Chemistry of Late Early Triassic Siliceous Claystone ('Toishi-type' Shale) from the Oritate Area, Sambosan Belt, Kyushu, Southwest Japan

Abstract. Inorganic chemical compositions are determined for late Early Triassic siliceous claystone ('Toishi-type' shale) and associated chert from Oritate area, Sambosan Belt, Kyushu, southwest Japan. The siliceous claystone is similar in chemical composition to Post-Archean Australian Shale (PAAS), but is depleted in Ca, Sr, Mn, and Fe and slightly enriched in Cu, Zn, P, and rare earth elements (REEs). The siliceous claystone and associated chert have flat REE patterns with positive Eu anomalies and no distinct Ce anomaly. The siliceous claystone and associated chert have largely constant Ti/Al, Th/Al, and Nb/Al ratios compared to the variable ratios found in siliceous shale and sandstone deposited close to land in a trench setting. This suggests that the claystone and chert were deposited in a deep-sea pelagic environment and were derived mainly from the suspended fraction, including eolian dust and material transported from distant lands, rather than from turbidity currents that occurred close to land. The low Ca contents of the analyzed rocks indicate deposition below the calcium-carbonate compensation depth. The depletion of Mn and Fe, and no distinct Ce anomaly in the Oritate siliceous claystone are also evident, being similar to those in samples from the Sasayama and Kinkazan sections in the Mino-Tanba Belt, where oceanic anoxia developed during the Late Permian to earliest Triassic. This might suggest that oceanic anoxia prevailed through to the late Early Triassic.     

Geochemistry of Late Permian to Early Triassic pelagic cherts from southwest Japan: implications for an oceanic redox change

Major, trace, and rare earth element abundances were determined for the southwestern Japanese pelagic chert sequence from the early Late Permian to early Early Triassic to investigate a redox change in deep-sea pelagic environments before and at the Permo-Triassic boundary (PTB) (251 Ma). The sequence was primarily deposited in the deep-sea of the superocean Panthalassa, and then was accreted to Japan in the Middle Jurassic. A remarkable lithostratigraphic change from red chert to siliceous∼carbonaceous claystone through gray chert is observed in this sequence. Constituent elements for these sedimentary rocks are essentially derived from two sources: (1) an ancient seawater via biogenic (mainly radiolarian), hydrothermal, and authigenic materials and (2) an average shale-like terrigenous material. The present measurement demonstrates significant stratigraphic changes of the Ce/Ce_non-ter* value (estimated Ce anomaly value of non-terrigenous component, recalculated by subtraction of terrigenous REEs from bulk REEs) and the (Mn/TE)_sample/(Mn/TE)_PAAS value (excess Mn component other than terrigenous one; TE=terrigenous elements including Ti, Al, Nb, Hf, Th; PAAS=Post-Archean Average Australian Shale) in the Permian chert. The Ce/Ce_non-ter* values increase from <0.2 to 1 and the (Mn/TE)_sample/(Mn/TE)_PAAS values decrease up-section, suggesting that the redox condition of deep-sea open-ocean changed from oxic to suboxic in an interval of approximately 10 Myr. The (∑Fe/TE)_sample/(∑Fe/TE)_PAAS and (Mn/TE)_sample/(Mn/TE)_PAAS values of carbonaceous claystone near or at the PTB are less than unity, suggesting that reductive dissolution of iron and manganese occurred under an anoxic condition. This supports the idea of the PTB oceanic anoxia in the superocean Panthalassa. The present data suggest that the anoxic condition prevailed in the deep-sea pelagic regions for an extremely long period, much more than 10 Myr, from the middle Late Permian to early Early Triassic. This long-term development of widespread oceanic anoxia may have been linked to the greatest mass extinction of the Phanerozoic.     

