A mixed seawater and hydrothermal origin of superior-type banded iron formation (BIF)-hosted Kouambo iron deposit,Palaeoproterozoic Nyong series,Southwestern Cameroon: Constraints from petrography and geochemistry

The Kouambo iron deposit contains banded iron formations (BIFs) and is located in the northwestern margin of the Congo craton. The BIFs are hosted in Palaeoproterozoic Nyong series, a dominantly metasedimentary formations, which were metamorphosed into greenschist to granulite facies. The Kouambo BIFs are medium- to coarse-grained banded rocks consisting of alternation of Si-rich and Fe-rich mesobands, and belong to oxide facies iron formations. Geochemistry analyses reveal that these iron formations are composed of > 96 wt% Fe₂O₃ and SiO₂ and have low concentrations of Al₂O₃, TiO₂ and trace HFSE, suggesting chemical precipitates of silica and iron. Moreover, these BIFs have low concentrations of Al₂O₃, TiO₂ and trace HFSEs (high field strength elements, e.g., Zr, Hf, Ta, Pb and Th), suggesting that terrigenous detrital materials contributed insignificantly to the sedimentation. The Post-Archean Australian Shale (PAAS)-normalized REE-Y patterns display seawater-like profile: minor LREE depletion and HREE enrichment, positive Y anomalies. However, they display positive Eu and negative Ce anomalies, and low Y/Ho ratio (average 29), which suggest the influence of the hydrothermal fluids. The weak positive Eu/Eu*(_PAAS) ratio (average 1.5), associated with the low V (17.5 ppm), Co (6.1 ppm) and Ni (27.5 ppm) contents similar to other Superior-type BIFs worldwide, are consistent with the deposition of the Kouambo BIFs in continental marginal sea or back-arc basin environment. In summary, the Kouambo BIFs show a seawater-like REE + Y signature, however, the positive Eu anomalies and reduced Y/Ho ratios relative to seawater indicates a possible mixing with hydrothermal fluids (∼ 0.5%).     

Precambrian iron formations from the Cauvery Suture Zone,Southern India: Implications for sub-marine hydrothermal origin in Neoarchean and Neoproterozoic convergent margin settings

Thick horizons of iron formations including Banded Iron Formations (BIFs) and Banded Silicate Formations (BSFs) occur as E–W trending bands in the eastern part of Cauvery Suture Zone (CSZ) in the Sothern Granulite Terrane of India. Some of these occur in close association with the Neoarchean-Neoproterozoic suprasubduction zone complexes, where as some others are associated with metamorphosed accretionary sequences including pyroxene granulites and other high grade rocks. The iron formations are highly deformed and metamorphosed under amphibolite to granulite facies conditions and are composed of quartz–magnetite–hematite–goethite–garnet–pyrite together with grunerite and pyroxene. Here we report the geochemical characteristics of twenty representative samples from the iron formations that reveal a widely varying composition with Fe₂O₃^(t) (22–65 wt.% as total iron) total- Fe₂O₃/TiO₂ (205–6532), MnO/TiO₂ (0.25–12.66) and SiO₂ (33–85 wt.%), broadly representing the two types of iron formations. These formations also show very low Al/(Al + Fe + Mn) ratio (0.001–0.01), Al₂O₃ (0.07–0.76 wt.%), Al₂O₃/TiO₂ ratio (2.7–21), MgO (0.01–4.41 wt.%), CaO (0.1–1.24 wt.%), Na₂O (0.01–0.05 wt.%) and K₂O (0.01 wt.%) together with low total REE (3.38–31.63 ppm). The trace and REE elemental distributions show wide variation with high Ni (274 ppm), and Zn contents (up to 87 ppm) when compared to mafic volcanics of the adjoining areas. Tectonic discrimination plots indicate that the iron formations of the Cauvery Suture Zone are of hydrothermal origin. Their chondrite normalized patterns show slight positive Eu anomaly (Eu/Eu* = up to 1.77) and relatively less fractionation of REE with slight LREE enrichment compared to HREE. However, the PAAS (Post Archean Average of Australian Sediments) normalized REE patterns display significant positive Eu anomaly (Eu/Eu* up to 2.32) with well represented negative Ce anomalies (Ce/Ce* = 0.66–1.28). The above results together with petrological characteristics and available geochronology of the associated lithologies suggest that the iron formations can be correlated to Algoma-type. The Fe and Si were largely supplied by medium to high temperature sub-marine hydrothermal systems in Neoarchean and Neoproterozoic convergent margin settings.     

