EGU 2015-137 Mineralogical and Geochemical Characteristics of the Noamundi-Koira Basin Iron Ore Deposits (India) AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India) 1 AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA INTRODUCTION • • The Singhbhum craton is made up North and South Singhbhum shear zones. The latter shear zone starts with the basement of Old metamorphic group, older metamorphic tonalite trondhjemite gneisses, banded iron formation, metasedimentary rocks and covered by metavolcanic rocks of the North Singhbhum shear zone. Fig 1: Simplified geological map of Singhbhum-Orissa Craton (after, Saha 1994)eastern India. EGU 2015-137 Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India) 1 AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA EGU 2015-137 • The presence of disseminated martite in banded hematite jasper (BHJ) suggests that the magnetite of protore was converted to martite. • In first stage, unaltered banded iron formation (BIF) by simultaneously oxidizing magnetite to martite and replacing quartz with hydrous iron oxides. • In the second stage of supergene processes, deep burial upgrades the hydrous iron oxides to microplaty hematite. • Removal of silica from BIF and successive precipitation of iron resulted in the formation of martite-goethite ore. • Soft laminated ores were formed where leached out space remains with time and the interstitial space is generally filled with kaolinite and gibbsite, which make it low grade. Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India) 1 AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA EGU 2015-137 GEOCHEMISTRY Plots of Fe2O3 (%) vs. Al2O3 Plots Fe2O3 (%) vs. SiO2 60 80 60 0.3 0.2 CaO SiO2 Al2O3 40 40 0.1 20 20 Plots of Fe2O3 (%) vs. MgO 0.2 0 0 Fig.1(d) 100 Fe2O3 200 0 Fig.1 (b) 1.2 1 0.8 0.6 0.4 0.2 0 6 1.5 100 Fe2O3 50 Fe2O3 100 150 0 50 Fig.1 (g) 100 Fe2O3 150 0 Fig.1(f) Plots of Fe2O3 (%) vs. TiO2 TiO2 K2O 0 100 Fe2O3 150 0 2 0.5 50 Plots of Fe2O3 (%) vs. Na2O 1 4 1 0 Fig.1(c) 150 0.5 0 (e) Plots Fe2O3 (%) vs. K2O 50 Na2O 150 6 MnO2 MgO 0.4 50 100 Fe2O3 P2O5 0 Fig.1(a) 2 0 0 0 Plots of Fe2O3 (%) vs. CaO 0 0 Fig.1 (h) 100 200 Fe2O3 50 100 Fe2O3 150 Plots of Fe2O3 (%) vs. MnO2 4 2 0 0 Fig.1(i) 50 Fe100 2O3 150 Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India) 1 AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA Relationship Between CIA With Other Shale Oxides Plot CIA Vs P2O5 Plot CIA Vs Mgo 0.12 0.1 0.06 P2O5 Mgo 0.08 0.04 0.02 0 85 90 Fig .2 (a) 95 100 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0 0 CIA 100 150 Fe2O3 100 Plot CIA Vs TiO2 6 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 5 4 TiO2 k2O Na2O Fig .2 (c) 95 95 100 CIA Plot CIA Vs Na2O 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 90 90 Fig .2 (b) PLOT CIA Vs k2O 85 50 Fig.1 (j) 85 CIA Plot of Fe2O3 (%) vs LOI 14 12 10 8 6 4 2 0 LOI • The chemical index of alteration (CIA) depends on the ratio of Al2O3 to CaO, Na2O and MgO. EGU 2015-137 3 2 1 0 85 Fig .2 (e) 90 95 CIA 100 85 Fig .2 (d) 90 95 100 CIA Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India) 1 AZIMUDDIN MIRZA1, S.H.ALVI2, NURDANE ILBEYLI1 Akdeniz University, Fac. of Eng., Dept. of Geol. Eng, Antalya-TURKEY 2 Aligarh Muslim University, Dept. of Geol., Aligarh-INDIA CONCLUSION • Shows that precipitates. they are detritus- EGU 2015-137 10 free chemical • Hard laminated ores, martite-goethite ore and soft laminated ore are resultant of desilicification process through the action of hydrothermal fluids. Passive Margin 1 Active Continental Margin 0.1 • Mineralogy study suggests that magnetite was the principal iron oxide mineral, now a relict phase whose depositional history is preserved in BHJ, where it remain in the form of martite. The platy hematite is mainly the product of martite. • The presence of martite in massive ore along with their gradational contact of with BHJ suggests its syngenetic origin with BHJ. Island Arc 0.01 0 10 20 30 40 50 60 70 80 90 100 Fig:4.1. SiO2 vs. Log K2O/Na2O discrimination diagram(after Roser and Korsch, 1986) showing all the studied Iron samples plot in the Island Arc Field. Screen PICO2.1. SUMMARY • In this study the banded iron formation and associated iron ores of Noamundi–Koira iron ore deposits (Singhbhum- Orissa craton) that points out the study of different iron ores along with the composition of major elements and geological characteristics. • The Singhbhum craton is made up North and South Singhbhum shear zones. The latter shear zone starts with the basement of Old metamorphic group, older metamorphic tonalite