Geochemistry of Fe and Mn in surficial sediments of a tropical river and estuary,India—a granulometric approach

Geochemical characteristics of Fe and Mn in sand, silt, and clay fractions as well as in bulk sediments of the tropical perennial Muvattupuzha river and the Central Vembanad estuary of the southwest coast of India have been studied and discussed. The results of a physical fractionation study of Fe and Mn indicated a substantial increase in the content of these metals in silt and clay fractions above that in sand. The riverine silt and clay fractions account for two to three times the enrichment of Fe and Mn than the corresponding sand fraction; the estuarine counterparts indicate four to eight times the enrichment. The observed enrichment of Fe and Mn towards the more finer size grades is mainly due to the increased surface area of the finer clastics, which in turn increase the absorptive ability. However, the mineralogical diversities of the three size fractions also influence the enrichment of Fe and Mn. The spatial distribution of Fe and Mn indicates a marked decrease in the content of the latter than the former towards the high saline zones of the river and the estuary. This variation could be due to the higher solubility of Mn towards the high saline zones of the aquatic environment where reducing condition prevails most of the year.     

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.     

东营凹陷古近系中深层湖盆演化中的无机元素响应

为查明无机元素分布与水深、盐度等沉积环境以及湖盆演化过程的关系,采用电感耦合等离子体发射光谱仪分析对东营凹陷郝科1科探井古近系深层微量元素含量进行了测试、分析,所涉及的研究层位是该凹陷的主要烃源岩层段（沙河街组三亚段、沙河街组四亚段、孔店组）,分析结果表明:在水体浅、蒸发作用强烈的孔店组—沙四下亚段强氧化性滨浅湖环境里,钙、锶含量和Ca/Mg、Sr/Ba、Sr/Ca参数值具低值响应,铁、铝、钡、钒含量和（Fe+Al）/(Ca+Mg)参数值具高值响应;在沙四中亚段膏岩、盐岩等普遍发育的盐湖环境中,钠、锶含量和Sr/Ba、Fe/Mn、Sr/Ca均出现高值响应,锰、钡、钒含量和V/Ni、(Fe+Al)/(Ca+Mg)出现低值响应;在还原性的沙四上亚段半咸化深湖环境中,钾、钠、铁含量和Fe/Mn值具低值响应,钙、锰含量具高值响应;在沙四中亚段膏盐与泥岩共生体系中元素分布离散性明显,呈现波动性特征;Sr/Ba、Sr/Ca在盐湖环境中出现显著的高值响应,被证实可以作为良好的水体盐度指标参数,Fe/Mn、(Fe+Al)/(Ca+Mg)随水体加深逐渐增大,是良好的水体深浅指标参数。元素分布受沉积环境、岩性特征等多种地质因素的影响,在利用元素含量分布及特征元素比值来判断某单个地质因素的变化时,应该应用多种参数,进行综合判断。     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

Major-element chemistry and micromorphology of Mn-oxide coatings on stream alluvium

The Mn-oxide coatings on alluvium of six small streams in the eastern U.S.A. have been studied using a scanning electron microscope equipped with an energy dispersive X-ray analyzer. Low magnification surface analyses show that Mn is generally the most abundant followed by either Fe or Si. Several percent each of Ca and Al also occur. The Mn/Fe ratios range from 0.29 to 7.69 but average 2.37. Point analyses of coating cross sections show considerable variation in Mn/Fe ratios but no evidence of regular layering or microchemical laminations such as occurs in rock varnish. Two micromorphologies predominate: roughly circular structures which have a cellular appearance and spherical structures. The cellular structures are remarkably similar to porous Mn-oxide precipitated by bacteria in cultures prepared by Mustoe, suggesting that Mn-oxidizing bacteria are important in forming stream Mn-oxide precipitates.     

