Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

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).     

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.     

Geology,geochemistry and genesis of the Godar Sabz Mn deposit in the Baft region,Iran

The Godar Sabz Mn deposit is located in the Nain-Baft ophiolitic belt in the northeast margin of the Sanandaj-Sirjan zone, Iran. The Nain-Baft back-arc extensional basin resulted from the subduction of the oceanic crust of Neo-Tethys under the southern margin of the Iranian Plate in the Early Cretaceous and hosts several mineral deposits, including volcanogenic massive sulfide, chromite, and Mn deposits. The mineralization in the Godar Sabz Mn deposit occurred predominantly as stratabound, massive, banded, layered, and lenticular orebodies in radiolarian cherts within Baft ophiolitic complex. The main ore minerals are pyrolusite, braunite, with minor amounts of todorokite. The significant geochemical features of the Godar Sabz ores, such as the high MnO content (21.82–80.65 wt%, average = 64.91 wt%), high Mn/Fe (average = 278), Si/Al ratios (average = 92.6), high Ba contents (average = 4495.6 ppm), the low average contents of Cu (81.8 ppm), Ni (106.2 ppm), Co (29.4 ppm), LREE > HREE, and trace element discrimination diagrams indicate a hydrothermal-exhalative source for mineralization. Chondrite-normalized REE patterns of studied ores have negative Ce and slightly positive Eu anomalies, which are similar to hydrothermal Mn deposits. The REE patterns of Mn ores coincide with basaltic lavas, suggesting that the Mn-mineralization in the Godar Sabz deposit was genetically related to the leaching of basaltic lavas. The Godar Sabz Mn deposit has many similarities with the main characteristics of the hydrothermal exhalative Mn deposits, including tectonic setting, host rock type, the morphology of orebodies, ore textures, mineralogy, and chemical features of ores.     

新疆富蕴县乔夏哈拉铜(铁)金矿床地质与微量元素地球化学

笔者简单介绍了乔夏哈拉铜(铁)金矿床的基本成矿及其微量元素地球化学特征,指出其主矿体具有“垂向分带”及“铜、金向下同步富集”的特点,认为其容矿火山岩与中基性侵入岩脉具有基本相似的微量元素地球化学行为,铜、金矿石同其容矿火山岩相比具有相对贫K、Rb、Th、Ba,相对富W、Ni、Co、As、Sb、Zn及明显偏低的Th／Ta、La／Yb值。研究稀土元素地球化学,发现铜、金矿石具有明显不同于其容矿火山岩的强Eu富集,后期形成的地质体一般具有相对更为偏低的∑REE值。综合分析表明,该铜(铁)金矿床为一与“层状夕卡岩”有关的火山热液型“层控”矿床。     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Genesis for Rare Earth Elements Enrichment in the Permian Manganese Deposits in Zunyi,Guizhou Province,SW China

