The upper Viséan–Serpukhovian in the type area for the Serpukhovian Stage (Moscow Basin,Russia): Part 1. Sequences,disconformities, and biostratigraphic summary

The upper Viséan–Serpukhovian strata in the type region for the Serpukhovian Stage is an epeiric‐sea succession ca. 90 m in thickness. The predominantly Viséan Oka Group (comprising the Aleksin, Mikhailov, and Venev formations) is dominated by photozoan packstones with fluvial siliciclastic wedges developed from the west. The Lower Serpukhovian Zaborie Group is composed of the Tarusa and Gurovo formations. The latter is a new name for the shale‐dominated unit of Steshevian Substage age in the studied area. The Zaborie Group is composed of limestones and marls in its lower (Tarusa and basal Gurovo) part and black smectitic to grey palygorskitic shales in the main part of the Gurovo Formation. The Gurovo Formation is capped by a thin limestone with oncoids and a palygorskitic–calcretic palaeosol. The Upper Serpukhovian is composed of a thin (3–12 m) Protva Limestone heavily karstified during a mid‐Carboniferous lowstand. The succession shows a number of unusual sedimentary features, such as a lack of high‐energy facies, shallow‐subtidal marine sediments penetrated by Stigmaria, the inferred atidal to microtidal regime, and palustrine beds composed of saponitic marls. The succession contains many subaerial disconformities characterized by profiles ranging from undercoal solution horizons to palaeokarsts. Incised fluvial channels are reported at two stratigraphic levels to the west of the study area. The deepest incisions developed from the Kholm Disconformity (top of the Mikhailov Formation). This disconformity also exhibits the deepest palaeokarst profile and represents the major hiatus in the Oka–Zaborie succession. The new sea‐level curve presented herein shows two major cycles separated by the Kholm Unconformity at the Mikhailov/Venev boundary. The Lower Serpukhovian transgression moved the base‐level away from falling below the seafloor so that the section becomes conformable above the Forino Disconformity (lower Tarusa). The maximum deepening is interpreted to occur in the lower dark‐shale part of the Gurovo Formation. The base of the Serpukhovian Stage is defined by FADs of the conodont Lochriea ziegleri and the foraminifer Janischewskina delicata in the middle of the sequence VN2. The Aleksinian–Mikhailovian interval is provisionally correlated with the Asbian (Lower–Middle Warnantian) in Western Europe. Based on FODs of Janischewskina typica and first representatives of Climacammina, the Venevian is correlated with the Brigantian in Western Europe. The Tarusian–Protvian interval contains diverse fusulinid and conodont assemblages, but few forms suitable for international correlation. FADs of the zonal conodont species Adetognathus unicornis and Gnathodus bollandensis at several metres above the Protvian base suggest correlation of the entire Zaborie Group and may be the basal Protvian to the Pendleian. Copyright © 2014 John Wiley & Sons, Ltd.     

Manganese ore deposits in Koira-Noamundi province of Iron Ore Group, north Orissa, India: In the light of geochemical signature

