Approaches to stratigraphy of the paleogene volcanogenic sequences in northwestern Kamchatka

“Volcanogenic Complex” as a stratigraphic term is substantiated. Also discussed are peculiarities of the volcanic process, the nature and evolution time of the volcanic structures, the complete and incomplete volcanic cycles. Data of comprehensive geological, stratigraphic and paleovolcanologic study are used to subdivide the Kinkil’skii Formation of Paleogene volcanogenic rocks in the northwestern Kamchatka, which has undivided previously, into the Shamanka, Rebro, Bozhedomova, and Geeklen volcanogenic complexes of concurrent or different ages. As a result, two epochs of volcanism (the late Ypresian-Lutetian and late Bartonian-Priabonian) are distinguished. A hiatus separating the epochs was a time of intense scouring and leveling the landforms and of the weathering crust formation. In conclusions, some problems of the paleogeography in Kamchatka and adjacent territories are discussed.     

The Mobility of Rare—Earth Elements During Hydrothermal Activity：A Review

The mobility of the rare-earth elements(REE)during hydrothermal activities is increasingly documented.Geological and experimental evidence suggests that REE may be mobile in solutions rich in F^-,Cl^-,HCO3^-,CO^2- 3,HPO4^2-,PO4^3-,or in combinations of the above ligands,even though little has been known about which ligand or which combination is most effective in mobilizing REE. The fractionation of REE resulting from hydrothermal activities is inconsistent.One set of field data implies the prererential mobility of the light rare-earth elements(LREE).whereas another set of field observations indicates the dominant mobilization of the heavy rare earth elements(HREE),and some theoretical prediction is comtradictory to the field evidence.The Eu anomalies due to hydrothermal activities are complex and plausible explanation is not available.The existing experimental approaches dealing with REE are not adequate for explanation ofREE behaviour in aqueous solutions.Systematic experimental approaches are suggested.     

Atmospheric sources and sinks of volcanogenic elements in a basaltic volcano (Etna, Italy)

This study reports on the first quantitative assessment of the geochemical cycling of volcanogenic elements, from their atmospheric release to their deposition back to the ground. Etna’s emissions and atmospheric depositions were characterised for more than 2 years, providing data on major and trace element abundance in both volcanic aerosols and bulk depositions. Volcanic aerosols were collected from 2004 to 2007, at the summit vents by conventional filtration techniques. Precipitation was collected, from 2006 to 2007, in five rain gauges, at various altitudes around the summit craters. Analytical results for volcanic aerosols showed that the dominant anions were S, Cl, and F, and that the most abundant metals were K, Ca, Mg, Al, Fe, and Ti (1.5-50 μg m⁻³). Minor and trace element concentrations ranged from about 0.001 to 1 μg m⁻³. From such analysis, we derived an aerosol mass flux ranging from 3000 to 8000 t a⁻¹. Most analysed elements had higher concentrations close to the emission vent, confirming the prevailing volcanic contribution to bulk deposition. Calculated deposition rates were integrated over the whole Etna area, to provide a first estimate of the total deposition fluxes for several major and trace elements. These calculated deposition fluxes ranged from 20 to 80 t a⁻¹ (Al, Fe, Si) to 0.01-0.1 t a⁻¹ (Bi, Cs, Sc, Th, Tl, and U). Comparison between volcanic emissions and atmospheric deposition showed that the amount of trace elements scavenged from the plume in the surrounding of the volcano ranged from 0.1% to 1% for volatile elements such as As, Bi, Cd, Cs, Cu, Tl, and from 1% to 5% for refractory elements such as Al, Ba, Co, Fe, Ti, Th, U, and V. Consequently, more than 90% of volcanogenic trace elements were dispersed further away, and may cause a regional scale impact. Such a large difference between deposition and emission fluxes at Mt. Etna pointed to relatively high stability and long residence time of aerosols in the plume.     