Jurassic microbial communities in hydrothermal manganese crust of the Rifian Calcareous Chain,Northern Morocco

The stratigraphic record of the Middle and Upper Jurassic in the Western Tethys is characterized by successive eustatic and tectonic events recorded as stratigraphic unconformities, which are revealed by hardgrounds, palaeokarsts, palaeosoils, and by the deposition of Fe–Mn crusts. The study of a Mn crust from the Middle-Upper Jurassic discontinuity in the Jbel Moussa Group (Rifian Cordillera), from stratigraphic, geomicrobiologic, mineralogical, and geochemical standpoints allows us to establish its hydrothermal origin. The manganese crust is composed by Ca-birnessite, cryptomelane and coronadite. Major- and trace-elements analyses of the whole crust show high contents in MnO (> 70 wt.%), a negative Ce anomaly and a positive Eu anomaly. Analysis of the microstructures under scanning electron microscopy reveals crystalline and microbial laminations, probably owing to fungal mycelium. Mineralogical and geochemical composition, together with microbial structures, suggest that this Mn crust formed as a result of venting hydrothermal fluids through synsedimentary faults. Chemosynthetic microbes were probably involved in the precipitation of Mn.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

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).     

陕南镇巴地区中-晚三叠世界线富锂黏土岩的发现及找矿意义

首次报道了扬子板块北缘镇巴地区中-晚三叠世界线黏土岩锂的超常富集,黏土岩产于关岭组(T₂g)/须家河组(T₃x)平行不整合界面,为古风化壳沉积物,Li₂O品位0.08%～0.11%,最高达0.22%,超过了该类型矿产的边界品位(0.06%),界线黏土岩的岩石学特征、矿物组成及岩石成因亟待查明。本文通过XRD分析、TIMA分析以及详细的地球化学研究,查明了界线黏土岩的矿物组成,探讨了黏土岩形成的沉积环境及物质来源,提出了不整合面黏土岩类关键金属矿产的综合找矿方向。研究表明,镇巴地区T₂/T₃界线黏土岩主要由石英、伊利石、高岭石组成,并含有极少量绿泥石、蒙脱石和铝绿泥石。主量元素(SiO₂、Al₂O₃、^TFe₂O₃、TiO₂)特征表明界线黏土岩属于铝土质泥岩,黏土岩CIA值(化学蚀变指数)为85～93,ICV值(成分变异指数)为0...     

Porphyroblastic manganaxinite metapelagites with incipient garnet in prehnite–pumpellyite facies, near Meyers Pass, Torlesse Terrane, New Zealand

Moderately manganiferous siliceous pelagites near Meyers Pass, Torlesse Terrane, South Canterbury, New Zealand, have been metamorphosed in the prehnite–pumpellyite facies. A conodont colour index measurement suggests T _max in the range 190–300 °C. Porphyroblastic manganaxinite, manganoan pumpellyite, manganoan chlorite and trace spessartine-rich garnet and sphalerite have formed in an extremely fine-grained quartz–albite–berthierine–phengite–titanite groundmass. Porphyroblastic manganaxinite semischists and schists are distinctive rocks in prehnite–pumpellyite to lower-grade greenschist and blueschist facies of New Zealand and Japan. Mn in the manganoan pumpellyites substitutes for Ca in W sites. Total Fe/(Fe+Mg) ratios in chlorite are dependent on oxidation state, being ≤0.22 in red hematitic hemipelagites, and ≥0.61 in low-f O₂ grey metapelagites. In the low-f O₂ metapelagites, manganoan berthierine with little or no chlorite is inferred in the groundmass and iron-rich chlorite occurs as porphyroblasts and veinlets, whereas in the red rocks, Mg-rich chlorite occurs both in groundmasses and veinlets. Variably high Si in the manganoan chlorites correlates with evidence for contaminant phases. The Mn content of chlorite contributing to garnet growth is dependent on metamorphic grade; incipient spessartine indicates a saturation value of 6–8% MnO in chlorite in low-f O₂ rocks at Meyers Pass. Lower MnO contents are recorded for otherwise analogous rocks with increasing metamorphic grade, but at a given grade coexisting chlorite and garnet are richer in Mn where f O₂ is high. Manganaxinite and manganoan pumpellyite also contributed to reactions forming grossular–spessartine solid solutions. Formation of garnet in siliceous pelagites is dependent on both Mn and Ca content. The spessartine component increases with grade into the greenschist facies. Partial recrystallization of berthierine to chlorite and the growth of porphyroblastic patches of other minerals was facilitated by brittle fracture and access of fluids to an otherwise impermeable matrix; to this extent the very low-grade metamorphism was episodic.     