trondhjemite gneisses, banded iron formation, metasedimentary rocks and covered by metavolcanic rocks of the North Singhbhum shear zone. • The iron ore of Noamundi-Koira can be divided into seven categories (Van Schalkwyk and Beukes 1986). They are massive, hard laminated, soft laminated, martite-goethite, powdery blue dust and lateritic ore. • It is more or less accepted that the parent rock of iron ore is banded hematite jasper (BHJ), the presence of disseminated martite in BHJ suggests that the magnetite of protore was converted to martite. • In the first stage, shallow, meteoric fluids affect primary, unaltered banded iron formation (BIF) by simultaneously oxidizing magnetite to martite and replacing quartz with hydrous iron oxides. • In the second stage of supergene processes, deep burial upgrades the hydrous iron oxides to microplaty hematite. • Removal of silica from BIF and successive precipitation of iron resulted in the formation of martite-goethite ore. Soft laminated ores were formed where precipitation of iron was partial or absent. The leached out space remains with time and the interstitial space is generally filled with kaolinite and gibbsite, which make it low grade. • Massive iron ores are devoid of any lamination and usually associated with BHJ and lower shale. The thickness of the massive ore layer varies with the location. The massive iron ore grades in to well-developed bedded BHJ in depth. • Blue dust occurs in association with BHJ as pockets and layers. Percolating water play an important role in the formation of blue dust and the subterranean solution offers the necessary acidic environment for leaching of quartz from the BHJ. • The dissolution of silica and other alkalis are responsible for the formation of blue dust. The friable and powdery ore on the other hand are formed by soft laminated ore. As it is formed from the soft laminated ore, its alumina content remains high similar to soft laminated ore compaired to blue dust. • Hard laminated ores, martite-goethite ore and soft laminated ore are resultant of desilicification process through the action of hydrothermal fluids. • The mineralogical and geochemical data suggest that the hard laminated, massive, soft laminated ores and blue dust had a genetic lineage from BIF’s aided with certain input from hydrothermal activity. • Geochemical data indicate that BIF are in general detritus free chemical precipitates. Fe2O3 content of BHJ are varies in between 36.6% to 65.04%. • In hard laminated ore, Fe2O3 content varies from 93.8% to 96.38%, soft laminated ore varies from 83.64% to 89.5% and laterite ore varies from 53.5% to 79.11%. • Fe2O3 content in Martite-Goethite ore varies from 86.38% to 89.42% and blue dust having 90.74% to 95.86% and all other oxides like SiO2, Al2O3, CaO, MgO, K2O, Na2O decrease. • 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 presence of intracalated tuffaceous shales pointing towards the genesis of iron, which could have leached from sea floor by volcanogenic process. Iron and silica of BIF were provided by the hydrothermal solutions emplaced at the vent sites situated at the Archean–Mid Oceanic Ridges. Banded Iron Formation • Banded iron formations (BIFs) are a distinctive type of rock often found in primordial (Precambrian) sedimentary rocks. • The structures consist of repeated thin layers of iron oxides, either magnetite (Fe 3O4) or hematite (Fe2O3), alternating with bands of iron-poor shale and chert. • The formations are abundant around the time of the Great oxygenation event, 2400 million years ago (mya), and become less common after 1800 mya. • The total amount of oxygen locked up in the banded iron beds is estimated to be perhaps twenty times the volume of oxygen present in the modern atmosphere. • Banded iron beds are an important commercial source of iron ore, such as the Noamundi–Koira Basin of the Singhbhum Craton. • Younger rocks superficially representing BIFs, commonly termed ‘ironstones’, are distinctly more Al2O3-, P2O5- and Fe2O3-rich and usually have an oolitic or pisolitic texture (Schopf, 1983). Table 1. Comparison of typical ironstones with iron formations (after James, 1966) Characteristics Ironstones Iron Formations Minimum age Major development Maximum age Thickness of major units Original areal extent, max. dimension Pliocene Lower Palaeozoic; Jurassic Palaeo-Proterozoic (~2.0 Ga) 1-50 m < 150 km Late Precambrian 2.5-3.0 Ga 3760 ± 70 Ma 50-600 m > 100 km Physical character massive to poorly banded; silicate thinly bedded; layers of haematite, and oxide- facies oolitic magnetite, siderite, or