Mineralogy and geochemical behavior of trace elements of hydrothermal alteration types in the volcanogenic massive sulfide deposits,NE Turkey

Volcanogenic massive sulfide (VMS) deposits of the Eastern Pontides, Turkey, are hosted by the Maastrichtian–Eocene dacite and rhyodacite series, accompanied by lesser andesite and basalts, as well as their pyroclastic equivalents, with tholeiitic to calc-alkaline affinity. The ore mineral assemblages are chalcopyrite, sphalerite, galena, chalcocite, covellite, bornite, and tetrahedrite. Potassic-, phyllitic- (sericitic), argillic- (kaolinitic and smectitic), silicic-, propylitic- and hematitic-alteration is commonly associated with these deposits.HFSE, LILE, TRTE and REE contents show strong variability in different alteration types resulting from interaction with acid or alkaline fluids. Sample groups showed chondrite-normalized enrichment of LREE relative to HREE and sub-parallel trends, except for the hematitic- and phyllitic-alteration types. MREE are strongly depleted in the zones of most intense silicification and kaolinization. Most sample groups have strongly- to slightly-negative Eu anomalies, ranging from 0.35 to 0.88 (mean); hematitic- (1.45) and propylitic-altered rocks (1.11) have slightly- to moderately-positive anomalies. The negative Eu anomalies indicate the low temperatures of fluids (< 200 °C). In contrast, the positive Eu anomalies result from high-temperature hydrothermal conditions (> 200 °C). No Ce anomaly was observed, except for phyllitic alteration where a slight positive anomaly was noted. The chondrite-normalized trace and REE patterns of the altered rocks are similar to each other, suggesting that they were derived from a common felsic source. The alteration groups formed from acid, intermediate, and alkaline hydrothermal solutions. Some transition, base and precious metals and volatile elements were clearly enriched, especially in the hematitic-, silicic-, kaolinitic- and phyllitic-altered samples. The other elements exhibit different behaviors in different sample groups. REE behavior is relatively immobile in the silicic-, hematitic-, kaolinitic- and partially in moderately- and propylitic-altered rocks, based on mass-balance calculations. LILE and HFSE appear mobile in the altered sample groups, except in the propylitic-altered rocks. TRTE behave as relatively immobile in most of samples, except in some of the silicic- and phyllitic-altered rocks, and especially in the hematitic-altered samples. HFSE, most of the transition (W, Mo, Cu, and Sb) and some other trace elements (Pb, As, Hg, Bi, Se and Tl), are enriched in the hematitic-altered samples and in the some silicic-altered samples. The highest As, Bi, Mo, Se and Hg concentrations in the hematite-altered samples can be used to distinguish other alteration types and may be a useful indicator in a prospect-scale base metal exploration.     

Quartz precipitation and fluid inclusion characteristics in sub-seafloor hydrothermal systems associated with volcanogenic massive sulfide deposits

Results of a numerical modeling study of quartz dissolution and precipitation in a sub-seafloor hydrothermal system have been used to predict where in the system quartz could be deposited and potentially trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the fact that quartz solubility depends on many inter-related factors, including temperature, fluid salinity and fluid immiscibility, and is further complicated by the fact that quartz exhibits both prograde and retrograde solubility behavior, depending on the fluid temperature and salinity. Using the PVTX properties of H₂O-NaCl, the petrographic and microthermometric properties of fluid inclusions trapped at various locations within the hydrothermal system have been predicted. Vapor-rich inclusions are trapped as a result of the retrograde temperature-dependence of quartz solubility as the convecting fluid is heated in the vicinity of the magmatic heat source. Coexisting liquid-rich and vapor-rich inclusions are also trapped in this region when quartz precipitates as a result of fluid immiscibility that lowers the overall bulk quartz solubility in the system. Fluid inclusions trapped in the shallow subsurface near the seafloor vents and in the underlying stockwork are liquid-rich with homogenization temperatures of 200?C400°C and salinities close to that of seawater. Volcanogenic massive sulfide (VMS) deposits represent the uplifted and partially eroded remnants of fossil submarine hydrothermal systems, and the relationship between fluid-inclusion properties and location within the hydrothermal system described here can be used in exploration for VMS deposits to infer the direction towards potential massive sulfide ore.     

