Ore potentiality of the Vanchin Graben, Primorye, Russia

New data on Cenozoic mineralization in the Vanchin coal basin are presented. In addition to the Au-Ag quartz-adularia veins known since the 1970s (Soyuzny deposit), stratified Au-Ag mineralization in tuffaceous-sedimentary rocks, porphyry tin mineralization in the extrusion of tourmalinized rhyolite, metalliferous coal seams enriched in Au, Ge, and REE are hosted in this graben. The localization and chemical and mineral compositions of these types of mineralization are considered. It is shown that Au-Ag mineralization is more widespread in the graben that was previously supposed. The anomalous and diverse mineralization of the Vanchin Graben is attributed, first of all, to long-term evolution of volcanism and hydrothermal activity developing synchronously with lacustrine and bog sedimentation and continuing after its termination. The main stages of ore formation are related to volcanic centers differing in age and conjugate hydrothermal systems functioning above a long-living magma chamber.     

The Nikolaevsky base-metal skarn deposit, Primorye, Russia

The study of the mineralogical and geochemical features of ores and their textural and structural relationships at the Nikolaevsky base-metal skarn deposit allowed us to establish the succession of mineral assemblages and to ascertain the complex distribution of elements in minerals, ores, and orebodies resulting from nonuniform development of metasomatic zones in the single ore-metasomatic process. The vertical mineralogical and geochemical zoning of the deposit is expressed in the replacement of economic Pb-Zn mineralization at the lower levels of the skarn orebodies with Ag-Pb-Zn mineralization at the upper levels of the major Vostok-1 orebody located at the contact of limestone and felsic volcanics and the block orebodies at the lower level of felsic volcanic rocks. Au-bearing vein Pb-Ag-Sb mineralization occurs in the near-surface zone of the deposit. Three mineralogical types of ores have been identified: sulfide-hedenbergite, quartz-carbonate-sulfide, and sulfide. The zonal distribution of these types within orebodies is combined with variations in mineralogy and in the distribution of major and minor elements. The statistical processing (the Geokhimiya-1 program) of 96 chemical analyses of monomineralic galena and sphalerite samples taken from skarn showed that an intimate Pb ? Bi assemblage is characteristic of the lower levels, whereas a Ag Bi assemblage is typical of the upper levels. The elemental assemblages correspond to definite mineral assemblages, determining the mineralogical and geochemical zoning of the deposit.     

Feldspathic metasomatic rocks from the Lermontovo deposit,Primorye, Russia

Drill cores of metasomatic rocks and ores from the Lermontovo skarn scheelite-sulfide deposit (Lermontovo ore field, Primorsky krai) have been studied. Feldspar-apatite-scheelite-sulfide metasomatic rocks containing more than 10% WO₃ have been identified and characterized. The relationships of these altered rocks to skarn, greisen, and sulfide ore are shown and the implications of these rocks for the formation of ore are determined. In addition, some genetic problems of the deposit are discussed.     

The petrology of greek brown coals

Results are given in the petrography of Greek coals collected from most of the major coal-bearing basins in Greece.Rank was determined by measuring reflectances on the maceral varieties eu-ulminite A and eu-ulminite B and on the maceral textinite. Reflectances obtained from these components indicate a coalification stage of brown coal for all samples. Within this group of samples there is, however, a fairly wide scatter of reflectance values indicating for some of them the transition zone from peat to brown coal and for others a coalification stage close to the transition into bituminous coals. Reflectances obtained from eu-ulminite A and eu-ulminite B were found to correlate well with chemical rank parameters such as volatile matter and calorific value.Composition was determined by maceral analysis. The coals are in general characterized by low amounts of macerals of the inertinite group, low to intermediate amounts of macerals of the liptinite group and high amounts of macerals of the huminite group. Within the latter group densinite, attrinite, eu-ulminite and textinite make up the bulk of the samples.Typical macerals observed in the coals are illustrated by two black and white and three colour plates.Cluster analysis based on maceral distribution, mineral matter and reflectance indicates that the samples studied can be divided into three major groups. The first one is dominated by eu-ulminite and densinite with relatively high reflectances. The second is dominated by attrinite, textinite and texto-ulminite with somewhat lower reflectances. The third is represented by a single sample in which textinite and resinite are the most abundant macerals. This sample also has the lowest reflectance.     