The Zunyi manganese deposits, which formed during the Middle to Late Permian period and are located in northern Guizhou and adjacent areas, are the core area of a series of large-medium scale manganese enrichment minerogenesis in the southern margin and interior of the Yangtze platform, Southern China. This study reports the universal enrichment of rare earth elements(REEs) in Zunyi manganese deposits and examines the enrichment characteristics, metallogenic environment and genesis of REEs. The manganese ore bodies present stratiform or stratoid in shape, hosted in the silicon–mud–limestones of the Late Permian Maokou Formation. The manganese ores generally present lamellar, massive, banded and brecciated structures, and mainly consist of rhodochrosite, ropperite, tetalite, capillitite, as well as contains paragenetic gangue minerals including pyrite, chalcopyrite, rutile, barite, tuffaceous clay rock, etc. The manganese ores have higher ΣREE contents range from 158 to 1138.9 ppm(average 509.54 ppm). In addition, the ΣREE contents of tuffaceous clay rock in ore beds vary from 1032.2 to 1824.5 ppm(average 1396.42 ppm). The REEs from manganese deposits are characterized by La, Ce, Nd and Y enriched, and existing in the form of independent minerals(e.g., monazite and xenotime), indicating Zunyi manganese deposits enriched in light rare earth elements(LREE). The Ce_(anom) ratios(average-0.13) and lithofacies and paleogeography characteristics indicate that Zunyi manganese deposits were formed in a weak oxidation-reduction environment. The(La/Yb)_(ch), Y/Ho,(La/Nd)_N,(Dy/Yb)_N, Ce/Ce* and Eu/Eu* values of samples from the Zunyi manganese deposits are 5.53–56.92, 18–39, 1.42–3.15, 0.55–2.20, 0.21–1.76 and 0.48–0.86, respectively, indicating a hydrothermal origin for the manganese mineralization and REEs enrichment. The δ~(13) C_(V-PDB)(-0.54 to-18.1‰) and δ~(18) O_(SMOW)(21.6 to 26.0‰) characteristics of manganese ores reveal a mixed source of magmatic and organic matter. Moreover, the manganese ore, tuffaceous clay rock and Emeishan basalt have extremely similar REE fractionation characteristic, suggesting REEs enrichment and manganese mineralization have been mainly origin from hydrothermal fluids.     

贵州省松桃县道坨超大型锰矿床的发现及其成因探讨

贵州省松桃县道坨锰矿床是新发现的一个超大型全隐伏锰碳酸盐矿床。文章阐述了该矿床的发现概况及基本的地质和地球化学特征,并应用锰矿石和含锰黑色页岩的元素和碳同位素地球化学特征对菱锰矿的形成机制提出了制约。道坨超大型锰矿床的发现是填图及对区域地质资料综合分析的结果。该矿床具有品位高、厚度大、呈层性好及展布广等特点。其锰矿石的主量元素特征为Al2O3、TiO2、Fe2O3含量较低,P2O5中等程度富集,MnO、MgO含量相对较高,Fe/Mn比值低。在微量元素方面,锰矿石显示出较为明显的Co富集,含锰黑色页岩则显示出较为明显的Co、Mo富集;在稀土元素方面,锰矿石具有较高的稀土元素总量,轻微的"帽式"稀土元素PAAS标准化配分模式及明显的Ce正异常,含锰黑色页岩的稀土元素总量与PAAS接近,其稀土元素PAAS标准化配分模式较为平坦,无Ce异常。碳同位素测试结果显示出菱锰矿富集碳的轻同位素,表明在菱锰矿形成过程中存在有机碳的参与。文章表明,道坨锰矿床内的锰是以氧化物或氢氧化物的形式沉淀,菱锰矿是在缺氧且富含有机物质的成岩环境中转化而成。     

Ore Genesis for Stratiform Ore Bodies of the Dongfengnanshan Copper Polymetallic Deposit in the Yanbian Area, NE China：Constraints from LA-ICP-MS in situ Trace Elements and Sulfide S–Pb Isotopes

The Dongfengnanshan Cu polymetallic deposit is one representative deposit of the Tianbaoshan ore district in the Yanbian area, northeast(NE) China. There occur two types of ore bodies in this deposit, the stratiform ore bodies and veintype ones, controlled by the Early Permian strata and the Late Hercynian diorite intrusion, respectively. Due to the ambiguous genetic type of the stratiform ore bodies, there has been controversy on the relationship between them and veintype ore bodies. To determine the genetic type of stratiform ore bodies, laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in situ trace elements and S–Pb isotope analysis have been carried on the sulfides in the stratiform ore bodies. Compared with that in skarn, Mississippi Valley-type(MVT), and epithermal deposits, sphalerite samples in the stratiform ore bodies of the Dongfengnanshan deposit are significantly enriched in Fe, Mn, and In, while depleted in Ga, Ge, and Cd, which is similar to the sphalerite in volcanic-associated massive sulfide(VMS) deposits. Co/Ni ratio of pyrrhotites in the stratiform ore bodies is similar to that in VMS-type deposits. The concentrations of Zn and Cd of chalcopyrites are similar to those of recrystallized VMS-type deposits. These characteristics also reflect the intermediate ore-forming temperature of the stratiform ore bodies in this deposit. Sulfur isotope compositions of sulfides are similar to those of VMS-type deposits, reflecting that sulfur originated from the Permian Miaoling Formation. Lead isotope compositions indicate mixed-source for lead. Moreover, the comparison of the Dongfengnanshan stratiform ore bodies with some VMStype deposits in China and abroad, on the trace elements and S–Pb isotope characteristics of the sulfides reveals that the stratiform ore bodies of the Dongfengnanshan deposit belong to the VMS-type, and have closely genetic relationship with the early Permian marine volcanic sedimentary rocks.     

