline and sodium–sulfate types. rocks of their basements. The sections at depths of 10– The interstitial water in the mud-volcanic sedi- 20 km in the southern Siberian area of mud volcanism ments of the Baikal basin is rich in chlorides, sulfates, consist of older rocks of the granite–metamorphic and and sodium. The deposits in mud-volcanic crater lakes ultrabasite–basite assemblages. Consequently, it can and thermal springs contain bitumen of the oil family, be asserted that the main zone of fluid generation is in occasionally even drops of oil in sulfates. Thermal the crystalline basement of the Mesozoic–Cenozoic waters of many springs and underwater reservoirs were basins. In addition to this, the Baikal region also con- found to contain dissolved oil components (neutral tains another shallow Baikal–Sukhoi-Log zone of bitumen, naphthenic acids, and phenols) whose total fluid generation that occasionally crops out (Bulin, concentration can reach 4 mg/L (Shpeizer et al., 1999). 2005) that intersects sedimentary Vendian–Riphean The rock assemblages in the mud-volcanic basins carbonaceous rock sequences in the Bodaibo basin of the Baikal region have parameters that are identical and probably the carboniferous Paleogene deposits in with those for the waters of oil–gas features in mobile the Barguzin basin. belts, which exhibit a wide occurrence of mud volca- We share the standpoint of A.N. Dmitrievskii et al. nism (Kerimov and Rachinskii, 2011). (2007) who expressed the opinion that primary oil is The composition of gas fluids. The gaseous com- formed at depths of 10–20 km in waveguide zones to ponents of mud-volcanic fluids are mostly CH , N , be transported from there into higher crustal horizons, 4 2 and even as far as the surface. Similar concepts were CO , and H with different combinations and quanti- 2 2 enunciated by Kissin (2011) who made the statement tative relationships among these (see Table 1). that “oil solutions” arise in waveguide fluid systems at Accordingly, the aqueous phase and dry gases of mud depths of 10–20 km at T = 300–400°C. Kireev (2012) volcanoes divide into several types as defined by the points out that the temperature regime and geobaric associated prevailing gas: methane, nitrogen, acidu- conditions that are the most favorable for oil genera- lous, nitrogen–acidulous, hydrogen–nitrogen, and tion and under which oil is synthesized occur in the acidulous–hydrogen types. crust at depths of 3–15 km. In application to the BRZ According to the gas composition all of the thermal oil-bearing features the inference about the existence springs were classified (Golubev, 2007) into nitrogen of liquid oil at depths of 10–20 km and about the springs (at faults in granite), methane springs (in basin transport of its components with gas–water fluids sediments), and acidulous springs (in areas of basite during the activity of mud volcanoes is advanced as volcanism). follows. Heavy hydrocarbons, H2S, He, Ra, Ar, and other The Baikal oil possesses a distinct hyperbasite geo- inert gases were detected in the gaseous components of chemical specialization (“signature”). ICP MS tech- mud-volcanic fluids in the form of admixtures that are niques were used to find the following concentrations: commonly below 2–3 vol %. In addition, some fluid Au = 660 mg/t, Pt = 137 g/t, Cr = 950 mg/t, Co = types contain significant concentrations of O2 (0.73– 1400 mg/t, Ni = 61 g/t (Bryukhanova, 2003). The Bai- 9.3 vol %). The southern Siberian gases differ from kal oil is different from the oils in the other oil–gas those of mud volcanoes that are situated in well- basins in having rather high concentrations of Pt. Even known mud-volcanic regions such as Azerbaijan, the light fraction of film oil as collected from the Bai- Turkmenia, the Kerch–Taman zone, and Sakhalin kal water surface contains 6 g/t Pt. The sand–mud Island in having a greater compositional diversity. deposits in crater lakes of mud volcanoes that contain

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 THE GENERATION AND MINERAL ASSOCIATIONS 259 an admixture of oil bitumen inherit the hyperbasite “sig- ground surface, the column is gradually saturated with nature” of the Baikal oil (our data): Au up to 720 mg/t, surface and atmospheric waters. This affects the com- Pt up to 300 mg/t, Pd up to 800 mg/t, and Ru up to position and quantitative relationships between the 10 mg/t. The concentrations of noble metals in traver- components of the original fluid system, which initi- tines of the Garga spring where oil bitumen has also ates mud-volcanic activity. been detected reach industrial values (Au = 2.3 g/t, Pt = 1.3 g/t, and Pd = 6.1 g/t). These data provide evidence of spatial and genetic relationships between oil-gener- Mineral Associations as Indicators of Fluid Dynamic ating zones and ultrabasites in the BRZ Precambrian Regime in the Formation of Mud Volcanoes basement. Since the depth range of these rocks Fluid dynamics not only controls the morpho- beneath the Baikal basin is estimated from geophysical structural features of mud volcanoes in the southern data as 7–32 km (Nefed’ev, 2013), it follows that the Siberian region, but also strongly affects the species main waveguide zone of oil generation in the area at variety of the minerals that make up the associations of depths of 10–20 km is situated in the middle of the their rock assemblages. There are three fluid dynamic section dominated by the ultrabasite–basite associa- regimes in the formation of mud-volcanic features, tion rocks. which are different in the dominant mechanisms of The highest seismicity in the Baikal region occurs mineral generation, viz., root (chamber) structures of at depths of 10–20 km (Radziminovich, 2010) where a fluid generation, channels for the transport of fluid– subhorizontal zone of fracturing (waveguide) and of rock substratum, and channels for the transport of active fluid generation was formed in rocks of the older hydrothermal fluids. ultrabasite–basite assemblage. We ascribe the genera- The fluid dynamic regime of root structures. This