G. A. Karpov

Diamonds and accessory minerals in products of the 2012–2013 Tolbachik Fissure Eruption

This paper discusses results from mineralogic, petrographic, and petrochemical studies of diamond-bearing volcanic rocks that were erupted by the 2012–2013 Tolbachik Fissure Eruption. This is the first time that the reader can find an integrated description of crystal-morphologic, spectroscopic, thermal, and isotopic-geochemical properties of diamonds extracted from fresh basaltoids. We examined the micromineralizations that are accessory to the diamonds and provide a rationale for why the type (previously unknown) of non-kimberlite diamond findings should exist in nature.

Oxysulfates of copper, sodium, and potassium in the lava flows of the 2012–2013 Tolbachik Fissure Eruption

Samples from the surface of lava flows discharged by the 2012–2013 Tolbachik Fissure Eruption were found to contain oxysulfates of copper, sodium, and potassium: K2Cu3O(SO4)2 (fedotovite), NaKCu2O(SO4)2, and Na3K5Cu8O4(SO4)8. The last two phases have no naturally occurring or synthetic analogues that we are aware of. They form flattened crystals of prismatic to long-prismatic habits. The crystals of Na3K5Cu8O4(SO4)8 have a chemical composition corresponding to the empirical formula Na2.22K5.47Cu8.02S8.05O36. An X-ray analysis of this compound showed that it has a monoclinic symmetry, P2/c, a = 13.909(4), b = 4.977(1), c = 23.525(6) Å, β = 90.021(5)°, V = 1628.3(7) Å3. The crystal structure was determined by direct techniques and refined to yield R1 for 3955 reflexes//web// with F2 > 4σF. The compound NaKCu2O(SO4)2 also belongs to the monoclinic system, P2/c, a = 14.111(4), b = 4.946(1), c = 23.673(6) Å, β = 92.052(6)°, V = 1651.1(8) Å3. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R1 = 0.135 for 4088 reflexes with F2 > 4σF. The crystal structure of Na3K5Cu8O4(SO4)8 is based on chains of [O2Cu4]4+ consisting of rib-coupled oxy-centered tetrahedrons of (OCu4)6+. The chains are surrounded by sulfate radicals, resulting in columns of {[O2Cu4](SO4)4}4− aligned along the b axis. The interchain space contains completely ordered positions of Na+ and K+ cations. The principle underlying the connection of NaKCu2O(SO4)2 columns in the crystal structure of {[O2Cu4](SO4)4}4− is different, in view of the relation Na:K = 1 as contrasted with 3:5 for the compound Na3K5Cu8O4(SO4)8. The presence of oxy-centered tetrahedrons in the structure of these new compounds furnishes an indirect hint at the importance of polynuclear copper-oxygen radicals with centering oxygen atoms as forms of transport of copper by volcanic gases.

The time-dependent variation of hydrogeochemical characteristics, thermal regime, and biocenoses in the fresh and thermal waters of the Lake Karymskii basin following the catastrophic underwater eruption of 1996 in the Akademii Nauk Caldera, Kamchatka

The results of biohydrogeochemical monitoring are used to study time-dependent variations in the hydrogeochemical characteristics of the Lake Karymskii water mass, the state and characteristics of underwater discharge zones in the Tokarev crater (formed in 1996), hydrogeochemical characteristics of thermal springs around the lake, and the biota succession in the lake for the period 1996–2006 (2007). We detected a stratification in the chemical composition of water over depth and the presence of persistent zones of increased concentrations of dissolved oxygen. We found an alkalization of lake water and a decrease in its total salinity. The new thermal springs and underwater discharges of thermal water and gases were found to be continuing. The first data were obtained on the concentration of microelements in the thermal springs of the Karymskii basin. The biodiversity of algae in Lake Karymskii was largely increased by the species diversity of benthic Bacillariophyta. The plankton phytocomponent of the precatastrophic period was found to have been regenerated in the lake as of April 2007.

Organic compounds in thermal water: The Mutnovskii area and the Uzon caldera

New data are reported relating to the presence and relative concentrations of organic compounds of medium volatility in samples from the water of hot springs and in the condensate of a steam–water mixture from wells drilled in the Mutnovskii geothermal area and from a well and springs in the Uzon caldera. The Mutnovskii area was found to contain 95 compounds belonging to 16 homologous series, with 71 compounds (12 series) in the Uzon caldera. Among these we found homologous series of biologically important compounds: carbonic acids, alcohols, ethers, aldehydes, ketones, and others. Evidence was obtained for a contribution of the abiogenic component in organic matter from sterile condensates of an overheated steam–water mixture from wells (alkanes, aromatic hydrocarbons, ketones, alcohols, and others) and in thermal water from natural discharges (in particular, alkanes and chlorine-containing hydrocarbons). The results of this study can be used for the preparation and conduction of laboratory experiments in prebiological chemistry under conditions that simulate a hydrothermal environment.