Cobalt‐Bearing Grunerite in the Metamorphosed Banded Iron Formation in Orissa,India

Banded iron formation (BIF) comprising high grade iron ore are exposed in Gorumahisani‐Sulaipat‐Badampahar belt in the east of North Orissa Craton, India. The ores are multiply deformed and metamorphosed to amphibolite facies. The mineral assemblage in the BIF comprises grunerite, magnetite/martite/goethite and quartz. Relict carbonate phases are sometimes noticed within thick iron mesobands. Grunerite crystals exhibit needles to fibrous lamellae and platy form or often sheaf‐like aggregates in linear and radial arrangement. Accicular grunerite also occur within intergranular space of magnetite/martite. Grunerite needles/accicules show higher reflectivity in chert mesoband and matching reflectance with that of adjacent magnetite/martite in iron mesoband. Some grunerite lamellae sinter into micron size magnetite platelets. This grunerite has high ferrous oxide and cobalt oxide content but is low in Mg‐ and Mn‐oxide compared to the ones, reported from BIFs, of Western Australia, Nigeria, France, USA and Quebec. The protolith of this BIF is considered to be carbonate containing sediments, with high concentrations of Fe and Si but lower contents of cobalt and chromium ± Mg, Mn and Ni. During submarine weathering quartz, sheet silicate (greenalite) and Fe‐Co‐Cr (Mg‐Mn‐Ni)‐carbonate solid solution were formed. At the outset of the regional metamorphic episode grunerite, euhedral magnetite and recrystalized quartz were developed. Magnetite was grown at the expense of carbonate and later martitized under post‐metamorphic conditions. With the increasing grade of metamorphism greenalite transformed to grunerite.     

Chemical Profiles across a Jurassic Stratiform Manganese Deposit at Katsuyama in the Mino Terrane of Central Japan: Implications for Depositional Environment, Diagenetic Metal Redistribution and Paleoceanography

Abstract. Inorganic chemical compositions are determined for a series of rocks crossing an Early Jurassic stratiform manganese ore deposit in a chert‐dominant sequence at Katsuyama, in the Mino Terrane of central Japan. The lithology in the vicinity of the manganese ore bed is classified into lower bedded chert, black shale, massive chert, manganese ore and upper bedded chert, in ascending order. The rocks surrounding the manganese deposit are anomalously high in certain elements: Pb (max. 29 ppm), Ni (1140) and Co (336) in the lower bedded chert, Mo (438), As (149), Tl (29) and U (12) in the black shales, V (210) and Cr (87) in the massive chert, and MnO and W (24) in the manganese ore. The aluminum‐normalized profiles reveal a distinct zonation of redox‐sensitive elements: Pb‐Zn, Ni‐Co‐Cu(‐Zn) and U‐Cr in the lower bedded chert, Mo‐As‐Tl in the black shale, V(‐Cr) in the massive chert, and Mn‐Fe‐Ba‐W in the manganese ore, in ascending order. The lower and upper bedded cherts and manganese ore generally exhibit flat rare earth element patterns with positive Ce anomalies, whereas the uppermost part of the lower bedded chert, the black shale and massive chert have flat patterns with weak or nonexistent negative Ce anomalies and weak positive Eu anomalies. The strong enrichment in Ni, Co, W, Tl and As detected in the Katsuyama section is not recognized in other sediments, including those of anoxic deposition origin, but is identified in modern ferromanganese nodules, suggesting that metal enrichment in the Katsuyama section is essentially due to the formation of ferromanganese nodules rather than to deposition in an anoxic environment. The observed elemental zonation is well explained by equilibrium calculations, reflecting early diagenetic formation and associated gradual reduction with depth. The concentration profiles in combination with litho‐ and biostratigraphical features suggest that formation of these bedded manganese deposits was triggered by an influx of warm, saline and oxic water into a stagnant deep ocean floor basin in Panthalassa at the end of the middle Early Jurassic. Paleoceanographic environmental controls thus appear to be important factors in the formation and preservation of this type of stratiform manganese deposit.     