silicate alternating with chert; chert ~50% Age Mineralogy goethite haematite magnetite chamosite glauconite dominant fairly common relatively rare dominant primary silicate Minor none common common absent absent siderite common common calcite common rare Mineralogy dolomite common fairly common pelletal collophane relatively abundant absent greenalite None dominant primary silicate quartz (chert) Rare major constituent pyrite common common Chemistry high iron lower P low Al, Na, K and minor elements; much lower P Genesis of banded iron formation • The interpretation of an active continental margin as the depositional environment of the Minas Supergroup in Brazil, with the results that the same environment could explain the origin of the Caue Itabirite, a well known iron-formation. • In active margins, during the powerful process of subduction, the ocean lithosphere is cut by faults and fractures through which seawater gains access and hydrothermally leaches the brittle yet hot lower layers. • Currently being studied near mid-ocean ridges when iron and silica, among other compounds, are driven by thermal convection to the sea floor. • In Early Precambrian time, both hydrosphere and atmosphere were anoxic: ferrous iron was soluble in seawater and the earth's surrounding ozone layer had not yet been formed. • A plume of FeO-SiO2-rich seawater was concentrated above and along the trench, covering the nearby cratonic border. During the sunny hours of the day, iron was oxidized into ferric hydroxide before precipitation. • Most banded iron-formations laid down in early Precambrian time were subducted with their ocean plates and the only fraction preserved was that deposited above cratonic borders. • The break in iron-formation deposition at the end of that era was due to seawater and atmosphere oxygenation which produced the ozone-filtering layer around the earth and also caused extinction of marine anaerobic microorganisms. • Banded iron-formations deposited in active or passive continental margins may assist in the interpretation of the palaeo-environment of the regions where they occur. • The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, deep purple, to rusty red. The iron itself is usually found in the form of magnetite (Fe3O4), hematite (Fe2O3), goethite (FeO(OH)), limonite (FeO(OH).n(H2O)) or siderite (FeCO3). • It occurs as hematite (Fe2O3) or as goethite (HFeO2) or limonite (Fe2(OH)3) or siderite (FeCO3). Pyrite (FeS) is mined more for the sulfur content rather than for iron. STRATIGRAPHY AND GENERAL GEOLOGICAL SETTING • The Singhbhum-Orissa craton forms a triangular crustal block between latitudes 21°0' and 23°15' N and longitudes 84°40' and 86°45' E of a surface area ~40,000 sq. km (Saha, 1994). • This crustal block is broadly bounded by Chotanagpur Gneissic Complex to the north, Eastern Ghat Granulite Belt and the Bastar craton to the south and west respectively. • The craton consists mainly of granitoids, ranging in composition from tonalite in the oldest to alkali feldspar granite in the youngest, with engulfed and overlying metasedimentary and metavolcanic rocks. • The central part of the craton is occupied by granitoids of relatively older ages, whereas the metasediments, basic volcanics and younger granites occur at the margins mainly along the north, west and east. • The basement of the Singhbhum metasedimentary rocks can be traced in a broadly elliptical pattern of granitoids, with patches of Tonalite-Trondhjemite Granitoids (TTG) rock assembly, surrounded by metasediments and metavolcanics of Greenstone Belt association. • Most of the intrusive rock area is occupied by the Singhbhum granitoid, dated at 3.1 Ga, (Saha, 1994) and crosscut in rectangular pattern by voluminous Neoarchaean mafic and ultramafic dike swarms (Roy et al., 2004). • An ancient core to the Singhbhum rocks is built by the relatively small remnant of the Older Metamorphic Group (OMG) and Older Metamorphic Tonalite Gneiss (OMTG) rocks, dated between 3.4 and 3.5 Ga and metamorphosed to amhibolite facies (Saha et al., 1994; Sharma, 1994). • The Palaeoproterozoic Dhanjori Formation overlies the Singhbhum granitoid and is in turn overlain by the Chaibasa and Dhalbhum Formations constituting the Singhbhum Group (Mazumder, 2005). • Dhalbhum Formation includes 2 to 4 km thick quartzites, schists and tuffs of an unknown age and the following Dalma Formation with thick lava and volcano clastic rocks was dated at a minimum of 1600 Ma. Fig 1: Simplified geological map of Singhbhum-Orissa Craton (after, Saha 1994) eastern