The composition and genesis of the Mesoarchean Dagushan banded iron formation (BIF) in the Anshan area of the North China Craton

The Dagushan BIF-hosted iron deposit in the Anshan–Benxi area of the North China Craton (NCC) has two types of iron ore: quartz–magnetite BIF (Fe₂O₃^T < 57 wt.%) and high-grade iron ore (Fe₂O₃^T > 90 wt.%). Chlorite-quartz schist and amphogneiss border the iron orebodies and are locally present as interlayers with BIFs; chlorite-quartz schist and BIFs are enclosed by amphogneiss in some locations. The quartz–magnetite BIFs are enriched in HREEs (heavy rare earth elements) with positive La, Eu and Y anomalies, indicating their precipitation from marine seawater with a high-temperature hydrothermal component. Moreover, these BIFs have low concentrations of Al₂O₃, TiO₂ and HFSEs (high field strength elements, e.g., Zr, Hf and Ta), suggesting that terrigenous detrital materials contributed insignificantly to the chemical precipitation. The high-grade iron ores exhibit similar geochemical signatures to the quartz–magnetite BIFs (e.g., REE patterns and Y/Ho ratios), implying that they have identical sources of iron. However, these ores have different REE (rare earth element) contents and Eu/Eu* values, and the magnetites contained within them exhibit diverse REE contents and trace element concentrations, indicating that the ores underwent differing formation conditions, and the high-grade ores are most likely the reformed product of the original BIFs.The chlorite-quartz schist and amphogneiss are characterized by high SiO₂ and Al₂O₃ contents and exhibit variable abundances of REEs, enrichment in LREEs (light rare earth elements), negative anomalies in HFSEs (e.g., Nb, Ta, P and Ti) and positive anomalies in LILEs (large ion lithophile elements, e.g., Rb, Ba, U and K). A protolith reconstruction indicates that the protoliths of the chlorite-quartz schist are felsic volcanic rocks. SIMS and LA-ICP-MS zircon U–Pb dating indicate that this schist formed at approximately 3110 to 3101 Ma, which could represent the maximum deposition age of the Dagushan BIF. However, two groups of zircons from the amphogneiss are identified: 3104 to 3089 Ma zircons that are most likely derived from the chlorite-quartz schist and 2997 to 2995 Ma zircons, which are interpreted to represent the time of protolith crystallization. Thus, the Dagushan BIF most likely formed before 2997 to 2995 Ma. The ~ 3.1 Ga zircons yield ε_Hf(t) values of − 8.07 to 5.46, whereas the ~ 3.0 Ga zircons yield ε_Hf(t) values of − 3.96 to 2.09. These geochemical features suggest that the primitive magmas were derived from the depleted mantle with significant contributions of ancient crust.     

Petrology and geochemistry of the banded iron-formations from Ntem complex greenstones belt,Elom area,Southern Cameroon: Implications for the origin and depositional environment