中国西北地区典型钢铁工业城市表土重金属污染的环境磁学响应

以嘉峪关市为研究靶区,系统采集城区表土样品58件,对其进行环境磁学和重金属元素（Cd、Cr、Cu、Mn、Pb、V、Zn、Fe）质量分数分析。结果表明：嘉峪关市表土以低矫顽力磁铁矿为主导,磁晶粒度以较粗的假单畴（PSD）和多畴（MD）颗粒为主;城区表土亚铁磁性矿物浓度和磁性颗粒大小远高于国内综合型大城市表土;市区反映磁性矿物含量的参数呈现出以酒钢厂和废渣场为中心的高值区域,并随着污染源距离的增加向周围递减;嘉峪关市表土重金属Cd、Cr、Cu、Mn、Pb、V、Zn、Fe质量分数与反映磁性矿物含量的参数具有显著共变性,二者的高值分布与反映磁晶粒度参数的高值分布成盈缺呼应关系。然而嘉峪关市土壤母质磁性颗粒本底值较粗,与污染土壤特征相似,因此对西北地区而言,亚铁磁性矿物浓度相对磁晶粒度可以更好地指示钢铁厂周边土壤重金属的污染程度。     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

Reductive biotransformation of Fe in shale-limestone saprolite containing Fe(III) oxides and Fe(II)/Fe(III) phyllosilicates

A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)_TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)_TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe²⁺, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)₂, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.     

Iron/manganese ratio and manganese content in shield lavas from Ko’olau Volcano, Hawai’i

Precise Fe/Mn ratios and MnO contents have been determined for basalts from the Hawaiian shields of Ko’olau and Kilauea by inductively coupled plasma mass spectrometry. It is well known that the youngest Ko’olau (Makapu’u-stage) shield lavas define a geochemical endmember for Hawaiian lavas in terms of CaO and SiO₂ contents and isotopic ratios of O, Sr, Nd, Hf, Pb, and Os. We find that their MnO content is also distinct. Despite the small range in MnO, 0.146 to 0.176 wt%, the precision of our data is sufficient to show that among unaltered Ko’olau lavas MnO content is correlated with Nd-Hf-Pb isotopic ratios, La/Nb and Al₂O₃/CaO elemental ratios, and contents of SiO₂, MgO and Na₂O + K₂O adjusted for olivine fractionation. These trends are consistent with two-component mixing; one endmember is a SiO₂-rich, MnO-, and MgO-poor dacite or andesite melt, generated by low degree (10-20%) partial melting of eclogite. Since this low-MgO endmember (dacite or andesite melt) has very low FeO and MnO contents, mixing of high Fe/Mn dacite or andesite melt with a MgO-rich picritic melt, the other endmember, does not significantly increase the Fe/Mn in mixed magmas; consequently, Ko’olau and Kilauea lavas have similar Fe/Mn. We conclude that the high Fe/Mn in Hawaiian lavas relative to mid-ocean ridge basalt originates from the high MgO endmember in Hawaiian lavas.     

Trace metal remobilization following the resuspension of estuarine sediments: Saguenay Fjord,Canada