India. Fig. 2.A simplified geological map of Singhbhum-Orissa craton showing different lithounits (after Saha, 1994, Mukhopadhyay et al. 1990) and their modified ages of formation as understood from recent studies .Some modification on distribution of SBG-I in the map is made following new findings of Ghosh et al. (1996). The expected ages of formation of the supracrustals and some other lithounits (which are not dated directly) are marked by star (*). Abbreviations of lithounit names in alphabetical order: AG- Arkasani Granite, BG- Bonai Granite, CG- Chakradharpur Granite Gneiss, CGC- Chotanagpur Gneissic Complex, DLV- Dalma Volcanics, DNV- Dhanjori Volcanics, GOND- Gondwana and equivalent sediments, IOG- Iron Ore Group, JPV- Jagannathpur Volcanics, KG- Kuilapal Granite Gneiss, MBG- Mayurbhanj Granite, MG- Mayurbhanj Gabbro, MTVMalangtoli Volcanics, NG- Nilgiri Granite, OMG- Older Metamorphic Group, OMTG- Older Metamorphic Tonalite Gneiss, SBG-I -Singhbhum Granite (phase I), SBG-II–Singhbhum Granite (Phase II), SBG-III –Singhbhum Granite (Phase III), SG- Soda Granite, SMB- Singhbhum Mobile Belt, SPLV- Simlipal volcano-sedimentary basin, UGG- Unclassified granite/ granulites. Solid ellipses- sample locations of Misra et al. (1999), solid pentagons- sample locations of Roy et al. (2000 a,b). FF- eastern extension of Singhbhum Shear Zone passing through Kendua. • Laterally extensive semi-circular Singhbhum Shear Zone (SSZ) which encompasses mainly Dhanjori quartzites and schists and can be followed for some 200 km along strike and for few km in width. • The thrusting, folding and metamorphism are generally thought to thoroughly obliterate stratigraphic and sedimentary facies relationships. • The degree of metamorphism decreases markedly towards the top of the section and is much lower in the Dalma and Chandil Formations, probably reaching lower greenschist facies at the top. • The timing of one of the metamorphic events is around 1600 Ma, as is the age of the shearing/ thrusting along the Singhbhum Shear Zone (Krishna Rao et al., 1977; Sengupta and Mukhopadhaya, 2000). Generalized Stratigraphy of Singhbhum Craton South of Singhbhum Shear Zone North of Singhbhum Shear Zone Kolhan Group Newer Dolerite Dykes (Phase-III) Newer Dolerite Dykes (Phase-III) Dalma Metavolcanic Suite Jagannathpur/Dhanjori/Ongarbio Volcanic Suite and Newer Dolerite Dykes (Phase-II) newer Dolerite Dykes (Phase-II) Dhanjori/Sahedba Metasedimentary Rocks Gabbro-anorthosite and associated Dolerite Gabbro-anorthosite Dykes (Phase-I) Noamundi-Koira Banded Iron Formation and Dhalbhum Formation associated Manganese Deposits Chakradharpur Granite-Gneiss Bonai Metavolcanic Suite/Simlipal Complex complex/Soda Granite/Arkasani Granophyre Chaibasa Formation Chaibasa Formation Singhbhum Granite Complex/Bonai Granite Gorumahisani-Badampahar Banded Iron Formation Older Metamorphic Tonalite-Trondhjemite (TTG) Gneisses (OMTG) Older Metamorphic Group (OMG) Basement(?) Basement(?) Noamundi-Koira Basin • The BIF in Noamundi-Koira Basin (NKB) trends N-NE and is low plunging synclinorium with an overturned western limb (Chakraborty and Majumdar, 1986). • The clear separation of Iron and manganese into discrete ore bodies in NKB suggest the dawn of an oxidizing atmosphere near the close of Bonai volcanism. • A lower volcanogenic facies devoid of either iron or manganese deposits is represented by tuff, tuffaceous shale (phyllite) and referred as Lower Shale. This occurs peripheral to the basin and is poorly exposed in the eastern part of the basin, where its thickness does not exceed 30 to 50 m (Banerjee, 1975). • The overlying transitional chemogenic facies is made up of 300 to 400 m thick Banded Hematite Jasper (BHJ). • The upper facies is represented by manganiferous shale, chert, dolomite and tuff, referred as Upper Shale in the forms of layers and isolated lenses, few associated with chert and few with dolomite beds (Murthy and Ghosh, 1971). • The shale is usually soft showing distinct lamination of varying thickness and wide range of colours-grey, pink, brown and yellowish white. • The colour band in the shale varies from few millimeters to several centimeters. The upper shale is distinct from typical Archean, Proterozoic and Phanerozoic shales, which commonly contain considerable amount of chlorite. • The Upper shale comprises kaolinite as a major phase with minor with minor quartz, plagioclase and calcite. • Sambasiva Rao and Das Gupta (1997) found that the majority of the sample contain only kaolinite and a small proportion of sample comprise both kaolinite