Banded iron-formations (BIFs) form an important part of the Archaean to Proterozoic greenstone belts in the Southern Cameroon. In this study, major, trace and REE chemistry of the banded iron-formation are utilized to explore the source of metals and to constraint the origin and depositional environment of these BIFs. The studied BIF belongs to the oxide facies iron formations composed mainly of iron oxide (mainly magnetite) mesobands alternating with quartz mesobands. The mineralogy of the BIF sample consists of magnetite and quartz with lesser amount of secondary martite, goethite and trace of gibbsite and smectite. The major element chemistry of these iron-formations is remarkably simple with the main constituents being SiO₂ and Fe₂O₃ which constitute 95.6–99.5% of the bulk rock. Low Al₂O₃, TiO₂, and HFSE concentrations show that they are relatively detritus-free chemical sediments. The Pearson’s correlation matrix of major element reveals that there is a strong positive correlation (r = 0.99) of Al with Ti and no to weak negative correlation of Ti with Mn, Ca and weak positive correlation of Si with Ca, suggesting the null to very minor contribution of detrital material to chemical sediment. The trace elements with minor enrichments are transition metals such as Zn, Cr, Sr, V and Pb. This is an indicator of direct volcanogenic hydrothermal input in chemical precipitates. The studied BIF have a low ΣREE content, ranging between 0.41 and 3.22 ppm with an average of 0.87 ppm, similar to that of pure chemical sediments. The shale-normalized patterns show depletion in light REE, slightly enrichment in heavy REE and exhibit weak positive europium anomalies. These geochemical characteristics indicate that the source of Fe and Si was the result of deep ocean hydrothermal activity admixed with sea water. The absence of a large positive Eu anomaly in the studied BIF indicates an important role of low-temperature hydrothermal solutions. The chondrite-normalized REE patterns are characterized by LREE-enriched (Mean La_CN/Yb_CN = 8.01) and HREE depletion (Mean Tb_CN/Yb_CN = 1.61) patterns and show positive Ce anomalies. With the exception of one sample (LBR133), all of the BIF samples analyzed during this study have positive Ce anomalies on both chondrite- and PASS-normalized plots. This may indicate that the BIFs within the Elom area were formed within a redox stratified ocean. The positive Ce anomalies in the studied samples likely suggest that the basin in which Fe formations were deposited was reducing with respect to Ce, probably in the suboxic or anoxic seawaters.     

Negative Ce Anomaly in the Indian Banded Iron Formations: Evidence for the Emergence of Oxygenated Deep-Sea at 2.9-2.7 Ga

Abstract: Major and rare earth element contents are reported for Late Archean banded iron formations (BIFs) in the Bababudan Group of the Dharwar Craton, South India. The BIFs are mostly composed of SiO₂ (average1ρ = 54.88.1 wt%) and Fe₂O₃* (44.38.2 wt%). The Al₂O₃ and TiO₂ contents are remarkably low, suggesting that detrital components were starved during the BIF deposition. The BIFs have a LREE-enriched pattern with a relatively high (La/Yb)_N (6.644.07). Total REE concentrations (RE) vary from 5.2 to 65.3 ppm. The REE patterns are characterized by the presence of a very large negative Ce anomaly (Ce/Ce*: 0.13-0.83) and a positive Eu anomaly (Eu/Eu*: 0.96-2.45). The Eu/Eu* decreases and (La/Yb)_N increases with a increase of RE. These correlations of REE indices are similar to those of modern hydrothermal iron-rich sediments near a mid-ocean ridge (MOR). Greenstones associated with the BIFs have MORB-like geochemical features. These geochemical and geological lines of evidence indicate that the depositional site of the BIFs was remote from a continent and/or island arc and that the BIFs were in situ hydrothermal sediments near a MOR. A striking negative Ce anomaly in the BIFs indicates that oxygenated deep-sea environments emerged at 2.9-2.7 Ga. The existence of contemporaneous Mn deposits in the Dharwar Craton supports this assertion. Our scenario of oxygen in the Earth's surface of the Late Archean is different from long-held notion that the atmosphere and ocean were persistently anoxic throughout the Archean.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

Precambrian banded iron formations in the North China Craton: Silicon and oxygen isotopes and genetic implications

Banded iron formations (BIFs) are Precambrian chemical marine sedimentary formations that record major transitions of chemical composition, and oxidation–reduction state of oceans at the time of their deposition. In this paper, we report silicon and oxygen isotope compositions of a variety of BIFs from the North China Craton (NCC) in order to deduce the mechanism of their formation. Quartz in the various types of BIFs from the NCC are generally depleted in ³⁰Si, where δ³⁰Si_NBS-28 values range from − 2.0‰ to − 0.3‰ (average, − 0.8‰), similar to δ³⁰Si_NBS-28 values measured from modern submarine black chimneys and sinters. The δ¹⁸O_V-SMOW values of quartz in the BIFs are relatively high (8.1‰–21.5‰; average, 13.1‰), similar to those of siliceous rock formed by hydrothermal activities. The δ³⁰Si_NBS-28 values of quartz in magnetite bands are commonly lower than those of quartz in adjacent siliceous bands within the same sample, whereas δ¹⁸O_V-SMOW values are higher in the magnetite bands. A negative correlation is observed between δ³⁰Si_NBS-28 and δ¹⁸O_V-SMOW values of quartz from siliceous and magnetite bands in BIF from Fuping, Hebei Province. The isotopic compositions of silicon and oxygen of quartz in BIFs provide insights for the formation mechanisms of silicon–iron cyclothems in BIFs. After the silicon- and iron-rich hydrothermal solution was injected onto the seabed, the abrupt temperature drop caused oversaturation of silicic acid, resulting in rapid precipitation of SiO₂ and deposition of siliceous layers. Ferric hydroxide was precipitated later than SiO₂ because of low free-oxygen concentration in the ocean bottom. Progressive mixing of hydrothermal solution with seawater caused a continuous drop in temperature and an increase in Eh values, resulting in gradual oxidation of hydrothermal Fe^2 + and deposition of iron-rich layers. In summary, each silicon–iron cyclothem marks a large-scale submarine hydrothermal exhalation. The periodic nature of these exhalations resulted in the formation of regular silicon–iron cyclothems. The widespread distribution of BIFs indicates that volcanism and submarine hydrothermal exhalation were extensive; the low δ³⁰Si_NBS-28 and high δ¹⁸O _V-SMOW values of the BIFs indicate that the temperature of seawater was relatively high at the time of BIF formation, and that concentrations of Fe^2 + and H₄SiO₄ in seawater were saturated.     