Microcrystalline diamonds in the oceanic lithosphere and their nature

The carbon isotope composition of microdiamonds found in products of the Tolbachik Volcano eruption, Kamchatka (porous lavas and ash), was studied. The isotope composition of microdiamonds (with an average value of δ13C =–25.05‰) is close to that of microsized carbon particles in lavas (from–28.9 to–25.3‰). The general peculiarities of the diamond-forming environment include (1) no evidence for high pressure in the medium; (2) a reduced environment; and (3) mineralogical evidence for the presence of a fluid. The geochemical data characterizing the type of diamonds studied allow us to suggest that they were formed in accordance with the mechanism of diamond synthesis during cavitation in a rapidly migrating fluid, which was suggested by E.M. Galimov.

Microparticles of native metals, sulfides, and oxides in andesitic ashes of Karymskii Volcano

New data on accessory mineral phases found in ashes of the erupting Karymskii Volcano as micro-dispersed particles of native metals (Al, Fe, and Zn), intermetallic compounds, sulfides and oxides of iron, and carbonaceous substances are presented. Dominating submicron particles of native Al and Fe are largely confined to coarse-grained ash fractions; this is supported by extensive observations. The co-occurrence of iron oxide and sulfide particles of the same size possibly indicates extremely heterogeneous conditions of gas transport reactions during the eruption. The presence of native metals and carbonaceous compounds may attest to periods of a highly reducing environment in the fluid system supplying Karymskii Volcano.

Ivsite, Na3H(SO4)2, a new mineral from volcanic exhalations of fumaroles of the Fissure Tolbachik Eruption of the 50th Anniversary of the Institute of Volcanology and Seismology, Far East Branch, Russian Academy of Sciences

Fine-granular (<0.1 mm) flattened colorless transparent crystals of ivsite form white aggregates. The empirical formula (Na2.793Cu0.056)2.849HS2.016O8 is close to the ideal Na3H(SO4)2. The structure was refined up to R = 0.040. Ivsite has a monoclinic symmetry, P21/c, a = 8.655(1) Å, b = 9.652(1) Å, c = 9.147(1) Å, β = 108.76(1)°, V = 723.61(1) Å3, Z = 4. Na atoms occur at six- and seven-fold sites (NaO6 and NaO7); S atoms, in isolated SO4 tetrahedrons; these polyhedrons form a three-dimensional framework. The diagnostic lines of powder diffraction patterns (d[Å]–I–hkl) are 4.010–53–12-1, 3.949–87–012, 3.768–100–210, 3.610–21–20-2, 3.022–22–031, 2.891–42–22-2, 2.764–49–31-1, and 2.732–70–13-1.

The evolution of the behavior and physico-chemical characteristics of solutions in the new geyser in Uzon Caldera, Kamchatka

This paper is a study of variations in the behavior and physico-chemical characteristics of solutions in the geyser that formed in 2008 in the place of a pulsating spring in Uzon Caldera. We describe the features of this geyser’s activity in 2009 and 2010. Overheating of water is for the first time described, rising to reach100.13°C at the mouth of a geyser during an eruption. We discuss the compositions of the solutions and free gases in the geyser, the possible source depths of the solutions, and the causes of geyser generation.

Post-eruptive process and products of volcanic rock alteration (transformation and synthesis of secondary products)

The conditions of transformation of the primary material of extrusive rocks and the synthesis of secondary products during post-eruptive processes have been considered using the example of three large areas of presentday volcanism and hydrothermal activity in Kamchatka, viz., the Great Tolbachik Fissure Eruption of 1975–1976 (GTFE), the Karymskii Volcanic Center (eruption of 1996 in Lake Karymskii), and the Uzon volcanic-hydrothermal system. Post-eruptive transformation of rocks causes volcanic-hydrothermal lithogenesis and low-middle-temperature mineralization in areas of present-day contrast (basalt-andesite) volcanism in zones of crustal extension. Based on the permanent presence of a wide range of acid rocks, such as dacites, rhyolites, and pumices in the areas of Holocene basalt volcanism of Kamchatka, we concluded that in conditions of pre-rift crustal extension, acid volcanism is preceded by deep-seated differentiation (similar to liquation) of primary mantle melts with separation of fluids enriched in ore-forming elements, first of all Cu, Zn, Pb, As, Sb, and Hg. During volcanogenic-hydrothermal lithogenesis in the discharge areas of those fluid systems, the destruction and replacement of primary minerals of igneous rocks and formation of complex-composition metasomatites take place. Clay minerals are major components of metasomatites in subaqueous conditions. The role of microbiota in processes of volcanogenic-hydrothermal lithogenesis and occurrences of local mineralization was studied.

The Hydrochemical Evolution of Water in Lake Karymskii during 1996‒2015 after an Underwater Eruption in Kamchatka

This study considers variations in the physical and chemical characteristics of water in Lake Karymskii for the period from January 1996, when a phreatomagmatic eruption occurred in the lake, until 2015. Our monitoring revealed two characteristic sets of components whose behavior characterizes the hydrochemical evolution of lake water: a comparatively rapid exponential decay of the concentrations of SO4, Ca, and Mg and a slow decrease in the concentrations of Cl, Na, and K. We arrived at the conclusion that two components of the fluid flow (a fumarolic and a hydrothermal component proper) simultaneously occurred during the eruption and thus had an effect on the lake water. We adduce evidence to show that the water balance and the chemical composition of Lake Karymskii stabilized toward 2015.