and illite. Hematite, goethite, mangnetite and very rarely ilmenite from the characteristic heavy mineral assemblage. GEOCHEMISTRY • Geochemical data indicate that BIF are in general detritus free chemical precipitates. Fe2O3 content of BHJ are varies in between 36.6% to 65.04%. • In hard laminated ore, Fe2O3 content varies from 93.8% to 96.38%, Soft laminated ore varies from 83.64% to 89.5% and laterite ore varies from 53.5% to79.11%. • Fe2O3 content in martite-goethite ore varies from 86.38% to 89.42% and blue dust having 90.74% to 95.86% and all other oxides like SiO2, Al2O3, CaO, MgO, K2O, Na2O are decreases. • Major element analysis reveals that the BHJ can contains very little amount of Al 2O3, TiO2, MgO, MnO2, and CaO. In BHJ with least alteration, the Fe is around 40% and the total Fe2O3 in the BHJ of Noamundi- Koira basin from 40.75% to 65.04%. • Fe2O3 (20% to 98%) and SiO2 (0.1% to 60%.) content of the studied BIF shows that variation from different localities show clear grouping and mainly discriminate between the groups on the basis of Fe2O3 and SiO2 content. • In the plot of Fe2O3 vs SiO2, Samples show negative trend indicating increase of Fe2O3 with decrease in SiO2. • The TiO2 concentration ranges between 0.035% and 0.062% in the BHJ and from 0.04% to 0.74% on an average in the iron ores. • The BHJ of Noamundi- Koira deposits are pure chemical precipitates and hence have low Al2O3 and TiO2. Both simultaneously increase in laterite and shale represent a time of increased detrital input. • BHJ and high grade ore are depleted in CaO+MgO, suggesting a near absence of calcite and dolomite which is also clear from the mineralogical information. TiO 2 shows a positive correlation with Al2O3 in ores. • Aluminum and Titanium are considered to be immobile during hydrothermal, diagenetic and weathering processes . Alkali content (K2O + Na2O) of shales, lateritic ore and BIF shows considerable variation. Shale samples contain high Na2O, but low K2O content indicating that the source of the clastic component was of variable composition. • The lower shale member contains more silica and higher percentage of silica is due to presence of quartz, the middle shale member is enriched in Fe2O3 as it is interbedded with iron ores. • The upper shale member shows almost similar Al2O3 content with middle shale member but lower Fe2O3.The shale samples are enriched in Na2O and K2O and the samples with high K2O reflect the micaceous nature of some of the terrigenous layers. • The lower shale of Noamundi-Koira area contain 0.84% of Na2O and 0.97% of K2O suggesting their origin from volcanoclastic debris. • The average oxide percentage values of various shale members fall in three different fields closely associated with tuffaceous volcanic/pyroclastics indicating a close relation between the lower shale and volcanic tuff / pyroclastic rocks. Plots of Fe2O3 (%) vs. Al2O3 40 CaO 30 20 10 0 0 Fig.1(a) 50 100 150 Fe2O3 0 Fig.1 (b) Plots of Fe2O3 (%) vs. MgO 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 50 100 150 1.2 1 1 0.8 Na2O P2O5 MgO Fig.1(d) Fe2O3 150 0.4 0.2 0.2 0 0 0 Fig.1(e) 100 0.6 0.4 200 50 Fe2O3 Plots of Fe2O3 (%) vs. Na2O Plots of Fe2O3 (%) vs. P2O5 0.6 100 0 Fig.1(c) Fe2O3 0.8 0 Plots of Fe2O3 (%) vs. CaO 0.3 0.25 0.2 0.15 0.1 0.05 0 50 70 60 50 40 30 20 10 0 Al2O3 SiO2 Plots Fe2O3 (%) vs. SiO2 50 100 Fe2O3 150 0 Fig.1(f) 50 100 Fe2O3 150 Plots of Fe2O3 (%) vs. TiO2 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 6 5 TiO2 K2O Plots Fe2O3 (%) vs. K2O 4 3 2 1 0 50 Fig.1 (g) 100 0 150 0 Fe2O3 50 Fig.1 (h) 100 150 Fe2O3 Plots of Fe2O3 (%) vs. MnO2 Plot of Fe2O3 (%) vs LOI 6 5 4 3 2 1 0 LOI MnO2 14 12 10 8 6 4 2 0 0 Fig.1(i) 0 Fig.1 (j) 50 100 50 100 Fe2O3 150 150 Fe2O3 FIg3.(k to t) Shows binary diagram Fe2O3 Vs SiO2, Al2O3, CaO, MgO, P2O5, Na2O, K2O, TiO2, MnO2, LOI. Fe2O3 is taken as the reference oxide. Relationship Between CIA With Other Shale Oxides Plot CIA Vs Mgo • The chemical index of alteration (CIA) depends on the ratio of Al2O3 to CaO, Na2O and MgO. 0.12 0.1 • If the values of CIA lie in between 50% to 60% then weathering is low, varies from 60% to 75% rock is moderately weathered and if they lie from 75% to 90% then rock is highly weathered. Mgo 0.08 0.06 0.04 0.02 0 85 • In the plot of CIA vs MgO shows increase percentage of CIA with decrease concentration of MgO. From the data it is observed that Mg+2 ions is easily mobilized during weathering. From binary diagram, the values of MgO declines (0.11% to 0.03%) 90 Fig .2 (a) 95 100 CIA Plot CIA Vs P2O5 0.14 0.12 • In the plot of CIA vs P2O5 shows a positive trend indicating that the increase in percentage of CIA with increase concentration of P2O5 are not easily mobilized because of its HFSE behavior. P2O5 0.1 0.08 0.06 0.04 0.02 0 85 Fig .2 (b) 90 95 CIA 100 • k2O PLOT CIA Vs k2O In the plot of CIA vs TiO2, it shows a positive trend indicating that increase of percentage of CIA with increase of TiO2 concentration. 