Geochemistry of rare-earth elements in thermal waters of Uzon-Geyzernaya hydrothermal system (Kamchatka)

Precisional analyses of the abundances of La, Ce, and major elements in thermal waters and rocks of the Uzon-Geyzernaya volcanotectonic depression, supplemented by published data on a number of modern high-temperature hydrothermal systems of Kamchatka and two other areas of the world, allowed defining genetically important patterns of rare-earth elements (REE) distribution. The La and Ce abundances positively correlate with silica contents both in fresh igneous rocks of the study areas and in the products formed by hydrothermal processes.All studied hydrothermal clays are enriched in La and Ce. The general enrichment trend is similar to the pattern of positive correlation between the La and Ce abundances. Geothermal waters display a strong relationship between REE enrichment and pH. Enhanced REE enrichment trend is observed in thermal waters with abundant SO₄^2 ? and K. The REE versus Cl and B diagrams show two individual fields reflecting the level of acidity-alkalinity of thermal waters. These data demonstrate that La and Ce concentrations in the products of modern hydrothermal systems (in fluids and secondary mineral phases) are governed by wallrock composition, anionic water composition, and pH/Eh-dependent adsorption processes.     

Abundances of chemical elements in the Earth’s crust

The evaluation of the abundances of chemical elements in the Earth’s crust is a pivotal geochemical problem. Its first solutions in the early 20th century formed the empirical groundwork for geochemistry and justified concepts about the unity of the material of the Universe, the genesis of the chemical elements, and the geochemical differentiation of the Earth. The accumulation of newly obtained data called for the revision of this problem, and a series of papers by A.P. Vinogradov, which were published in Geokhimiya in 1956–1962, presented reevaluated contents of elements in the continental crust. In these papers, A.P. Vinogradov relied on the classic idea of the geochemical balance of the sedimentary process. These generalizations provided the foundation for the quantitative characterization of the geochemical background of the biosphere and allowed Vinogradov to formulate the principles of the melting and degassing of material in the outer Earth’s shells during the geologic history, a concept that became universally acknowledged in modern geochemistry and geology. The composition of the Earth’s crust can also be evaluated based not on the principle of geochemical balance in the sedimentary process but on data on the actual abundances of major magmatic, metamorphic, and sedimentary rock types. The possibility of this solution was provided after the extensive research of A.B. Ronov, who managed to develop a quantitative model for the structure of the Earth’s sedimentary shell. Based on these data, A.B. Ronov, A.A. Yaroshevsky, and A.A. Migdisov published a series of papers in Geokhimiya in 1967–1985 that presented a model for the chemical structure of the Earth’s crust with regard for the material composing not only the upper part of the continental crust but also its deep-seated granulite-basite layer and the oceanic crust. The quantitative estimates thus obtained led the authors to important conclusions: first, it was demonstrated that the estimated abundances of elements in the granite-metamorphic layer of the continental crust presented in the classic works by A.P. Vinogradov are confirmed by independent materials, which are based on data on the actual abundance of rocks. Second, incredible as it was, the principle of geochemical balance in the sedimentary process in application to Ca and carbonates appeared to be invalid. This problem remains unsettled as of yet and awaits its resolution.     

Abundances of neutron-capture elements in atmospheres of cool giants

We have determined the atmospheric abundances of Y, Ba, La, Ce, Pr, Nd, and Eu for a sample of 171 giants selected as clump giants with metallicities [Fe/H] between ?0.7 and 0.3 dex, based on photometric criteria. In our analysis, we assumed local thermodynamic equilibrium and fit the parameters of model atmospheres to high-resolution (R = 42 000) echelle spectra with high signal-to-noise ratios. The Ba and Eu abundances were derived using synthetic spectra, including hyperfine structure. We find no significant difference in the abundances of s-or r-process neutron-capture elements between clump giants and ascending-branch giants selected by us earlier. We also analyze the relation between the abundances of neutron-capture elements and [Fe/H].     