The Saguenay Fjord sediments are characterised by high trace metal, organic matter and Fe monosulfide (AVS) concentrations. The presence of important maritime activities, dredging operations around harbour installations, and natural slumpling events contribute to the resuspension of the Fjord sediments, their exposure to an oxidising environment, and the remobilization of a variety of contaminants to the water column.In order to simulate these processes, sediments collected from various depths in a box core recovered on the landward slope of the fjord's interior basin were resuspended in aerated seawater in the laboratory at room temperature. The slurries were sampled at various time intervals over a period of nearly 2000 h and the dissolved Fe, Mn and As concentrations were determined. Results of this study indicate that the amount of Fe and As released to the solution is strongly correlated to the acid volatile sulfide (AVS) content of the resuspended sediments. The release of Mn to the water phase, however, appeared to be mainly controlled by the dissolution of a solid phase, other than the Fe monosulfides but soluble in 1 N HCl, to which Mn (II) is associated. This phase could be a Mn carbonate or a mixed Mn–Ca carbonate.The dissolved metal concentrations measured at any time during the resuspension experiments reflect the reactivity of the carrier phases and the competing kinetics of the release and removal mechanisms. Upon their release to solution, Fe, Mn and As were scavenged by the newly precipitated Fe and Mn oxyhydroxides. The differential rate of formation of these phases and removal of associated metals in solution reflects their respective oxidation kinetics. The residence time of As in solution was very similar to that of Mn, implying that it was more efficiently removed with the slowly precipitated Mn oxyhydroxides. This observation is consistent with the faster oxidation kinetics of As (III) to As (V) in the presence of Mn oxyhydroxides. Nevertheless, results of As speciation analyses also suggest that a portion of the solubilized As was adsorbed and possibly oxidised by the rapidly precipitated Fe oxyhydroxides.     

Geological and geochemical constraints on the Cheshmeh-Frezi volcanogenic stratiform manganese deposit,southwest Sabzevar basin,Iran

The Cheshmeh-Frezi Mn deposit belongs to the southwest Sabzevar basin to the north of the Central Iranian microcontinent. This basin, which hosts abundant mineral deposits including Mn exhalative and Besshi-type Cu-Zn volcanogenic massive sulfide deposits, followed an evolution closely related to the subduction of the Neo-Tethys oceanic crust beneath the Central Iranian microcontinent. Two major sedimentary sequences are recorded within this basin: (I) the Lower Late Cretaceous volcano-sedimentary sequence (LLCVSS) and (II) the Upper Late Cretaceous sedimentary dominated sequence (ULCSS). The Cheshmeh-Frezi Mn deposit is hosted within red tuff with interbeds of green tuffaceous sandstone of the LLCVSS. Mineralization occurs as stratiform blanket-like and tabular orebodies. Psilomelane, pyrolusite and braunite are the main minerals of the ore, which display a variety of textures. Such as layered, laminated, disseminated, massive, replacement or open space fillings. The footwall and hanging-wall volcanic rocks are predominantly andesite and trachyandesite rocks. Footwall and hangingwall volcanic rocks at Cheshmeh-Frezi are enriched in light rare earth elements (LREEs) compared to chondrite, have steep REE patterns, and generally show Ta and Nb depletions relative to chondrite which are characteristic of back-arc environments. The significant geochemical characteristics of ore such as high Mn content (12.41–33.14 wt%; average 19.41 wt%), low concentration of Fe (0.64–2.27 wt%; average 1.63 wt%), high Ba (49.7–9901 ppm, average 2728.67 ppm), LREE > HREE, and negative Ce and Eu anomalies reveal a primary distal hydrothermal-exhalative source for mineralization. Cheshmeh-Frezi deposit, in comparison with different types of volcanogenic manganese deposits shows broad similarities with the Cuban-type Mn deposits such as tectonic, host and associated rock types, geometry, textures, structures, mineralogy and lithogeochemistry.     

新疆西天山莫托萨拉热水沉积型铁锰矿床矿物学与地球化学特征

莫托萨拉铁锰矿床位于西天山阿吾拉勒成矿带东端,研究程度相对薄弱,在矿床成因方面存在热水沉积、沉积-热液改造、胶体化学沉积等争论.本文详细研究了莫托萨拉最上层锰矿及其围岩的矿物组成、结构构造和地球化学特征,并综合前人资料对整个铁锰矿床的成因做了进一步探讨.本研究首次在矿区发现了热液长石岩,其主要由钠长石、钾长石以及少量重...     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998