Several small Mn–Fe oxide and Mn-oxide ore bodies associated with Precambrian Iron Ore Group of rocks are located within Koira-Noamundi province of north Orissa, India. These deposits are classified into in situ (stratiform), remobilized (stratabound) and reworked categories based on their field disposition. Volcaniclastic/terrigenous shale in large geographic extension is associated with these ore bodies.The in situ ore bodies are characterised by cryptomelane-, romanechite- and hematite-dominating minerals, low Mn/Fe ratio (1.1) and relatively lower abundance of trace (1500–2500 ppm) constituents. In such type of deposits the stratigraphic conformity of oxides with the tuffaceous shale suggests precipitation of Mn and Fe at a time of decreased volcaniclastic/terrigenous contribution. The minor and trace elements were removed from solution by adsorption rather than by precipitation. Both Mn and Fe oxides when precipitated adsorb trace elements strongly but the partitioning of elements takes place during diagenesis. The inter-elemental relationship reveals that Cu, Co, Ni, Pb and Zn were adsorbed on precipitating hydrous Mn oxides and form manganates. Some of these elements probably get desorbed from Fe oxide because of their inability to substitute for Fe³⁺ in the lattice of its oxide. However, P, V, As and Mo were less partitioned and retained in Fe-oxide phase. Positive correlation between Al₂O₃ and SiO₂, MgO, Na₂O, TiO₂ and some traces like Li, Nb, Sc, Y, Zr, Th and U points to their contribution through volcaniclastic/terrigenous detritus of both mafic and acidic composition.The remobilized ore bodies are developed in a later stage through dissolution, remobilization and reprecipitation of Mn oxides in favorable structural weak planes under supergene environment. Increase in average Mn/Fe ratio (8) and trace content (5000–8500 ppm) by 5–2.5 orders of magnitude, respectively, or more above its abundance in adjoining/underlying protore is characteristic of these deposits. The newly formed Mn ores constituting lithiophorite, cryptomelane/romanechite and goethite get quantitatively enriched in traces like Cu, Co, Ni, Pb and Zn. Positive correlation between Mn, Li, Co and Zn is due to the formation of mineral of lithiophorite–chalcophanite group during redistribution and reconcentration of Mn oxide. P and V, which were present in Fe oxide, also get dissolved and reprecipitate with Fe oxyhydroxide in these ores. Some other elements like Y, Th and U show positive relation with Fe. This is probably due to leaching of these elements during chemical weathering of associated shale and getting re-adsorbed in Fe-oxyhydroxide phase.However, under oxidizing environment selective cations like Ba, K, etc. resorb from Mn-structure, resulting in the development of pyrolusite (Mn/Fe>20). In such transformation, trace metals from pyrolusitic structure expels out, resulting thereby in a considerable reduction in total trace value (<3000 ppm).The reworked ore bodies are allochthonous in nature and developed through a number of stages during terrain evolution and lateritisation. Secondary processes such as reworking of pre-existing crust; solution and remobilization; precipitation and cementation and transport, etc. are responsible for their development. Such deposits are usually very low in Mn/Fe ratio (3) and trace content (<2000 ppm).     

准噶尔盆地东南缘芦草沟组油页岩元素地球化学特征及沉积环境指示意义

本文通过XRF和ICP-MS测试方法对油页岩样品进行测试,根据常量元素和微量元素特征、组分含量及某些元素的比值,探讨了研究区油页岩样品的地球化学特征,进一步阐述了其沉积环境的指示意义.结果表明,P和B元素强烈富集,相当硼及古盐度值都表明属于半咸水沉积环境,B/Ga、Sr/Ba值也说明受到海水影响或间歇性受海水影响,沉积环境以半咸水湖泊为主;Fe2+/Fe3+、V/(V+Ni)、V/Ni、Cu/Zn、Ni/Co和U/Th值及Ni的含量说明沉积环境为咸化的弱还原—还原环境;Mn/Fe和Mn/Ti值也较小,反映近岸的沉积环境;Sr/Cu表明主力油页岩形成时期处于温湿—干热气候.总体上反映出,研究区油页岩的沉积介质环境的显著特征是半咸水状态的弱还原—还原环境.     

Early Serpukhovian (late Mississippian) microflora from the Guadiato Area (southwestern Spain)