REE redistribution during hydrothermal alteration of ores of the Kalahari Manganese Deposit

The Kalahari Manganese Deposit (KMD) is the largest land-based manganese deposit, hosting approximately 80% of the world's known, mineable manganese resources. The deposit, located near Kuruman in the Northern Cape Province of South Africa, is one of five erosional relics of the Paleoproterozoic (ca. 2.2 Ga) Hotazel Formation, with sedimentary manganese ores occurring as up to 50 m thick beds interbedded with banded iron-formation (BIF) and hematite lutite.The study focuses on the manganese ores of the Nchwaning–Gloria mining area of the northern KMD. In this area, pronounced mineralogical and major element alteration was imparted on the sedimentary manganese ores by a structurally-controlled hydrothermal fluid flow event. Most notable effects of hydrothermal alteration are the decomposition and leaching of Ca- and Mg-carbonate, and marked residual enrichment of manganese. On the basis of mineral assemblage, grade, texture and geochemical characteristics, three ore types were distinguished in the studied sample set, classified into least altered (LA), partially altered (PA) and advanced altered (AA) types. Advanced altered ores may be further classified into five different types, based on mineral assemblages that contain hausmannite and/or braunite as significant minerals. The rare earth element (REE) geochemistry of these fundamental ore types was studied in detail, to document REE mobility during hydrothermal alteration.Total REE concentrations in LA ores were found to be very low (14–22 ppm) and remarkably uniform, within the range typically observed for BIF. Hydrothermal alteration results in residual enrichment and a much larger scatter in REE contents. A small Ce anomaly observed in the protolith remains similar in magnitude when observed in PAAS-normalised REE plots. The data define, however, a power trend in the (Ce/Ce*) vs (Pr/Pr*) diagram. Such behaviour is interpreted in terms of a conservative system that was predominantly protolith-buffered. Local remobilisation of REE during hydrothermal alteration is attributed to the dissolution of diagenetic apatite and redistribution of hydrothermal trace minerals, including neoformed apatite, monazite and cerianite.     

Investigation on the role of microorganisms in manganese mineralization from Abadeh-Tashk area,Fars Province,southwestern Iran by using petrographic and geochemical data