Changes of Ge/Si,REE + Y and SmNd isotopes in alternating Fe- and Si-rich mesobands reveal source heterogeneity of the ~ 2.54 Ga Sijiaying banded iron formation in Eastern Hebei,China

The North China Craton (NCC) is one of the most important regions hosting abundant banded iron formations (BIFs). The ~ 2.54 Ga Sijiaying BIF, the best-preserved and most extensive deposit in Eastern Hebei, is intercalated and closely associated with meta-volcanic rocks of the Luanxian Group. In this context, major and trace element and SmNd isotopic analyses of individual mesobands of a Sijiaying BIF specimen were conducted to characterize the source and depositional environment over a transient period.Low Al₂O₃, TiO₂ and high field strength elements (HFSEs) concentrations show that the BIF is relatively detritus-free. Shale-normalized rare earth and yttrium distributions (REE + Y) of individual BIF mesobands exhibit positive La anomalies, enrichment in HREE relative to LREE and MREE and suprachondritic Y/Ho ratios, which are typical features of marine waters throughout the Archean and Proterozoic. The presence of consistently positive Eu anomalies indicates a significant high-T hydrothermal input, while the absence of true Ce anomalies suggests deposition from an anoxic water column. By comparison with other typical BIFs (e.g., the Isua BIF from Greenland; the Kuruman BIF from South Africa), the Sijiaying BIF is depleted in HREE, and appears to record variations in solute fluxes related to changing intensities of hydrothermal activity. These features, coupled with SmNd isotopic relations and Ge/Si distributional patterns, point to two decoupled sources controlling the depositional environment of the BIF and thus reveal source heterogeneity for silica and iron of the Sijiaying BIF. High Fe fluxes were associated with seafloor-vented hydrothermal fluids, which received their SmNd isotopic signature from alteration of depleted oceanic crust; whereas significant amounts of silica were associated with ambient seawater whose REE signature was controlled by solutes derived from weathering of nearby Mesoarchean continental landmasses. The old (up to ~ 3.0 Ga) Nd (T_DM) model ages of Si-rich mesobands of the BIF support such a scenario.     

Mineralogy,geochemistry and the origin of high-phosphorus oolitic iron ores of Aswan,Egypt

The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe₂O₃, the studied iron ores show relatively high contents of SiO₂ and Al₂O₃ due to the abundance of quartz and chamosite. P₂O₅ ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO₂, Al₂O₃, and TiO₂ suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P₂O₅ indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)_N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO_2, and Al₂O₃ around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO₂ and Al₂O₃, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.     