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 85 90 Fig .2 (c) 95 100 95 100 CIA Because Titanium ions are immobilized during weathering. It remains in the rock even when the rock is completely weathered. Plot CIA Vs Na2O Plot CIA Vs TiO2 6 5 4 Na2O • In the plots of CIA vs K2O and Na2O. Both shows a negative trend indicating that increase of weathering with decrease of K2O and Na2O concentrations. The K+ and Na+ ions are easily dissolved and mobilized during excessive weathering. The values of K2O declines 1.7% to 0.1% and Na2O from 1% to 0.3%. TiO2 • 3 2 1 0 85 Fig .2 (d) 90 95 CIA 100 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 85 Fig .2 (e) 90 CIA Depositional Environment 10 • In order to distinguish the tectonic setting of the depositional site of the Upper shale K2O/Na2O vs. SiO2 discrimination diagram (Roser and Korsch, 1986) is used. • All the samples having low silica concentration and K2O/Na2O ratio falls in the field of island arc and continental margin setting. • Calc-alkaline affinity of Bonai volcanic suite (Banerjee, 1982), Bonai Granite (Sen Gupta et al., 1991) and volcanic arc affinity of the Singhbhum Granite which forms the basement and/or intrudes the BIF (Saha, 1994) also support this observation. Passive Margin 1 Active Continental Margin 0.1 Island Arc 0.01 0 10 20 30 40 50 60 70 80 90 100 Fig:4.1. SiO2 vs. Log K2O/Na2O discrimination diagram(after Roser and Korsch, 1986) showing all the studied Iron samples plot in the Island Arc Field. • Alumina is positively correlated with SiO2, K2O, Na2O and MgO, which suggests the major composition of volcaniclastics to be potassium aluminum silicates, and/or sodium aluminum silicates and/or magnesium aluminum silicates. • Alumina also shows a strong positive correlation with titanium in both tuffaceous shale (associated country rock) and in situ Mn ores, indicating their contribution through the volcaniclastics/terrigenous detritus. • Al2O3 is positively correlated with SiO2, Na2O and Mgo and TiO2 like that of associated manganiferrous shale and hence considered as primary depositional. • Partition of minor and trace elements between the Mn oxides and Fe oxides probably took place during diagenesis of the oxides rather than during their deposition. • Preferential enrichment of traces like Li, Co, Ni, Cu, Zn and Pb in Mn oxides during diagenesis is because of diavalent, trivalent, and tetravalent valence state of Mn. • The smaller ionic radius of trivalent Fe and the lesser tendency of Fe to form minerals other than its simple hydroxide and oxides in oxidizing sedimentary and diagenetic environments may explain the lower concentration of many trace elements. • Positive correlations between Mn oxide and Li, Co, Ni, Cu, Zn and Pb and between Fe oxide and Y suggest that trace elements get dissolved during leaching, remobilized and co-precipitated with Mn hydroxides/Fe hydroxides, respectively. • During the process of oxidation and recrystallization, many of the trace elements get expelled from the Mn+4 structure. • Some elements (Ba, Cu, and Zn) desorbed from Fe–hydroxide get into solution and are re-deposited with Mn, As, V and P2O5 showing positive relation with Fe in the insitu ores did not show any significant relationship in remobilized ores, indicating thereby their resistance to dissolution. DISCUSSION • High grade BIF –hosted deposits are the world’s most important source of iron ore. • The loss of silica and redistribution of iron is the result of strong sub-tropical weathering (Cope et al 2008).Hard ores rich in hematite and martite in most of the Indian deposits are believed to have formed during early hydrothermal events (Mukhopadhyay et al. 2008). • Chemical weathering in wet tropical humid-monsoonal climate resulted in extensive supergene modification of these hydrothermally upgraded iron ores to hematite-martite ore (Beukes et al 2008). • Hard hematite-martite ores in Noamundi region was found by hydrothermal replacement of BIF protolith through leaching of silica and introduction of iron by hydrothermal fluids of meteoric origin (Beukes et al. 2008). • The iron ore of Noamundi–Koira can be divided into seven categories. They are massive, hard