Calcareous microflora occur commonly in the early Serpukhovian (late Mississippian) rocks from the Guadiato Area (southwestern Spain) despite the fact that this area contains mostly siliciclastic sediments. The microflora recorded in the carbonate beds is regarded as representative of both relatively deep‐water and shallow‐water facies and can be compared with the slope and shelf facies environments distinguished in the Guadiato Area. Up to 45 algal taxa have been identified in the carbonate beds, of which 26 taxa occur in the relatively deep‐water assemblages, whereas the shallow‐water assemblages are composed of up to 43 taxa. The entire algal assemblage is dominated by calcifoliids, common cyanobacteria and incertae sedis, but the shallow‐water assemblages contain more commonly dasyclads, red algae and aoujgaliids. Most of these taxa are present, but poorly known, in other Serpukhovian carbonate platforms in the western Palaeotethys. Some algae (Hortonella uttingii, Kamaenella tenuis and Koninckopora inflata), usually regarded as being restricted to the Viséan, have been found in Serpukhovian rocks in the Guadiato Area, and also in Algeria, thus their stratigraphic ranges might be extended up to the Serpukhovian. Other important taxa include: Archaeolithophyllum, Cabrieropora, Calcifolium, Falsocalcifolium, Fourstonella, Frustulata, Kulikia, Neoprincipia and ‘Windsoporella’, which are exceptionally recorded in Serpukhovian rocks, or not recorded at all, because they are typically recorded in the Pennsylvanian (cf. Clavaporella), although some of them show earlier occurrences in Viséan rocks (Claracrusta, Paraepimastopora and Sparaphralysia). Some of the algal taxa can be considered as potential regional markers for the Serpukhovian, such as Archaeolithophyllum, cf. Clavaporella, Frustulata and Girvanella (?) sp. The algal assemblages found in the Guadiato Area show the greatest similarities with those in the Béchar‐Mézarif (Algeria), Pyrenees and Montagne Noire (southern France). Copyright © 2005 John Wiley & Sons, Ltd.     

Geochemistry of magnesian ilmenites from kimberlites in South Africa and Lesotho

Magnesium ilmenite from discrete nodules and lamellar intergrowths with pyroxene from the Kao, Sekameng, Frank Smith, and Monastery kimberlites has been analysed for Ti, Fe, Mg, Nb, Zr, Cr, Cu, Zn, Mn, Co, and Ni. Each kimberlite contains discrete ilmenites which exhibit a wide compositional range within the ilmenite-geikeilite series. Lamellar ilmenites from Frank Smith and Monastery differ in composition but both show a limited range in composition which lies within the compositional range shown by discrete ilmenites from these pipes. The ilmenites are enriched in Nb, Zr, Cr, Co, and Ni and depleted in Mn, Cu, and Zn relative to Mg-poor ilmenites from basic intrusions. Nb, Zr, and Ni correlate with Fe, Ti and Mg variations but the abundances of the other trace elements are independent of major element variation. R-mode factor analysis is interpreted to imply that the geochemistry cannot be interpreted in terms of a differentiation hypothesis in which trace elements are removed from or concentrated in residua. Factor scores and major element abundances indicate that each pipe is characterized by a particular suite of discrete ilmenite nodules, which are considered to be phenocrysts in a proto-kimberlite magma. Lamellar ilmenite-pyroxene intergrowths are unlikely to have had a eutectic origin, and show no simple relationship to the discrete ilmenites.     

Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale,southern Ordos Basin,China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.     

Plankton: Its chemical composition and its significance as a source of pelagic sediments

The absolute concentrations of minor and trace elements vary considerably in plankton. However, normalization of elemental abundances versus the minor elements Fe, Al and Zn (instead of the commonly used normalization versus seawater concentrations) demonstrates that these elements show remarkably constant proportions vis à vis each other. Thus, Ti, Fe, Al, Mn, V, and Zr occur in marine lower organisms in the same proportions as in the average shale, whereas Ba, Cr, Cu, Ni, Cd, Pb, Zn and B are enriched relative to the shale abundances, as are also Ca, Mg, Na, K, and Sr. These patterns appear to suggest that marine plankton are rich in lithogenic matter, but this is probably not the normal case.Contrary to the uniformity of plankton, sediments from the Pacific vary considerably in composition. Under the Equatorial high-productivity region the sediments show striking similarities with a mixture of average shale and average plankton mass, as could be expected, whereas sediments from the East Pacific Rise differ considerably from such mixtures. An iron—manganese phase (of deep-seated origin?), mixed with biological matter, on the other hand, yields model sediments with remarkable similarities to the East Pacific Rise deposits. It is therefore likely that biological processes account for a considerable fraction of some elements such as Cu, Ni, Zn and Ba also in the East Pacific Rise metalliferous sediments.     

Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.     

Elemental characteristics of lacustrine oil shale and its controlling factors of palaeo-sedimentary environment on oil yield: a case from Chang 7 oil layer of Triassic Yanchang Formation in southern Ordos Basin

As an important unconventional resource, oil shale has received widespread attention. The oil shale of the Chang 7 oil layer from Triassic Yanchang Formation in Ordos Basin represents the typical lacustrine oil shale in China. Based on analyzing trace elements and oil yield from boreholes samples, characteristics and paleo-sedimentary environments of oil shale and relationship between paleo-sedimentary environment and oil yield were studied. With favorable quality, oil yield of oil shale varies from 1.4% to 9.1%. Geochemical data indicate that the paleo-redox condition of oil shale’s reducing condition from analyses of V/Cr, V/(V + Ni), U/Th, δU, and authigenic uranium. Equivalent Boron, Sp, and Sr/Ba illustrate that paleosalinity of oil shale is dominated by fresh water. The paleoclimate of oil shale is warm and humid by calculating the chemical index of alteration and Sr/Cu. Fe/Ti and (Fe + Mn)/Ti all explain that there were hot water activities during the sedimentary period of oil shale. In terms of Zr/Rb, paleohydrodynamics of oil shale is weak. By means of Co abundance and U/Th, paleo-water-depth of oil shale is from 17.30 to 157.26 m, reflecting sedimentary environment which is mainly in semi deep–deep lake facies. Correlation analyses between oil yield and six paleoenvironmental factors show that the oil yield of oil shale is mainly controlled by paleo-redox conditions, paleoclimate, hot water activities, and depth of water. Paleosalinity and paleohydrodynamics have an inconspicuous influence on oil yield.     

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies.Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.     

Intercomparison of PIXE and ICP‐AES Analyses of Aeolian Dust from Owens (Dry) Lake,California

Particle‐induced X‐ray emission (PIXE) and ICP‐AES can be combined to obtain a wider range of detected elements, augment previous data and/or to verify measured concentrations of heavy and trace metals in geological samples. Intercomparison of data sets generated by multiple techniques is challenging due to the differing processes and methods of each technique. Here, we compare elemental data obtained by both techniques for aeolian dust from Owens (Dry) Lake, California. Nineteen elements were detected by PIXE, sixteen by ICP‐AES and ten elements were detected by both techniques. Statistical analyses of data set groupings illustrated which parameters differed significantly between PIXE and ICP‐AES. Relative variation (%) showed that PIXE gave higher concentrations than ICP‐AES for Al, As, Cu, Fe, K, Mn, Ni, Sr, Ti and Zn in all samples. For As, Cu, Sr and Zn, relative variation was variable between the techniques. PIXE detection limits exceeded ICP‐AES concentrations for Ba, Cd, Co, Cr, Pb and Mo. Low ICP‐AES percentage recoveries of Al, Fe, K, Mn and Ti for NIST SRM 2710 indicated incomplete dissolution during digestion (EPA Method 3050B), since elements were bound in silicate structures. Variability between the two data sets is explained by differences between analytical techniques, sample preparation methods and/or variability in sample matrices.     

Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources

Ferromanganese (Fe–Mn) crusts are strongly enriched relative to the Earth's lithosphere in many rare and critical metals, including Co, Te, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REEs). Fe–Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, Y, and REEs. Compared to Fe–Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo and crusts are more enriched in the other metals. The metal ions and complexes in seawater are sorbed onto the two major host phases, FeO(OH) with a positively charged surface and MnO₂ with a negatively charged surface. Metals are also derived from diagenetically modified sediment pore fluids and incorporated into most nodules. Seafloor massive sulfides (SMS), especially those in arc and back-arc settings, can also be enriched in rare metals and metalloids, such as Cd, Ga, Ge, In, As, Sb, and Se. Metal grades for the elements of economic interest in SMS (Cu, Zn, Au, Ag) are much greater than those in land-based volcanogenic massive sulfides. However, their tonnage throughout the global ocean is poorly known and grade/tonnage comparisons with land-based deposits would be premature.The Clarion–Clipperton Fe–Mn Nodule Zone (CCZ) in the NE Pacific and the prime Fe–Mn crust zone (PCZ) in the central Pacific are the areas of greatest economic interest for nodules and crusts and grades and tonnages for those areas are moderately well known. We compare the grades and tonnages of nodules and crusts in those two areas with the global terrestrial reserves and resources. Nodules in the CCZ have more Tl (6000 times), Mn, Te, Ni, Co, and Y than the entire global terrestrial reserve base for those metals. The CCZ nodules also contain significant amounts of Cu, Mo, W, Li, Nb, and rare earth oxides (REO) compared to the global land-based reserves. Fe–Mn crusts in the PCZ have significantly more Tl (1700 times), Te (10 times more), Co, and Y than the entire terrestrial reserve base. Other metals of significance in the PCZ crusts relative to the total global land-based reserves are Bi, REO, Nb, and W. CCZ nodules and PCZ crusts are also compared with the two largest existing land-based REE mines, Bayan Obo in China and Mountain Pass in the USA. The land-based deposits are higher grade but lower tonnage deposits. Notably, both land-based deposits have < 1% heavy REEs (HREEs), whereas the CCZ has 26% HREEs and the PCZ, 18% HREEs; the HREEs have a much greater economic value. Radioactive Th concentrations are appreciably higher in the land-based deposits than in either type of marine deposit. A discussion of the differences between terrestrial and marine impacts and mine characteristics is also presented, including the potential for rare metals and REEs in marine deposits to be recovered as byproducts of mining the main metals of economic interest in nodules and crusts.     

Geological and Geochemical Investigation of Three Ophiolite‐Hosted Manganese Prospects,Southeast of Birjand,South Khorasan,East of Iran

The studied ophiolite‐hosted manganese prospects are located in southeast of Birjand, South Khorasan, in the east of Iran. The manganese ores within the ophiolitic sequence in this region occur as small discrete patches, associated with radiolarian chert and shale. Manganese ores in the host rocks are recognizable as three distinct syngenetic, diagenetic, and epigenetic features. The syngenetic manganese ores occurred as bands associated with light‐red radiolarian chert. The diagenetic Mn ores occurred as lenses accompanied by dark‐red to brown radiolarian chert. The epigenetic Mn ores occurred as veins/veinlets within the green radiolarian shale. The major manganese ore minerals are pyrolusite, braunite, bixbyite, ramsdellite, and romanechite showing replacement, colloidal, and brecciated textures. The high mean values of Mn/Fe (15.32) and Si/Al (15.65), and the low mean concentration values of trace elements, such as Cu (85.9 ppm), Ni (249.9 ppm), and Zn (149 ppm), as well as the high concentration values of Si, Fe, Mn, Ba, Zn, Sr, and As in the studied manganese ores furnished sufficient evidence to postulate that the sea‐floor Mn‐rich hydrothermal exhalatives were chiefly responsible for the ore formation, and the hydrogenous processes had negligible role in generation of the ores. The further geological and geochemical evidence also revealed that the ores deposited on the upper parts of the ophiolitic sequence by submarine exhalatives. The intense hydrothermal activities caused leaching of elements such as Mn, Fe, Si, Ba, As and Sr from the basaltic lavas (spilites). After debouching of the sea‐floor exhalatives, these elements entered the sedimentary basin. The redox conditions were responsible for separation of Fe from Mn.     