Hydrothermal manganese and ferromanganese deposits associated with Neyriz ophiolite colored mélange occurred as small ore deposits in the Abadeh-Tashk area, SE of Fars Province, SW Iran. The deposits are found in three types: a) banded syngenetic ores, b) massive boudin and lens shaped diagenetic ores and c) vein and veinlet epigenetic ores. Microtextural, geochemical and mineralogical data associated with petrographic Raman, FTIR and SEM studies indicated that the primary Fe compounds formed series of microbially mediated biomats and Mn compounds were precipitated as an amorphous oxide on an active oxide surface accompanying silica gels. Field relationships between ore and host rock, high Mn/Fe ratio (17.43 to 40.79), ΣLREE, positive Eu and negative Ce anomalies in syngenetic ore types reveal that the ores were formed by hydrothermal fluid in an oceanic floor environment. Manganese was fractionated from iron due to physicochemical changes as well as microbial activities in the sedimentary environment. Microbial remains as filamentous beads with regular circular shapes, vermiform structures, series of Fe-rich biomats, traces of embedded organic material besides trace metals and REE concentrations in Mn ores emphasize the role of microorganisms in Fe and Mn precipitation. Syngenetic mineralization took place under suboxic neutrophilic conditions, while diagenetic processes resulted in variably reduced Fe- and Mn-oxides via organic matter decomposition, forming rhodochrosite as the end product. Braunite formation occurred most probably as a biogeochemically mediated early diagenetic product. Diagenetic and epigenetic Mn ores were formed when primary Mn deposits underwent subsequent diagenetic and remobilization–redeposition events respectively.     

The formation of Palæoproterozoic banded iron formations and their associated Fe and Mn deposits,with reference to the Griqualand West deposits,South Africa

This paper models the physico-chemical conditions of a Neoarchæan to Palæoproterozoic marine basin in which the sedimentary sequence of BIF, Fe and Mn ores of the Lake Superior-type formed. The model is based on Eh-pH diagram stability fields for Fe, silica and Mn solubilities (taken from the literature) and on field observations of the lithological sequences. BIF formation took place in epicontinental marine basins with free access to the ocean. The main Fe source for BIF formation was ocean enriched with about 6–10 ppm ferrous Fe of hydrothermal geochemical affinity. Land-derived Fe influxes into the BIF-forming basins certainly contributed, but the lack of clastic sedimentation precludes estimation of element budgets. The main silica source for formation of chert layers is sea water. If silica was precipitated by evaporation, the silica concentration of the BIF-forming sea must have been close to saturation (15–20 ppm). Biogenic silica concentration from a possible silica undersaturated sea may not be excluded. These inferred BIF-forming conditions fit the global occurrence of Lake Superior-type BIF in general, whereas special sedimentary environments were probably responsible for the formation of highly enriched laminated Fe ore at the Maremane Dome and in the Sishen-Kathu mining district in Griqualand West, and for the FeMn ores in the Kalahari field. Formation of laminated Fe ore in the Maremane Dome and in the Sishen-Kathu areas were restricted to local deeps within the BIF basins, caused by karst collapse in the underlying Campbellrand dolomites. In such deeps, increased pH values relative to the normal BIF-forming sea caused sufficiently increased silica solubility, resulting in the almost exclusive sedimentation of colloidal Fe precipitates.In the Kalahari field, the BIF sedimentation pile became silica-depleted when approaching the Mn layers. This was genetically controlled by the increased pH of sea water and increased silica solubility. Under such increased pH conditions, Mn oxides become stable for precipitation if minimum Mn activity is achieved in the sedimentary basin. The sedimentation sequence of low silica BIF - kutnahoritic BIF - jacobsitic BIF - braunitic Mn ore can be explained, using combined Eh-pH diagrams, as reflecting a precipitation path of increasing redox potential in a pH environment slightly above 9. These conditions were achieved by closing the access of the basin to the open ocean, resulting in the reduction of water level by evaporation and thereby increasing salinity and pH. Precipitation of low silica BIF followed and, in the presence of sufficient Mn activity with increasing Eh in the precipitating water stratum, deposition of the Mn mineral associations occurred.     