laminated, soft laminated, martite-goethite, powdery blue dust and lateritic ore. • Although it is more or less accepted that the parent rock of iron ore is BHJ, the presence of disseminated martite in BHJ suggests that the magnetite of protore was converted to martite. • In the first stage, shallow, meteoric fluids affect primary, unaltered BIF by simultaneously oxidizing magnetite to martite and replacing quartz with hydrous iron oxides. • In the second stage of supergene processes, deep burial upgrades the hydrous iron oxides to microplaty hematite. Small and large scale faults and folds similar to those in BIF are also common in the hard laminated ore body. • The porosity of hematite lamina is presented as evidence of leaching of primary silica by alkaline fluids. Which subsequently precipitated ferric hydroxide as a precursor to goethite and eventually hematite (Van Schalkwyk and Beukes 1986). • Removal of silica from BIF and successive precipitation of iron resulted in the formation of martite-goethite ore. Soft laminated ores were formed where precipitation of iron was partial or absent. The leached out space remains with time and the interstitial space is generally filled with kaolinite and gibbsite, which make it low grade. • Massive iron ore are devoid of any lamination and usually associated with BHJ and lower shale. The thickness of the massive ore layer varies with the location. The massive iron ore grades in to well-developed bedded BHJ in depth. • Blue dust occurs in association with BHJ as pockets and layers. Although blue dust and friable ore are both powdery ores, and subjected to variable degree of deformation, leading to the formation of folding, faulting and joints of complex nature produce favourable channels. • Percolating water play an important role in the formation of blue dust and the subterranean solution offers the necessary acidic environment for leaching of quartz from the BHJ. • The dissolution of silica and other alkalis are responsible for the formation of blue dust. The friable and powdery ore on the other hand are formed by soft laminated ore. As it is formed from the soft laminated ore, its alumina content remains high similar to soft laminated ore compared to blue dust. CONCLUSION • From the above discussion it is concluded that, Geochemistry of banded iron formations of the Noamundi-Koira iron ore deposits belongs to Singhbhum-North Orissa Craton Shows that they are detritus- free chemical precipitates. • Presence of intercalated tuffaceous shales point towards genesis of the iron, which could have leached from sea floor by volcanogenic process. Iron and silica of the BIF were provided by the hydrothermal solutions emplaced at the vent sites situated at the Archean Mid-Oceanic Ridges. • Due to thermal and chemical potential variation and upwelling, the iron and silica rich water was transported to the sites of deposition at the shallow shelf. • Increased hydrothermal flux, and higher exit temperature appear responsible for bringing such large quantities of iron and silica into the oceans of Archean Singhbhum-Orissa basins. • Mineralogy study suggests that magnetite was the principal iron oxide mineral, now a relict phase whose depositional history is preserved in BHJ, where it remain in the form of martite. The platy hematite is mainly the product of martite. • The different types of iron ores are intricately related with the BHJ. Hard laminated ores, martite-goethite ore and soft laminated ore are resultant of desilicification process through the action of hydrothermal fluids. • Removal of silica from BIF and successive precipitation of iron by hydrothermal fluids of meteoric origin in the formation of martite-goethtite ore. • The hard laminated ore has been formed in the second steps of supergene processes, where the deep burial upgrades the hydrous iron oxides to hematite. • Soft laminated ores and biscuity ore were formed where precipitation of iron was partial or absent In this case, the leached out space remains with time and the ore becomes very fragile in between the laminae. • Blue dust has been formed owing to circulating waters, which leached away the silica from protore. The presence of martite in massive ore along with their gradational contact of with BHJ suggests its syngenetic origin with BHJ. Table 2: Shows major element constituents of Banded heamatite jasper in Noamundi –Koira iron basin ore deposits of Singhbhum Orissa Craton. Sample Fe2O3 BHJ1 BHJ3 BHJ5 BHJ7 BHJ9 BHJ11 BHJ13 BHJ15 59.5 36.6 49.3 45.75 51.1 51.2 61.5 65.04 47.04 50.49 45.12 45.35 34.52 29.86 35.54 