Petrography and geochemistry of the Shilu Fe–Co–Cu ore district,South China: Implications for the origin of a Neoproterozoic BIF system

The Shilu Fe–Co–Cu ore district is situated in the western Hainan Province of south China. This district consists of the upper Fe-rich layers and the lower Co–Cu ores, which are mainly hosted within the Neoproterozoic Shilu Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Three facies of metamorphosed BIFs, the oxide, the silicate–oxide and the sulfide–carbonate–silicate, have been identified within the Shilu Group. The oxide banded iron formation (BIF) facies (quartz itabirites or Fe-rich ores) consists of alternating hematite-rich and quartz-rich microbands. The silicate–oxide BIF facies (amphibolitic itabirites or Fe-poor ores) comprises alternating millimeter to tens of meter scale, magnetite–hematite-rich bands with calc-silicate-rich macro- to microbands. The sulfide–carbonate–silicate BIF facies (Co–Cu ores) contain alternating cobaltiferous pyrite, cobaltiferous pyrrhotite and chalcopyrite macrobands to microbands mainly with dolomite–calcite, but also with minor sericite–quartz bands. Blasto-oolitic, pelletoidal, colloidal, psammitic, and cryptocrystalline to microcrystalline textures, and blasto-bedding structures, which likely represent primary sedimentation, are often observed in the Shilu BIF facies.The Shilu BIFs and interbedded host rocks are generally characterized by relatively low but variable ∑ REE concentrations, LREE depletion and/or MREE enrichment relative to HREE, and no Ce, Gd and Eu anomalies to strongly positive Ce, Gd and Eu anomalies in the upward-convex PAAS-normalized REY patterns, except for both the banded or impure dolostones with nil Ce anomaly to negative Ce anomalies and negative La anomalies, and the minor sulfide–carbonate–silicate BIF facies with moderately negative Eu anomalies. They also contain relatively low but variable HFSE abundances as Zr, Nb, Hf, Th and Ti, and relatively high but variable abundances of Cu, Co, Ni, Pb, As, Mn and Ba. The consistently negative ε_Nd(t) values range from − 4.8 to − 8.5, with a T_DM age of ca. 2.0 Ga. In line with the covariations between Al₂O₃ and TiO₂, Fe₂O₃ + FeO and SiO₂, Mn and Fe, Zr and Y/Ho and REE, and Sc and LREE, the geochemical and Sm–Nd isotopic features suggest that the precursors to the Shilu BIFs formed from a source dominated by seafloor-derived, high- to low temperature, acidic and reducing hydrothermal fluids but with variable input of detrital components in a seawater environment. Moreover, the involved detrital materials were sourced dominantly from an unknown, Paleoproterozoic or older crust, with lesser involvement from the Paleo- to Mesoproterozoic Baoban Group underlying the Shilu Group.The Shilu BIFs of various facies are interpreted to have formed in a shallow marine, restricted or sheltered basin near the rifted continental margin most likely associated with the break-up of Rodinia as the result of mantle superplume activity in South China. The seafloor-derived, periodically upwelling metalliferous hydrothermal plume/vent fluids under anoxic but sulfidic to anoxic but Fe^2 +-rich conditions were removed from the plume/vent and accumulated in the basin, and then variably mixed with terrigenous detrital components, which finally led to rhythmic deposition of the Shilu BIFs.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

Geochemistry and genesis of the banded iron formations of the Cauê Formation,Quadrilátero Ferrífero,Minas Gerais,Brazil

The Cauê Formation of the Paleoproterozoic Minas Supergroup hosts banded iron formations (BIFs), locally called itabirites, deposited in shallow marine passive margin settings. Two major compositional types of itabirite, dolomitic and quartz itabirites, are found in the northwestern part of QF. The former consists of alternating dolomite-rich and hematite-rich bands, whereas the latter is formed with alternating quartz-rich and hematite-rich bands. Accessory minerals are chlorite, sericite, and apatite in both types.Dolomitic and quartz itabirites have a very simple chemical composition. In the dolomitic itabirite, Fe₂O₃ plus CaO, MgO, and LOI range from 95.8 to 97.8%, while in the quartz itabirite, Fe₂O₃ plus SiO₂ range from 94.4 to 99.6%. Both itabirites are highly oxidized and present Fe³⁺/(Fe²⁺ + Fe³⁺) ratios higher than 0.98, by far superior than the average ratios of Paleoproterozoic BIFs. Trace element concentrations in itabirites are very low, ranging from <10 to 55 ppm. Dolomite shows negative δ¹³C values varying from −2.5 to −0.8‰ versus PDB, while the oxygen isotope data display δ¹⁸O values varying from −12.4 to −8.5‰ versus PDB. The δ¹³C values of the dolomitic itabirite are in the same range of those of the overlying stromatolitic dolomites of the Gandarela Formation. C and O isotopes, REE signatures, and Y/Ho ratios suggest a marine origin for the sediments of the Cauê Formation. The HREE enrichment pattern exhibited by the itabirites shows a modern seawater REE signature overprinted by a hydrothermal pattern marked by positive Eu anomalies. Very low contents of Al₂O₃ and TiO₂ and a strong positive correlation between them indicate a minor terrigenous component in the chemically-precipitated marine sediments of the Cauê Formation. Differences in the HREE signatures of itabirites suggest that dolomitic itabirite precipitated in shallower waters receiving sediments from the continent, while quartz itabirite precipitated in deeper waters. Sea-level fluctuations caused by marine transgression–regressions possibly contributed to changes in the composition and varied input of the terrigenous sediments. These changes are expressed by the co-existence of dolomitic, quartz, and amphibolitic itabirites in the Cauê Formation, which represent lateral and vertical facies transitions of dolomitic, cherty, and shaly BIFs, respectively.     