中国花岗岩类化学元素丰度及特征

在全国范围内 750个有代表性的大中花岗岩类岩体上,采集了 6 080件样品,组合成 768件组合样.所有样品完全采用无污染加工方案进行加工和制备.选用了以电感耦合等离子体质谱 (ICP-MS)、仪器中子活化和 X射线荧光光谱为主的多种先进的分析方法对这些花岗岩类样品进行了分析测试,实测元素近 70种.使用国家一级地球化学标准物质和重复测试样品进行质量监控,确保了分析数据的准确性和可靠性.依据这些实测分析数据,计算并提出了中国花岗岩类和不同构造单元、不同时代花岗岩类的近 70种化学元素或成分的丰度,探讨了中国花岗岩类和不同构造单元、不同时代花岗岩类元素丰度的特征.     

Environmental mercury and arsenic sources in fossil hydrothermal systems, Northland, New Zealand

 Northland, New Zealand has been affected by natural hot water spring systems depositing elevated concentrations of mercury and arsenic over the past 5 million years. Due to the different erosion levels of these hot water systems, four principal types of mercury and arsenic occurrences are found: active hot springs; layered surface deposits (sinters) deposited by hot springs; highly fractured rock zones formed immediately beneath hot springs; and chemically altered and mineralized rock from the deeper roots of hot spring systems. Mercury occurs principally as cinnabar and as a minor impurity (<1 wt%) in phosphate minerals and iron sulfides, particularly marcasite. Mercury is irregularly distributed through limonitic cements formed during oxidation. Arsenic occurs as a minor impurity (<1 wt%) in phosphate minerals and iron sulfides, particularly marcasite. Arsenic is also variably dispersed through limonite, but not necessarily with mercury. Decomposition of marcasite constitutes the most significant source of mercury and arsenic pollution from the studied sites. Release of mercury and arsenic into the environment from marcasite, phosphates and limonite is enhanced by acidification of the sites (down to pH of 2), caused by oxidation of iron sulfides. Mercury and arsenic concentrations of up to 100 parts per billion should be expected in waters near the deposits; these concentrations are in excess of recommended drinking water levels. Received: 9 April 1999 · Accepted: 2 August 1999     

Trace elements as indicators of the physicochemical conditions of mineral formation in hydrothermal sulfide systems

The three-mode distribution of trace-element (TE) concentrations is observed in accordance with three main forms of TE occurrence in mineral: structural, surficial, and phase (native TE phases). Minerals of hydrothermally synthesized pyrite–pyrrhotite–magnetite–greenockite assemblage in the presence of Au and Mn are studied. Discrimination of modes is made, using the method of statistical sample of analytical data for single crystals (SSADSC), which is based on the postulate that individual crystals can contain predominantly one of possible forms. This is supported by study of Cd modes of occurrence by element thermorelease atomic-absorption spectrometry. X-ray photoelectron spectroscopy and atomic-force microscopy were used to examine the surficial TE forms. It has been confirmed that the dependence of the TE content on the crystal size in the sample is mainly due to surficial nonautonomous phases absorbing TEs. The effect of correspondence of chemical-component forms on the surfaces of coexisting minerals is also corroborated. This phenomenon is not related to the mutual contamination of phases but is due to the induction of the corresponding states of chemical forms in coexisting nonautonomous phases. It is possible to obtain true coefficients of interface distribution, characterizing structural TE impurities. These coefficients differ strongly from apparent distribution coefficients calculated from the bulk contents of impurities, except for Mn in pyrrhotite and magnetite, where its structural mode is predominant. The results obtained show that TEs can be used as quantitative geochemical indicators, which help to obtain correct information about the parameters of mineral formation and TE contents in the fluid phase.     