58.2 1.5 1.5 1.5 1.2 2 2.4 2.7 2.5 CaO 0.09 0.16 0.13 0.09 0.19 0.26 0.08 0.2 MgO 0.06 0.09 0.32 0.12 0.16 0.21 0.19 0.19 P2O5 0.0511 0.0549 0.0525 0.045 0.0592 0.0412 0.0323 0.0518 Na2O 0.15 0.13 0.14 0.13 0.15 0.15 0.15 0.15 K2O 0.13 0.06 0.14 0.13 0.07 0.08 0.05 0.08 Total S 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 TiO2 0.058 0.061 0.05 0.035 0.046 0.045 0.061 0.056 MnO2 0.171 0.11 0.154 0.085 0.065 0.055 0.198 0.085 LOI 1.41 1.56 1.25 1.42 1.2 1.82 1.46 1.85 Total 100 100.01 100 100 100 100 100 100 SiO2 Al2O3 Sample Fe2O3 BHJ17 BHJ19 HLO1 HLO3 HLO5 HLO7 SLO1 SLO3 41.4 41.15 95 95.1 96.38 95 89.5 83.64 55.37 53.93 1.53 1.62 0.67 1.65 5.8 7.1 0.7 2.3 1.33 1.4 0.3 1.5 1.8 4.7 CaO 0.19 0.09 0.05 0.05 0.02 0.09 0.11 0.15 MgO 0.23 0.13 0.06 0.09 0.2 0.2 0.06 0.09 P2O5 0.0425 0.0549 0.046 0.022 0.046 0.023 0.046 0.055 Na2O 0.17 0.17 0.0412 0.042 0.0356 0.0462 0.042 0.05 K2O 0.12 0.13 0.078 0.065 0.044 0.052 0.051 0.076 Total S 0.04 0.04 0.042 0.043 0.042 0.043 0.043 0.043 0.056 0.062 0.041 0.042 0.042 0.046 0.047 0.072 SiO2 Al2O3 TiO2 MnO2 0.095 0.028 0.187 0.055 0.055 0.055 0.055 0.055 LOI 1.59 1.92 1.56 1.47 2.17 1.27 2.45 3.97 Total 100 100 99.97 100 100 99.98 100 100 Shows various oxides with iron ore deposits like soft laminated ore, laterite ore, martite- goethite ore, hard laminated ore ,blue dust and different layered shale in Noamundi –Koira basin of iron ore deposits of Singhbhum Orissa Craton. Sample Fe2O3 SLO5 LO1 LO3 LO5 LO7 85.9 55.5 79.11 70.81 SiO2 5.3 18.02 6.42 11.52 Al2O3 4.2 14.89 5.32 CaO 0.06 0.13 MgO 0.07 P2O5 MGO1 MGO5 88.54 87.72 86.38 19.11 4.32 4.36 5.34 9.52 16.57 3.24 3.5 4.65 0.05 0.06 0.08 0.11 0.11 0.098 0.07 0.2 0.07 0.12 0.087 0.093 0.098 0.046 0.096 0.062 0.066 0.969 0.057 0.056 0.065 Na2O 0.054 0.12 0.13 0.143 0.098 0.043 0.053 0.059 K2O 0.068 0.129 0.12 0.072 0.15 0.053 0.056 0.067 Total S 0.043 0.074 0.044 0.061 0.065 0.041 0.043 0.044 TiO2 0.059 0.86 0.625 0.612 0.852 0.043 0.045 0.053 MnO2 0.055 0.211 0.11 0.084 0.211 0.167 0.198 0.128 4.1 9.8 7.8 6.97 8.2 3.23 3.7 3 99.97 99.9 99.99 99.99 99.93 99.93 99.93 99.98 LOI Total 53.5 MGO3 Sample Fe2O3 BD1 BD3 BD5 US1 US3 US5 MS1 MS3 94.55 95.86 91.36 18.7 18.83 15.95 50.25 54.12 SiO2 1.89 1.75 4.18 20.69 22.93 28.93 16.7 12.46 Al2O3 1.23 0.55 2.14 33.02 29.84 38.12 23.18 21.89 CaO 0.02 0.02 0.02 0.178 0.19 0.167 0.013 0.012 MgO 0.2 0.2 0.2 0.041 0.031 0.036 0.052 0.065 P2O5 0.046 0.046 0.046 0.073 0.08 0.117 0.055 0.057 Na2O 0.054 0.042 0.061 0.343 0.355 0.321 0.529 0.437 K2O 0.065 0.076 0.068 0.246 0.204 0.284 0.02 0.13 Total S 0.038 0.041 0.044 0.043 0.085 0.04 0.04 0.04 TiO2 0.051 0.045 0.058 3.68 5.58 3.31 0.59 0.72 MnO2 0.045 0.045 0.045 5.015 4.047 0.935 0.056 0.057 1.8 1.3 1.7 10.21 11.55 10.3 8.4 9.9 99.99 99.98 99.92 92.24 93.72 98.51 99.89 99.89 LOI Total Sample Fe2O3 MS5 LS1 LS3 LS5 45.6 27.82 25.46 24.7 SiO2 18.4 39.67 45.14 43.93 Al2O3 23.97 19.16 19.52 18.6 CaO 0.16 0.137 0.144 0.186 MgO 0.058 0.087 0.083 0.075 P2O5 0.05 0.048 0.053 0.055 Na2O 0.535 0.81 0.871 0.932 K2O 0.129 1.84 0.129 1.11 Total S 0.04 0.04 0.04 0.04 TiO2 0.96 0.94 1.05 1.68 0.068 0.043 0.049 0.014 9.9 9.32 7.36 8.63 99.87 99.92 99.9 99.95 MnO2 LOI Total Table (continued). CIA of various oxides Sample CIA Sio2 Al2o3 Cao Mgo P2O5 Na2O k2O Tio2 Mn02 LoI US1 97.7 20.69 33.02 0.178 0.041 0.073 0.343 0.246 3.68 5.015 10.21 US2 98 27.63 33.67 0.056 0.041 0.057 0.366 0.235 3.63 0.253 12.32 US3 97.5 22.93 29.84 0.19 0.031 0.08 0.355 0.204 5.58 4.047 11.55 US4 97.8 23.24 35.66 0.163 0.045 0.082 0.324 0.304 5.43 1.215 12.53 US5 98 28.93 38.12 0.167 0.036 0.117 0.321 0.284 3.31 0.935 10.3 MS1 97.6 16.7 23.18 0.013 0.052 0.055 0.529 0.02 0.59 0.056 8.4 MS2 96.8 15.5 22.11 0.021 0.051 0.117 0.524 0.17 0.55 0.021 8.9 MS3 97.4 12.46 21.89 0.012 0.065 0.057 0.437 0.13 0.72 0.057 9.9 MS4 97.6 16.6 25.13 0.032 0.052 0.055 0.432 0.13 0.89 0.071 10.2 MS5 96.6 18.4 23.97 0.16 0.058 0.05 0.535 0.129 0.96 0.068 9.9 LS1 87.3 39.67 19.16 0.137 0.087 0.048 0.81 1.84 0.94 0.043 9.32 LS2 91.6 41.83 20.2 0.066 0.064 0.055 0.71 1.07 1.21 0.027 8.12 LS3 94.4 45.14 19.52 0.144 0.083 0.053 0.871 0.129 1.05 0.049 7.36 LS4 90.7 44.03 18.452 0.126 0.098 0.057 0.951 0.811 1.06 0.038 7.63 LS5 89.3 43.93 18.6 0.186 0.075 0.055 0.932 1.11 1.68 0.014 8.63 LS6 90.4 44.29 17.08 0.151 0.082 0.073 0.754 0.905 1.58 0.056 8.565 REFERENCES Alibert C and McCulloch M T 1993 Rare earth and neodymium composition of the Banded Iron Formation and associated Shales from the Hamersley, Western Australia;Geochim Cosmochim.Acta 57,187-204. 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