Detrital type manganese ore bodies in the iron ore group of rocks, Orissa, Eastern India

Detrital type of manganese ore bodies in the Precambrian Iron Ore Group of rocks occur in the Bonai-Keonjhar belt, Orissa besides stratiform (bedded type) and stratabound-replacement types of deposits. These ores appear in form of large boulders within lateritised aprons at various depths, often reaching beyond 30 m from the surface. Overprinting of primary structures, presence of mixed Fe-clasts and Mnooliths/pisoliths, mineral species of different generations and wide chemical variation amongst morphological varieties and from boulder to boulder are the characteristic hallmarks of such ore bodies. Features associated with ores occurring in different morphologies, namely: spongy, platy, recemented, and massive varieties from a typical profile of Orahari Mn-ore body in Keonjhar district are described. Recemented variety may be further classified into sub-varieties such as canga, agglomerate, and mangcrete. Common primary Fe-minerals are hematite, martite with relict magnetite. The secondary Fe-Mn phases are goethite, specularite, cryptomelane, lithiophorite, chalcophanite, manganite, and pyrolusite.These are ore bodies of allochthonous nature developed through a number of stages during terrain evolution and lateritisation. Secondary processes such as reworking of pre-existing crust through remobilisation, solution, precipitation, cementation, transport, etc. are responsible for the development of such detrital ore bodies in the Bonai-Keonjhar belt of Eastern India.     

Geochemical Constraints on the Origin of Banded Iron Formation‐Hosted Iron Ore from the Archaean Ntem Complex (Congo Craton) in the Meyomessi Area,Southern Cameroon

Banded iron formations (BIFs) are the most significant source of iron in the world. In this study, we report petrographic and geochemical data of the BIF from the Meyomessi area in the Ntem Complex, southern Cameroon, and discuss their genesis and the iron enrichment process. Field investigations and petrography have revealed that the studied BIF samples are hard; compact; weakly weathered; and composed of magnetite, subordinate quartz, and geothite. The geochemical composition of the whole rock reveals that iron and silica represent more than 98 wt% of the average composition, whereas Al₂O₃, TiO₂, and high‐field strength elements (HFSE) contents are very low, similar to detritus‐free marine chemical precipitates. The total iron (TFe) contents range from 48.71 to 65.32 wt % (average of 53.29 wt %) and, together with the low concentrations of deleterious elements (0.19 wt % P on average), are consistent with medium‐grade iron ores by global standards. This interpretation is confirmed by the SiO₂/Fe₂O_3total versus (MgO + CaO + MnO)/Fe₂O_3total discrimination plot in which most of the Meyomessi BIF samples fall in the field of medium‐grade siliceous ore. Only one sample (MGT94) plots in the high‐grade magnetite–geothite ore domain. The high Fe/Ti (376.36), Fe/Al (99.90), and Si/Al (29.26) ratios of the sample are consistent with significant hydrothermal components. The rare earth elements (REE) contents of the studied BIF samples are very low (∑REE: 0.81–1.47 ppm), and the Post‐Archaean Australian Shale (PAAS)‐normalized patterns display weak positive Eu anomalies (Eu/Eu*: 1.15–1.33), suggesting a syngenetic low‐temperature hydrothermal solutions, similar to other BIF worldwide. However, the Meyomessi BIFs show high Fe contents when compared to the other BIFs. This indicates an epigenetic mineralization process affected the Meyomessi BIF. From the above results and based on the field and analytical data, we propose that the genetic model of iron ores at the Meyomessi area involves two stages of the enrichment process, hypogene enrichment of BIF protore by metamorphic and magmatic fluids followed by supergene alteration as indicated by the presence of goethite in the rocks.     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: The Bayan Obo Fe-REE-Nb deposit,North China