Molybdenum mineralization in the ores of the Tigriny tin deposit (Primorye,Russia)

The molybdenum mineralization at the Tigriny tin deposit is considered for the first time in the light of possible recovery of Mo as a by-product of selective mining. It is established that Mo has a positive correlation with Bi and does not show a correlation with Sn, W, or Zn. The highest Mo grade (>0.1%) in the ore stockwork is related to hornfels near the exposed granite porphyry stock and decreases downward by an order of magnitude. At the level of adit 5, the most numerous quartz-molybdenite veinlets develop at a distance of 50–100 m from the granite porphyry stock. The molybdenite-quartz, pegmatoid, and autogreisen generations of molybdenum mineralization are related to different substages of the first ore stage. All these generations predated crystallization of wolframite, cassiterite, and other ore minerals. The formation temperature for each molybdenite generation was determined by homogenization of fluid inclusions in quartz and decrepitation of samples characterizing each molybdenite-bearing assemblage. These data allowed us not only to estimate the crystallization temperature of each molybdenite generation but also to establish that the molybdenite crystallized from a pneumatolytic-hydrothermal melt-solution at the early stage of the deposit formation. The molybdenum mineralization is genetically related to the granite porphyry stock. The structure of the quartz-molybdenum stockwork was studied to determine the clusters of quartz-molybdenite veinlets and establish their orientation. Molybdenite 1 occurs in variably oriented veinlets that make up a stockwork around the apical portion of the porphyry stock. Disseminations and pockets of molybdenites 2 and 3 are hosted in pegmatoid rocks, greisen, and greisenized granite porphyry. The density of the Tigriny stockwork varies from 0 to 40–50 quartz-molybdenite veinlets per 5 m. Their orientation and spatial distribution were studied in quantitative terms. The most promising targets for selective mining of molybdenite from the Tigriny deposit are the framework of the Minor porphyry stock and the apical portion of the Main stock. The Tigriny deposit demonstrates a clear relationship between ore formation and granitic magmatism.     

Polycyclic aromatic hydrocarbons in Australian coals II. Novel tetracyclic components from Victorian brown coal

Gas chromatographic-mass spectrometric (GC-MS) analysis of a polycyclic aromatic hydrocarbon (PAH) fraction of a Victoria brown coal sample has revealed the presence of a novel series of tetracyclic triterpenoid derived components. The base peak of their mass spectra, at m/z 169, suggests an 8, 14-seco (C-ring cleaved) structural configuration with the triterpenoid derived A- and B-rings fully aromatized. Photochemically induced or acid-catalyzed processes are seen as two possibilities to account for the diagenetic formation of these compounds.     

Graben width controlling syn-rift sedimentation: the Palaeogene southern Upper Rhine Graben as an example

Eocene to Early Oligocene syn-rift deposits of the southern Upper Rhine Graben (URG) accumulated in restricted environments. Sedimentation was controlled by local clastic supply from the graben flanks, as well as by strong intra-basinal variations in accommodation space due to differential tectonic subsidence, that in turn led to pronounced lateral variations in depositional environment. Three large-scale cycles of intensified evaporite sedimentation were interrupted by temporary changes towards brackish or freshwater conditions. They form three major base level cycles that can be traced throughout the basin, each of them representing a stratigraphic sub-unit. A relatively constant amount of horizontal extension (ΔL) in the range of 4–5 km has been estimated for the URG from numerous cross-sections. The width of the rift (L _f ), however, varies between 35 and more than 60 km, resulting in a variable crustal stretching factor between the bounding masterfaults. Apart from block tilting, tectonic subsidence was, therefore, largely controlled by changes in the initial rift width (L ₀). The along-strike variations of the graben width are responsible for the development of a deep, trough-like evaporite basin (Potash Basin) in the narrowest part of the southern URG, adjacent to shallow areas in the wider parts of the rift such as the Colmar Swell in the north and the Rhine Bresse Transfer Zone that delimits the URG to the south. Under a constant amount of extension, the along-strike variation in rift width is the principal factor controlling depo-centre development in extensional basins.     

Hydrothermal precious opals of the Raduzhnoe deposit,north Primorye: The nature of the opalescence

This paper reports the results of the study of hydrothermal precious opals. It was established that, in terms of their nanostructure and formation conditions, the hydrothermal opals differ from exogenic precious opals. They are made up of small globules and do not show any structuring of their nanoparticles on the basis of closest packing, which is typical of exogenic precious opals. During their formation, these opals were subjected to pneumatolytic annealing—they experienced the impact of a high-temperature vapor under elevated pressure. The influence of the thermal effect led to the formation of two-dimensional photonic band gaps in the chaotic opal matrix. These bands are composed of sheets whose cells were formed owing to the thermal effects according to the principle of “Benard cells.” Precisely these structured blocks and thin films are responsible for the spectral dispersion of light and iridescence.     