Geochemistry of late Archaean metagreywackes from the Western Dharwar Craton,South India: Implications for provenance and nature of the Late Archaean crust

Late Archaean metagreywackes of the Ranibennur Formation, Dharwar Supergroup, in the Dharwar–Shimoga schist belt of the Western Dharwar Craton (WDC) are texturally and mineralogically immature of the quartz-intermediate type. The SiO₂ content in them ranges from 60.58 to 65.26 wt.%. Chemical Index of weathering (CIW) values varies between 50 and 65. 4 indicating a low degree of chemical alteration of the provenance rocks. A high degree of correlation between K₂O and Al₂O₃ (r = ? 0.73) and low Rb/Sr ratios also suggest a low degree of alteration of provenance rocks. Abundances of transition group elements (Cr = 118–221; N = 89–154; V = 89–192 and Sc = 11–16 ppm) as well Zr (132–191 ppm) suggest a mixed mafic–felsic provenance for the metagreywackes. Low HREE and Y content, and low Tb/Yb ratios (0.23–0.41) suggest the presence of tonalite as an important component in the provenance areas. Values of Eu/Eu?(0.78) and Th/Sc (0.55) suggest that the granodioritic upper crust had evolved prior to serving as the provenance. Mixing calculations suggest 50–55 vol.% tonalite, 20–25 vol.% granite, 18–20 vol.% basalt and ~ 5 vol.% komatiite composition for the provenance. Geochemical characteristics of the Ranibennur metagreywackes suggest that sedimentary basin formed in the vicinity of a magmatic arc in a continental island arc setting, and the detritus were shed from the arc rock.     

Geology, geochemistry and genesis of BIF of Kushtagi schist belt, Archaean Dharwar Craton, India

The Banded Iron-Formation (BIF) of the Kushtagi schist belt, Dharwar Craton is interbedded with metavolcanics. The oxide fades cherty (Al₂O₃ < 2%) and shaley (Al₂O₃ > 2%) BIFs show large-scale variations in their major and trace elements abundance. Cherty Banded Iron-Formation (CBIF) is depleted in Al₂O₃, TiO₂, Zr, Hf and other trace elements like Cr, Ni, Co, Rb, Sr, V, Y and REE in comparison to Shaley Banded Iron-Formation (SBIF). Depleted REE, positive Eu anomalies and the flat to HREE-enriched pattern of CBIF indicate that Fe and SiO₂ for these BIFs were added to ambient ocean water by hydrothermal solutions at the AMOR vent sites. It is inferred that the higher amount of hydrothermal fluid flux with a higher exit temperature provided enormous quantities of iron and silica. Fine-grained sedimentation in the basin gave rise to the observed variability in the composition of BIF. During transgression a wave base was raised up, consequently deposition of CBIF became possible, whereas, during the regressive stage, these chemical sediments were buried by and/or mixed with the terrigenous sediments resulting in deposition of SBIF and interbedded shales. Volcaniclastic activity within the basin appears to have contributed significantly to the composition of some SBIF and shales. The hydrothermal exhalative hypothesis combined with the Archaean miniplate model explains most of the chemical features of the BIFs of greenstone belts.     