The influence of rivers on the geochemistry of shelf sediments, southwestern coast of India

Geochemical and magnetic susceptibility studies of shelf sediments off Mangalore were carried out to understand the influence of rivers on sediment geochemistry, to study the elemental distribution patterns, and to evaluate the importance of the shelf as a source/sink for base metals. The contents of Cu, Pb, Mn, Fe and Al in the surficial sediments are lower by factors of 1.6–5.6, except Ca which is higher by a factor of 3.4 in relation to riverine suspended particulate matter (SPM). This is due to the seaward decrease of terrigenous influx which is reflected in the offshore protrusion of contours of Al, Fe, Cu, Zn, Ni and magnetic susceptibility values, particularly off Netravati and Gurpur rivers. Lower Mn content is also due to its remobilization from the anoxic-sulphidic shelf sediments. In contrast to the elements mentioned above, Ca increases seaward, suggesting that it is biogenic. The enrichment factor (EF) indicates that the surficial sediments are depleted in Cu, Zn and Mn compared to average shale and other anoxic sediments, and marginally enriched with Ni, Co, and Pb in relation to the average shale. However, a comparison between the EF of SPM of Netravati-Gurpur rivers in the hinterland and surficial sediments indicates that the latter are depleted in Mn and Co, but enriched with Ni, Pb, and Fe, thereby suggesting a source and a sink for the former and latter elements, respectively, to the Arabian Sea.     

贵州水城二叠系茅口组含锰岩系地质地球化学特征与锰矿成因分析

贵州水城二叠系茅口组内发现新锰矿。通过对含锰岩系的地质地球化学研究,其富集Zn,Ni,As,Sb,Sr,Ba,Ga,Ag,V,U元素;锰含量较高层位,Th/U比值小于1,锰含量较低层位,Th/U比值往往高达4～5。Co/Ni比值小于1。含锰岩石的(Fe+Mn)/Ti均大于47,高于20,特别是含锰高的岩石,其(Fe+Mn)/Ti值在300以上。含锰岩石的Al/(Al+Fe+Mn)均远远低于0.35,一般为小于0.02。稀土配分模式与峨眉山玄武岩相似,∑REE较高,LREE/HREE值偏低等特征。根据锰岩系地球化学和区域构造特征分析,水城二叠系茅口组含锰岩系属于热水喷流沉积的产物。     

Element mobility during alteration of silicic ash to kaolinite—a study of tonstein

A laterally persistent kaolinitic mudstone parting (tonstein) occurring in a Wyoming coal bed of Eocene age was sampled to estimate the compositional contrast with a probable silicic ash precursor, and to determine the compositional influence of leached ash on immediately adjacent coal. With the exception of Al, and possibly Ti, the tonstein is highly to moderately leached of major elements, relative to a range of compositions estimated for silicic ash of the region. In agreement with the behaviour of geochemically similar major elements, alkali trace elements (Rb, Cs) are highly leached, transition-series metals moderately leached, and Ga is residual. Additional immobile trace elements are Zr and Hf but some other trace elements that are considered relatively immobile during low-temperature alteration (Th, Ta, Nb, REE, Y) were apparently leached by the low-Eh, low-pH, organic-rich pore fluids of the coal-forming swamp. The migrational range of many of the leached elements is highly limited by the intimate association of tonstein with enclosing organic matter. Mixtures of coal + minor tonstein that occur within 20 mm of contacts are consistently enriched in some elements relative to either tonstein or nearby coal (U, Cu), or relative to calculated mixtures of tonstein and coal in their measured proportions (Th, Y, REE, Pb, Ba, V, Ti). Direct observations by fission-track radiography and electron microprobe indicate a preference of U and Fe for the organic component of mixtures. Metal fixation is probably by adsorption on insoluble organic matter (humic acids), or by precipitation as minor sulphides in these low-sulphur coals.     

Trace Elements in Olivines from the Giant Jinchuan Ni-Cu-(PGE) Deposit,NW China,and Its Geological Implication