The Bayan Obo Fe-REE-Nb deposit in northern China is the world's largest light REE deposit, and also contains considerable amounts of iron and niobium metals. Although there are numerous studies on the REE mineralization, the origin of the Fe mineralization is not well known. Laser ablation (LA) ICP-MS is used to obtain trace elements of Fe oxides in order to better understand the process involved in the formation of magnetite and hematite associated with the formation of the giant REE deposit. There are banded, disseminated and massive Fe ores with variable amounts of magnetite and hematite at Bayan Obo. Magnetite and hematite from the same ores show similar REE patterns and have similar Mg, Ti, V, Mn, Co, Ni, Zn, Ga, Sn, and Ba contents, indicating a similar origin. Magnetite grains from the banded ores have Al + Mn and Ti + V contents similar to those of banded iron formations (BIF), whereas those from the disseminated and massive ores have Al + Mn and Ti + V contents similar to those of skarn deposits and other types of magmatic-hydrothermal deposits. Magnetite grains from the banded ores with a major gangue mineral of barite have the highest REE contents and show slight moderate REE enrichment, whereas those from other types of ores show light REE enrichment, indicating two stages of REE mineralization associated with Fe mineralization. The Bayan Obo deposit had multiple sources for Fe and REEs. It is likely that sedimentary carbonates provided original REEs and were metasomatized by REE-rich hydrothermal fluids to form the giant REE deposit.     

Mineralogy and geochemistry of banded iron formation and iron ores from eastern India with implications on their genesis

The geological complexities of banded iron formation (BIF) and associated iron ores of Jilling-Langalata iron ore deposits, Singhbhum-North Orissa Craton, belonging to Iron Ore Group (IOG) eastern India have been studied in detail along with the geochemical evaluation of different iron ores. The geochemical and mineralogical characterization suggests that the massive, hard laminated, soft laminated ore and blue dust had a genetic lineage from BIFs aided with certain input from hydrothermal activity. The PAAS normalized REE pattern of Jilling BIF striking positive Eu anomaly, resembling those of modern hydrothermal solutions from mid-oceanic ridge (MOR). Major part of the iron could have been added to the bottom sea water by hydrothermal solutions derived from hydrothermally active anoxic marine environments. The ubiquitous presence of intercalated tuffaceous shales indicates the volcanic signature in BIF. Mineralogical studies reveal that magnetite was the principal iron oxide mineral, whose depositional history is preserved in BHJ, where it remains in the form of martite and the platy hematite is mainly the product of martite. The different types of iron ores are intricately related with the BHJ. Removal of silica from BIF and successive precipitation of iron by hydrothermal fluids of possible meteoric origin resulted in the formation of martite-goethite ore. The hard laminated ore has been formed in the second phase of supergene processes, where the deep burial upgrades the hydrous iron oxides to hematite. The massive ore is syngenetic in origin with BHJ. Soft laminated ores and biscuity ores were formed where further precipitation of iron was partial or absent.     

Magnetite Dyke in Precambrian Banded Iron Formation,Singhbhum Craton,India: Mineralogical and Chemical Characteristics

Banded iron formation (BIF) of the Gorumahisani–Sulaipat–Badampahar (GSB) belt in Singhbhum Craton, India, consists predominantly of magnetite. This BIF is intruded by a magnetite dyke. The magnetite dyke is massive and compact with minor sulphide minerals while the host banded magnetite ore, a component of the BIF, shows thin lamination. The magnetite ore of the dyke is fine to medium grained and exhibits interlocking texture with sharp grain boundaries, which is different from the banded magnetite that is medium to coarse grained and show irregular martitised and goethitised grain boundaries. Relics of Fe–Ca–Mn–Mg‐carbonate and iron silicates (grunerite and cummingtonite) are observed in the banded magnetite. The intrusive magnetite is distinctly different in minor, trace and REE geochemistry from the banded magnetite. The banded magnetite contains higher amounts of Si, Al, Mn, Ca, Mg, Sc, Ga, Nb, Zr, Hf, Co, Rb and Cu. In contrast, the massive magnetite is enriched in Cr, Zn, V, Ni, Sr, Pb, Y, Ta, Cs and U with higher abundance of HREE. In the chondrite normalized plot, the massive magnetite shows a slight positive Eu anomaly while the banded ore does not show any Eu anomaly. Field disposition, morphology, mineralogy and chemistry show that the intrusive magnetite dyke is of igneous origin, while magnetite in BIF formed from a carbonate protolith through the process of sedimentation.