冀东、五台和吕梁地区条带状铁矿的稀土元素特征及其地质意义

详细报道了冀东、五台和吕梁地区条带状铁矿全岩样品的稀土元素分析结果。结果表明,研究区BIF具有非常相似的特征：稀土总量均较低;经页岩标准化的稀土元素配分模式均呈现轻稀土亏损、重稀土富集的特征;Y/Ho比值较高;具有明显的Eu、Y、La的正异常,且这些特征表明研究区BIF的稀土元素来源于火山热液和海水的混合溶液。虽然BIF均显示Eu正异常,但不同类型、不同沉积年龄BIF的铕异常程度不同：与吕梁地区Superior型铁矿相比,冀东和五台地区的Algoma型铁矿显示了更大的Eu正异常;并且自中太古代-新太古代-古元古代,BIF的铕正异常逐渐减小,这可能反映了随着BIF沉积年龄的减小,进入到该地区海水中的高温热液流体逐渐减少;同时,研究区BIF缺乏明显的Ce负异常,可能暗示在BIF沉积时海水的氧化还原状态为缺氧环境。     

http://www.sciencedirect.com/science/article/pii/S1674987112001478

REE composition of the carbonates of the auriferous quartz carbonate veins (QCVs) of the Neoarchean Ajjanahalli gold deposit, Chitradurga schist belt, Dharwar Craton, is characterized by U-shaped chondrite normalized REE patterns with both LREE and HREE enrichment and a distinct positive Eu anomaly. As positive Eu anomaly is associated with low oxygen fugacity, we propose that the auriferous fluids responsible for gold mineralization at Ajjanahalli could be from an oxygen depleted fluid. The observed positive Eu anomaly is interpreted to suggest the derivation of the auriferous fluids from a mantle reservoir. The location of Ajjanahalli gold deposit in a crustal scale shear zone is consistent with this interpretation.     

Continental lithospheric evolution: Constraints from the geochemistry of felsic volcanic rocks in the Dharwar Craton,India

Felsic magmatism associated with ocean–ocean and ocean–continent subduction processes provide important evidence for distinct episodes of crust-generation and continental lithospheric evolution. Rhyolites constitute an integral component of the tholeiitic to calc-alkaline basalt–andesite–dacite–rhyolite (BADR) association and contribute to crustal growth processes at convergent plate margins. The evolution of the Dharwar Craton of southern peninsular India during Meso- to Neoarchean times was marked by extensive development of greenstone belts. These granite-greenstone terranes have distinct volcano-sedimentary associations consistent with their geodynamic setting. The present study deals with geochemistry of rhyolites from the Chitradurga-Shimoga greenstone belts of western (WDC) and the Gadwal-Kadiri greenstone belts of eastern (EDC) sectors of Dharwar Craton to compare and evaluate their petrogenesis and geodynamic setting and their control on the continental lithospheric evolution of the Dharwar Craton. At a similar range of SiO₂, Al₂O₃, Fe₂O₃, the rhyolites of WDC are more potassic, whereas the EDC rhyolites are more sodic and less magnesian with slight increase in TiO₂. Minor increase in MgO content of WDC rhyolites reflects their ferromagnesian trace elements which are comparatively lower in the rhyolites of EDC. The relative enrichment in LILE (K, Rb) and depletion in HFSE (Nb, Ta, Zr, Hf) marked by negative Nb–Ta, Zr–Hf and Ti anomalies endorse the convergent margin processes for the generation of rhyolites of both the sectors of Dharwar Craton. The high silica potassic rhyolites of Shimoga and Chitradurga greenstone belts of WDC showing prominent negative Eu and Ti anomalies, flat HREE patterns correspond to Type 3 rhyolites and clearly point towards their generation and emplacement in an active continental margin environment. The geochemical characteristics of Gadwal and Kadiri rhyolites from eastern Dharwar Craton marked by aluminous compositions with low and fractionated HREE patterns and minor negative Eu anomalies are in conformity with Type 1 rhyolites and suggest that they were erupted in an intraoceanic island arc system. The overall geochemical systematics of the rhyolites from both the sectors of Dharwar Craton suggest a change in the geodynamic conditions from intraoceanic island arc of eastern Dharwar Craton and an active continental margin of western Dharwar marked by ocean–ocean subduction and migration of oceanic arc towards a continent followed by arc-continent collision that contributed for the evolution of continental lithosphere in the Dharwar Craton.     