tion of the bulk of liquid oil to this zone. It is hypoth- occurs in the sources where mud volcanoes are initi- esized that thermal solutions are present in the depth ated with an accompanying mechanism of mineral interval 13–18 km, while oil–gas-bearing features generation. The association of these minerals mostly produce the bulk of the CO2 and CH4 (Polyak et al., includes part of the xenogenic group that was formed 1992). V.A. Golubev (2007) came to the conclusion by dynamic metamorphism of ultrabasite–basite that atmospheric water also penetrates to depths of assemblages that are represented by water-containing 10–15 km. In view of these data, we believe that the silicates (amphiboles, serpentine, and fuchsite) that oil-generating zone at depths of 10–20 km in the crys- make grain aggregates and by anhydrous silicates (gar- talline basement of the Baikal basin is most probably a net, zircon, plagioclase, and quartz) that make por- hydrothermal fluid gas–oil–bitumen system (T = phyroblasts in a cataclasite–mylonite matrix. The sub- 350–600°C) with different relationships between the sequent long-term transport of porphyroblastic min- temperature-dependent components, as is shown by eral grains make them rounded with a lusterless experiments (Balitskii et al., 2009; Kissin, 2011). From polished surface that results from the abrasive action these experiments it follows that the transition of oil of mud-volcanic pulps. components into the aqueous solution starts at T = The fluid dynamic regime in the channels of fluid– 100–150°C, while at T = 350–400°C the bulk of the rock substratum transport This characterizes the oil is dissolved in hydrothermal fluids and part of it is movement of fluid–rock masses from zones of frac- in a liquid dropwise state; at 400–500°C the oil sepa- turing and fluid generation along subvertical and rates into a light and a heavy fraction with accompany- inclined channels (vents) of mud volcanoes, which ing liberation of hydrocarbon gases (mostly CH4), and mostly have tubular, cylindrical, and fissure shapes. especially of bitumen. At 600°C the liquid oil is trans- The fluid dynamic regime is rather variable there, formed to pyrobitumen with accompanying liberation because the activity of mud volcanoes is impulsive and of hydrocarbon gases. intermittent. Periods of active movement that are occasionally accompanied by high velocities of the As well, it cannot be excluded that the f luid system, ascent of rising fluids and clastogene material, as well including gases and oil, in the southern Siberian mud- as by oxidation of reduced gases, give way to passive volcanic region was also formed at higher crustal hori- phases during which mud-volcanic eruptions decay zons, that is, in the oil-generating zone of the Baikal– and cease. Accordingly, the parameters of a fluid Sukhoi-Log waveguide. dynamic system such as pressure, temperature, pH of Sources (volumes) with increased (above the litho- solutions, and quantitative parameters of fluid com- static pressure) fluid pressure are formed in crustal ponents, vary in wide ranges. A rapidly changing ther- nearly horizontal zones of primary fluid generation, modynamic and physico-chemical situation in the life that is, a necessary condition arises for the transport of a fluid system results in the generation of numerous (eruption) of fluid-charged dispersed rock masses into minerals of the gas–explosive and gas–water–litho- the upper crust and farther onto the ground surface. As clastic phases, which combines species that, on the time goes on during the activity of mud volcanoes and one hand, are characteristic for typical igneous and as the column of fluid components moves from contact–metamorphic rocks and, on the other, for destructive zones of fluid generation toward the low-temperature hydrothermal sedimentary hyper-

JOURNAL OF VOLCANOLOGY AND SEISMOLOGY Vol. 10 No. 4 2016 260 TATARINOV et al. gene formations. The fluid dynamic regime that is canoes may be insufficient to reach the Precambrian under consideration here has produced several mech- rocks. anisms of mineral generation, viz., the pyrometamorphic, pyrolytic, microliquational, cavitational, hydrothermal, and hydrothermal sedimentary mechanisms; ACKNOWLEDGMENTS the latter involved microorganisms. We are grateful to N.M. Baryshnikova, V.Yu. Barysh- The fluid dynamic regime of channels of hydro- nikova, and N.G. Smetanina for technical help during thermal fluid transport.This characterizes the water– the preparation of the manuscript. drainage system of mud-volcanic features. Its aqueous This work was supported by the Russian Founda- component is mostly represented by thermal waters tion for Basic Research (project Baikal 08-05-98009), that contain insignificant amounts of fine mineral and by the Geosciences Section of the Presidium of the rock particles and an admixture of hydrocarbons. The Russian Academy of Sciences ONZ-5.1, and by part- process affects the PT parameters of the fluid system, nership integration projects of the Siberian Branch of but this effect is not as pronounced as that in the chan- the Russian Academy of Sciences nos. 29 and 89. nels of fluid–rock substratum transport. The fluctua- tions in the composition of fluids and in their physico- chemical and thermodynamic parameters are due to REFERENCES heterogenization (boiling) of ascending hydrothermal Adushkin, V.V., Andreev, S.N., and Popel’, S.I., A cavita- solutions and by surface and atmospheric waters that tion mechanism for the formation of nano- and micro- are added to them (Golubev, 2007), in addition to the particles in the Earth’s interior, Dokl. Akad. Nauk, work done by bacterial communities. These factors 2004, vol. 399, no. 1, pp. 107–109. control the species composition of minerals that are Antipin, V.S., Fedorov, A.M., Dril’, S.I., and Voronin, V.I., being generated (see Table 2). The channels of hydro- New evidence for the origin of the Patom crater, eastern thermal fluid transport beneath mud volcanoes are Siberia, Dokl. Akad. 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