Modes of trace element occurrence in galena from the Partizansky base metal-skarn deposit, Primorye

The localization and chemical composition of the galena from the Partizansky base metal-skarn deposit have been studied in the Second Contact ore body and Bol’nichnaya ore lode. The Partizansky deposit was formed during two stages: base metal-skarn and silver-sulfosalt. Much of the galena was deposited with the productive galena-sphalerite assemblage at the first stage. The galena of the productive stage of the Second Contact body shows wide variations in trace element composition. The galena from the root zone of the ore-bodies (the level of ?135 m) is characterized by steady high contents of economically important isomorphic and mechanical admixtures of bismuth and silver. The galena from the middle levels is almost devoid of isomorphic admixtures and occasionally contains fine inclusions of Ag-tetrahedrite. The high silver (and stibium) contents in the galena from the uppermost horizon (the level of +285 m) are mainly related to mineral inclusions of diverse silver minerals of the late silver-bearing assemblage. The galena from the Bol’nichnaya lode over a large depth interval has elevated contents of isomorphic silver and bismuth, with abundant inclusions of native bismuth.     

Low-temperature thermochronology of the flanks of the southern Upper Rhine Graben

The Upper Rhine Graben (URG) is the most perceptible part of the European Cenozoic Rift System. Uplifted Variscan basement of the Black Forest and the Vosges forms the flanks of the southern part of the graben. Apatite and zircon fission-track (FT) analyses indicate a complex low-temperature thermal history of the basement that was deciphered by inverse modelling of FT parameters. The models were tested against the observed data and independent geological constraints. The zircon FT ages of 28 outcrop samples taken along an E–W trending transect across the Black Forest and the Vosges range from 136 to 312 Ma, the apatite FT ages from 20 to 83 Ma. The frequency distributions of confined track lengths are broad and often bimodal in shape indicating a complex thermal history. Cooling below 120°C in the Early Cretaceous to Palaeogene was followed by a discrete heating episode during the late Eocene and subsequent cooling to surface temperature. The modelled time–temperature (t–T) paths point to a total denudation of the flanks of URG in the range of 1.0–1.7 km for a paleogeothermal gradient of 60°C/km, and 1.3–2.2 km for a paleogeothermal gradient of 45°C/km since the late Eocene.     

Anomalous Trace Elements Contents in the Spetsugli Germanium Deposit (Pavlovka Brown Coal Deposit) Southern Primorye: Communication 1. Antimony

The first data are presented on large-scale Sb accumulation (up to 1175 ppm on a whole coal basis) in the Spetsugli (Special Coals) germanium deposit (Pavlovka brown coal deposit). The distribution of anomalous Sb contents is considered in the coal-bearing molasse section. The close correlation between Ge and Sb abundances in coals together with SEM data indicate an organic mode of Sb occurrence. Such a significant Sb accumulation was caused by the filtration of volcanogenic metalliferous solutions in molasse rocks during early diagenesis of organic matter in the Late Miocene. Extremely high contents and organic mode of Sb occurrence make it possible to consider Ge-bearing coals of the Pavlovka deposit not only as a complex raw material suitable for the extraction of Sb, but also as a potential source of ecological hazard.     

A review of coal properties pertinent to carbon dioxide sequestration in coal seams: with special reference to Victorian brown coals

This paper presents reviews of studies on properties of coal pertinent to carbon dioxide (CO₂) sequestration in coal with specific reference to Victorian brown coals. The coal basins in Victoria, Australia have been identified as one of the largest brown coal resources in the world and so far few studies have been conducted on CO₂ sequestration in this particular type of coals. The feasibility of CO₂ sequestration depends on three main factors: (1) coal mass properties (chemical, physical and microscopic properties), (2) seam permeability, and (3) gas sorption properties of the coal. Firstly, the coal mass properties of Victorian brown coal are presented, and then the general variations of the coal mass properties with rank, for all types of coal, are discussed. Subsequently, coal gas permeability and gas sorption are considered, and the physical factors which affect them are examined. In addition, existing models for coal gas permeability and gas sorption in coal are reviewed and the possibilities of further development of these models are discussed. According to the previous studies, coal mass properties and permeability and gas sorption characteristics of coals are different for different ranks: lignite to medium volatile bituminous coals and medium volatile bituminous to anthracite coals. This is important for the development of mathematical models for gas permeability and sorption behavior. Furthermore, the models have to take into account volume effect which can be significant under high pressure and temperature conditions. Also, the viscosity and density of supercritical CO₂ close to the critical point can undergo large and rapid changes. To date, few studies have been conducted on CO₂ sequestration in Victorian brown coal, and for all types of coal, very few studies have been conducted on CO₂ sequestration under high pressure and temperature conditions.     