Geochemistry of black shales from the Lower Cretaceous Paja Formation,Eastern Cordillera,Colombia: Source weathering,provenance, and tectonic setting

The major and trace element characteristics of black shales from the Lower Cretaceous Paja Formation of Colombia are broadly comparable with those of the average upper continental crust. Among the exceptions are marked enrichments in V, Cr, and Ni. These enrichments are associated with high organic carbon contents. CaO and Na₂O are strongly depleted, leading to high values for both the Chemical Index of Alteration (77–96) and the Plagioclase Index of Alteration (86–99), which indicates derivation from a stable, intensely weathered felsic source terrane. The REE abundances and patterns vary considerably but can be divided into three main groups according to their characteristics and stratigraphic position. Four samples from the lower part of the Paja Formation (Group 1) are characterized by LREE-enriched chondrite-normalized patterns (average La_N/Yb_N = 8.41) and significant negative Eu anomalies (average Eu/Eu¹ = 0.63). A second group of five samples (Group 2), also from the lower part, have relatively flat REE patterns (average La_N/Yb_N = 1.84) and only slightly smaller Eu anomalies (average Eu/Eu¹ = 0.69). Six samples from the middle and upper parts (Group 3) have highly fractionated patterns (average La_N/Yb_N = 15.35), resembling those of Group 1, and an identical average Eu/Eu¹ of 0.63. The fractionated REE patterns and significant negative Eu anomalies in Groups 1 and 3 are consistent with derivation from an evolved felsic source. The flatter patterns of Group 2 shale and strongly concave MREE-depleted patterns in two additional shales likely were produced during diagenesis, rather than reflecting more mafic detrital inputs. An analysis of a single sandstone suggests diagenetic modification of the REE, because its REE pattern is identical to that of the upper continental crust except for the presence of a significant positive Eu anomaly (Eu/Eu¹ = 1.15). Felsic provenance for all samples is suggested by the clustering on the Th/Sc–Zr/Sc and Gd_N/Yb_N–Eu/Eu¹ diagrams. Averages of unmodified Groups 1 and 3 REE patterns compare well with cratonic sediments from the Roraima Formation in the Guyana Shield, suggesting derivation from a continental source of similar composition. In comparison with modern sediments, the geochemical parameters (K₂O/Na₂O, La_N/Yb_N, La_N/Sm_N, Eu/Eu¹, La/Sc, La/Y, Ce/Sc) suggest the Paja Formation was deposited at a passive margin. The Paja shales thus represent highly mature sediments recycled from deeply weathered, older, sedimentary/metasedimentary rocks, possibly in the Guyana Shield, though Na-rich volcanic/granitic rocks may have contributed to some extent.     

Relationships between major and trace elements during weathering processes in a sedimentary context: Implications for the nature of source rocks in Douala,Littoral Cameroon

In Douala (Littoral Cameroon), the Cretaceous to Quaternary formation composed of marine to continental sediments are covered by ferrallitic soils. These sediments and soils have high contents of SiO₂ (≥70.0 wt%), intermediate contents of Al₂O₃ (11.6–28.4 wt%), Fe₂O₃ (0.00–20.5 wt%) and TiO₂ (0.04–4.08 wt%), while K₂O (≤0.18 wt%), Na₂O (≤0.04 wt%), MgO (≤0.14 wt%) and CaO (≤0.02 wt%) are very low to extremely low. Apart from silica, major oxides and trace elements (REE included) are more concentrated in the fine fraction (<62.5 μm) whose proportions of phyllosilicates and heavy minerals are significant. The close co-associations between Zr, Hf, Th and ∑REE in this fraction suggest that REE distribution is controlled by monazite and zircon. CIA values indicate intense weathering. Weathering products are characterized by the association Al₂O₃ and Ga in kaolinite; the strong correlation between Fe₂O₃ and V in hematite and goethite; the affinity of TiO₂ with HFSE (Hf, Nb, Th, Y and Zr) in heavy minerals. The ICV values suggest mature sediments. The PCI indicates a well-drained environment whereas U/Th and V/Cr ratios imply oxic conditions. La/Sc, La/Co, Th/Cr, Th/Sc and Eu/Eu* elemental ratios suggest a source with felsic components. Discrimination diagrams are consistent with the felsic source. The REE patterns of some High-K granite and granodiorite of the Congo Craton resemble those of the samples, indicating that they derive from similar source rocks.