Mineral-chemical studies of metamorphosed hydrothermal alteration in the Kristineberg volcanogenic massive sulfide district,Sweden

Mineralium Deposita - The massive sulfide deposits of the Kristineberg area, Sweden, occur within a 2- to 3-km-thick succession of felsic volcaniclastic rocks belonging to the Skellefte Group. The...     

Results of paleomagnetic study of an upper Cenozoic volcanogenic sequence,in central part of Kamchatka median range

Analyses and correlations of profiles through the Ermanovka Series (Kamchatka) of a still controversial age suggest, among other things, a gap of some 1 m. y. between the Series and the overlying sheet of basalts. Comparisons of the Kamchatkan paleomagnetic zones with the Apsheron- Transcaspian generalized paleomagnetic profiles indicate 3.5 m. y. as the absolute age of the tops of the Ermanovka Series. — IGR Staff.     

稀土元素在岩浆和水热系统的实验岩石学和地球化学研究进展

稀土元素对绿色科技的发展具有至关重要的作用,随着世界范围内新兴技术的发展进程对稀土的需求日益提高,稀土矿床成矿机理的研究已经成为目前国际地学的研究热点。稀土元素分配行为的高温高压实验能够为研究稀土在岩浆和水热系统中的迁移、分异和沉淀机制提供有效制约,为了解稀土元素地球化学行为和稀土成矿作用提供重要的理论基础。本文总结了近年来关于稀土元素在岩浆-热液体系中分配行为的高温高压实验研究进展,其中包括部分熔融作用稀土的分配行为,液态不混熔过程中稀土在共轭熔体相之间的分配系数,分离结晶作用过程中稀土在结晶矿物相与残余熔体相之间的分配系数,岩浆演化后期稀土在熔体和分异流体相之间的分配行为,以及稀土在热液流体中的迁移、分异和沉淀机制的相关研究。基于目前的实验研究结果,本文提出了稀土实验地球化学研究中依旧存在的一些问题：部分熔融作用对于成矿物质组成的影响,碳酸盐熔体和硅酸盐熔体液态不混熔对于碳酸岩稀土成矿作用的影响,岩浆晚期演化的热液流体对于稀土成矿作用的影响,稀土元素在液态不混熔、分离结晶和热液交代过程中的分异和富集机制等,并对未来需要继续完善和拓展的方向提出了展望。

     

Specific mineral associations of hydrothermal shale (South Kamchatka)

The sequence of hydrothermal shale from the East Pauzhet thermal field within the Pauzhet hydrothermal system (South Kamchatka) was studied in detail. It was established that the formation of shale resulted from argillization of an andesitic lava flow under the influence of an acidic sulfate vapor condensate. The horizons with radically different compositions and physical properties compared to those of the overlying homogeneous plastic shale were distinguished at the base of the sequence. These horizons are characterized by high (up to two orders of magnitude in comparison with average values in hydrothermal shale) concentrations of F, P, Na, Mg, K, Ca, Sc, Ti, V, Cr, Cu, and Zn. We suggested a geological–geochemical model, according to which a deep metal-bearing chloride–hydrocarbonate solution infiltrated into the permeable zone formed at the root of the andesitic lava flow beneath plastic shale at a certain stage of evolution of the hydrothermal system.     

Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids

The mineral fluorite is utilized as a probe to investigate the behaviour of the pseudolanthanide yttrium with respect to the lanthanides (rare-earth elements, REE) in fluorine-rich hydrothermal solutions. Hydrothermal vein fluorites are characterized by the close association of Y and REE, but in contrast to igneous and clastic rocks they show variable and nonchondritic Y/Ho ratios of up to 200. This suggests that Y and Ho, although similar in charge and size, may be fractionated in fluorine-rich medium-temperature aqueous fluids. In such solutions Y acts as a pseudolanthanide heavier than Lu. Y/Ho ratios of hydrothermal siderites are slightly below those of chondrites, suggesting that in (bi)carbonate-rich siderite-precipitating solutions Y may act as a Sm-like light pseudolanthanide. This indicates that Y-Ho fractionation is not a sourcerelated phenomenon but depends on fluid composition. Based on these results it is strongly recommended that discussions of normalized REE patterns in general should be extended to normalized Rare-Earth-and-Yttrium (REY) patterns (Y inserted between Dy and Ho), because the slightly variable behaviour of the pseudolanthanide yttrium with respect to the REE may provide additional geochemical information. Available thermodynamic data suggest a negative correlation between Y/Ho and La/Ho during migration of a fluoriteprecipitating hydrothermal solution. Cogenetic fluorites, therefore, should display either similar Y/Ho and similar La/Ho ratios, or a negative correlation between these ratios. This criterion may help to choose samples suitable for Sm-Nd isotopic studies prior to isotope analysis. However, in cogenetic hydrothermal vein fluorites the range of Y/Ho ratios is often almost negligible compared to the range of La/Ho ratios. This may be explained by modification of REE distributions by post-precipitation processes involving (partial) loss of a separate LREE-enriched phase. The presence of variable amounts of such an accessory phase in most fluorite samples is revealed by experiments employing stepwise incomplete fluorite decomposition. Fluorites derived from and deposited near to igneous rocks apparently display chondritic Y/Ho ratios close to those of their igneous source-rocks. However, a positive Y_SN anomaly is likely to develop as the distance between sites of REY mobilization and deposition increases.     

Western Kamchatka-Koryak continental-margin volcanogenic belt: Age,composition, and sources

The isotope-geochemical study of the Eocene-Oligocene magmatic rocks from the Western Kamchatka-Koryak volcanogenic belt revealed a lateral heterogeneity of mantle magma sources in its segments: Western Kamchatka, Central Koryak, and Northern Koryak ones. In the Western Kamchatka segment, magmatic melts were generated from isotopically heterogeneous (depleted and/or insignificantly enriched) mantle sources significantly contaminated by quartz-feldspathic sialic sediments; higher ⁸⁷Sr/⁸⁶Sr (0.70429–0.70564) and lower ¹⁴³Nd/¹⁴⁴Nd(ɛ_Nd(T) = 0.06–2.9) ratios in the volcanic rocks from the Central Koryak segment presumably reflect the contribution of enriched mantle source; the high positive ɛ_Nd(T) and low ⁸⁷Sr/⁸⁶Sr ratios in the magmatic rocks from the Northern Koryak segment area indicate their derivation from isotopically depleted mantle source without significant contamination by sialic or mantle material enriched in radiogenic Sr and Nd. Significantly different contamination histories of the Eocene-Oligocene mantle magmas in Kamchatka and Koryakia are related to their different thermal regimes: the higher heat flow beneath Kamchatka led to the crustal melting and contamination of mantle suprasubduction magmas by crustal melts. The cessation of suprasubduction volcanism in the Western Kamchatka segment of the continentalmargin belt was possibly related to the accretion of the Achaivayam-Valagin terrane 40 Ma ago, whereas suprasubduction activity in the Koryak segment stopped due to the closure of the Ukelayat basin in the Oligocene time.     

中国不同岩石类型花岗岩类元素丰度及特征

依据采自全国范围内约750个有代表性的大、中型花岗岩类岩体上的768件组合样的实测分析数据,这里计算并提出了碱长花岗岩、正长花岗岩、二长花岗岩、花岗闪长岩、石英二长岩、石英二长闪长岩等中国不同岩石类型的花岗岩类岩石近七十种化学元素或成份的丰度,探讨了中国不同花岗岩类岩石的岩石化学特征和微量元素丰度的特征。