Geochemistry of carbonated mineral waters from the Fadeevskoe deposit of the Primorye region

The geochemical study of bed rocks, underground and surface waters, and associated gases in the Fadeevskoe deposit of carbonated waters (Sikhote Alin, Primorye region) revealed that the chemical composition of these waters is formed in the zone of active water exchange in the limited area of the discharge zone, where hydro carbonate calcic waters with mineralization of up to 1 g/1 are formed in largely potassic-sodic rocks. Calculations of the saturation indices show that the mineral waters are characterized by the early stage of Ca saturation, being undersaturated with carbonates and aluminosilicates. The main factors that influence the water mineralization are the excess carbon dioxide in water and the circulation time. The oxygen and carbon isotope ratios indicate the atmospheric genesis of the aqueous component (δ²H = —117; δ¹⁸O = —15.4%o) and the carbon isotope content in the CO₂ implies the mantle nature of the carbon dioxide (δ¹³C = -9.9%o).     

Humic acids in brown coals from the southern Russian Far East: General characteristics and interactions with precious metals

Brown coals with high Au and PGE concentrations from six deposits in the southern Russian Far East were analyzed for elemental composition, acid-base properties, and the molecular-size distribution of humic acids (HA). The ash contents of the coals were determined to be negatively correlated with their Au concentrations, and the content of “organic Au” (which is chemically bound to humic substances, HS) reaches 95%. The most probable mode of Au occurrence in the brown coals is submicrometer-sized particles of elemental gold stabilized by HA. Quantum-mechanical calculations of interactions between Au(0) clusters with model HS fragments confirm that HS could be originally strongly chemically adsorbed on the surface of elemental gold particles. Different stability of colloids during centrifuging of alkali extracts of the gold-bearing brown coals was proved to be likely responsible for the selective separation of free HA and those bound with gold particles, and this can be used to develop a technology for gold recovery from coals without decomposing their organic matrix.     

Stratigraphy of the Oligocene-Miocene boundary sediments in the Nezhinsky brown coal field (Primorye) and the problem of the Paleogene-Neogene boundary in the region

The geological characteristics of the productive coaliferous sequence and the overlying strata (the Nezhino Sequence) at the Nezhinsky brown coal field are provided with detailed geological and paleobotanical data on the Nezhino Sequence (operating quarry), which is proposed as its type section. Based on the analysis of the macro- and microfloral assemblages, the transitional Late Oligocene-early Miocene age is inferred for these sediments. The floras from both the sequences demonstrate no principal differences, being moderately thermophilic in composition, although the Nezhino flora is more thermophilic. The coaliferous and Nezhino sequences are assumed to be separated by a stratigraphic hiatus. It is shown that they are similar to the Oligocene-Miocene boundary sections in the adjacent regions. The Nezhino Sequence (lower Miocene) most likely corresponds to the upper Aquitanian-Burdigalian interval in the Standard stratigraphic scale. The Paleogene-Neogene boundary in the Primorye region is proposed to be placed at the top of the Pavlovka Horizon. In the Nezhino brown coal field, it coincides with the upper boundary of the coaliferous sequence.     

Anomalous Concentrations of Trace Elements in the Spetsugli Germanium Deposit (Pavlovka Brown Coal Deposit,Southern Primorye): Communication 2. Rubidium and Cesium

Data on Rb and Cs concentrations in typical (in terms of Ge content) and Ge-bearing coals, as well as host sedimentary rocks and underlying granites, are reported. It is shown that all Miocene deposits within ore zone are strongly enriched in these elements relative to Ge-barren areas of the deposit. The relative Cs accumulation is several times higher relative to Rb, because Ge-bearing sediments are characterized by anomalously low Rb/Cs ratio (up to 0.9). The average Cs concentration in coals (30.3 ppm) is more than one order of magnitude higher than the typical content in such rocks, while the maximal contents (57.2 ppm) exceed all known highest Cs contents found in solid fuel. Differences in Rb and Cs accumulation were found in the following sequence: coals (A^d < 50%)–coaly siltsones (50% < A^d < 75%)–coal-free and low-coaly silty sandstones and mudstones (A^d > 75%). The Rb content in this sequence increases, while the Cs content reaches maximum (up to 118.1 ppm) in the coaly siltstones. The anomalous Rb and Cs accumulation in Ge-bearing sediments is related to the circulation of volcanogenic thermal solutions, which are enriched in Ge, Rb, and Cs. It is suggested that Rb is mainly sorbed by clayey particles, whereas Cs is concentrated in the organic matter as well. This work presents the first data on high contents and distribution of Rb and Cs in Ge-bearing coals of the Pavlovka deposit. The data obtained make its possible to consider Rb and Cs as new associated elements of Ge mineralization, although their occurrence mode differs from that of Ge.