The giant Jinchuan magmatic sulfide deposit in China is the third largest mining deposits in the world. Although many research have been done, there still exist some debates in the genesis of deposit. This study using the LA-IC-MS to obtain the trace elements concentrations of the olivine in order to discuss the mechanism of influence the element variability and illustrate the process of magmatism and ore-forming. The analytical results show that Ni, Co correlate negatively with Fo in the olivine, Mn/Fe is positively correlate with Fo, while Mn/Zn and Zn/Fe show no obvious correlation with Fo. The primitive mantle olivine-normalized trace element patterns of the Jinchuan olivine show that Jinchuan Ⅰ, Ⅱ intrusions have the same trace elements characteristics, which display negative Cr, V, Ni, Co and Ti anomalies and enrichment of Zr, Y, Ti, Sc and Ca. The multi-element patterns of the Jinchuan olivine imply same parental magma in the intrusion Ⅰ and Ⅱ. The spinel which cocrystallization with the olivine make it display negative Cr, V and Ti anomalies. The contents of Ni and Co in olivine are influenced by the process of sulfide segregation and the reaction between sulfide and olivine. The lower content of Cr and V in olivine of the intrusion Ⅱ compared with the intrusion Ⅰ imply that the parental magma of the intrusion Ⅱ was more evolved. Higher Mn/Zn (>13) ratios and lower Zn/Fe (<11) ratios indicate that the magma of Jinchuan intrusion likely originate from partial melting of peridotite mantle possibly, instead of pyroxene mantle sources.     

Taxonomical and Biogeochemical Investigation of Elements in Holocene Mollusk Shells in the South and Southwestern Marmara Basin,Turkey

Concentrations of some heavy metals and trace elements such as Cr, Ga, Ni, Zn, Mo, Cu, Pb, Yb, Y, Nb, Ti, Sr, Ba, Mn, Sc, Co, V, Zr, Fe, Al, W, Se, Bi, Sb, As, Cd in recent mollusk shells and factors affecting their distribution and deposits collected from various depths in the southern and southwestern parts of the Marmara Sea are investigated. The distribution of the elements in the shells is categorized into four groups. Of these, concentrations of 12 elements （As, Bi, Cd, Co, Ga, Mo, Nb, Sb, Se, Sc, W and Yb） are below zero [（0.053-0.79）×10^-6]; concentrations of seven elements （Cr, Ni, Pb, V, Y, Zr and Cu） are （1.0-6.0）×10^-6; concentrations of four elements （Ti, Mn, Ba and Zn） are 10- 20×10^-6; and concentrations of five elements （Si, Al, Fe, Mg and Sr） are （47.44-268.11）×10^-6. The taxonomic characteristics of the 29 elements were studied separately in mollusk shells such as Chamalea gallina （Linn6）, Pitar rudis （Poli）, Nassarius reticulatus （Linn6）, Venerupis senescens （Coocconi）, Mytilus galloprovincialis （Lamarck）, Mytilaster lineatus （Gemelin in Linne） and Chlamys glabra. It was found that, in mollusk taxonomy, the elements have unique values. In other words, element concentrations in various mollusk shells depend mainly on the taxonomic characteristics of mollusks. In various bionomic environments different element distributions of the same species are attributed to the different geochemical characters of the each environment. Data obtained in this study indicate that the organisms are the most active and deterministic factors of the environment.     

Chemical variations in sedimentary facies of an inner continental shelf environment,Northern Gulf of Mexico

Four major sedimentary provinces of the inner continental shelf off the Louisiana coast have been recognized by textural studies (Krawiec, 1966): deltaic, non-deltaic, and relict sediments; and deltadestructional sands. Samples from these provinces have been analyzed for Rb, Sr, Ni, Fe,Mn, Ti, and Zr; trend surface analysis has been used to discern regional trends of these elements. These trends substantiate the previous division of shelf provinces. Although deltaic and non-deltaic sediments cannot be distinguished by chemical criteria, they are distinctive from relict sediments, which are low in Mn, Fe, Ti, Zr, Rb, and Ni, and high in Sr. The delta-destructional sands are distinctive from the other three provinces by their low contents of Mn, Fe, Rb, and Ni, and high Ti, Zr, and Sr.In an energetic environment such as this, processes subsequent to deposition tend to disperse Rb, Fe, Ni, and Mn, as these elements are closely associated with the clays; these processes may give rise to enrichment of Zr due to the high stability and density of the mineral zircon, or the enrichment of Sr by accumulation of organic remains.