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.     

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.     

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.     

U–Pb zircon chronology,geochemistry and isotopes of the Changyi banded iron formation in the eastern Shandong Province: Constraints on BIF genesis and implications for Paleoproterozoic tectonic evolution of the North China Craton

The Changyi banded iron formation (BIF) in the eastern North China Craton (NCC) occurs within the Paleoproterozoic Fenzishan Group. The BIF shows alternating quartz-rich light and magnetite-rich dark bands with magnetite (15–65 vol.%), quartz (25–65 vol.%) and amphibole (15–30 vol.%) constituting the major minerals. Minor garnet, epidote, chlorite, calcite, biotite and pyrite occur locally. The BIF bands are interlayered with amphibolite, hornblende gneiss, biotite quartz schist, garnet biotite schist, biotite gneiss and leptynite, and are intruded by granites. LA-ICP-MS U–Pb dating on zircons separated from the BIF bands and the wallrocks constrains the depositional age as 2240–2193 Ma and metamorphic age as ~ 1864 Ma. The dominant composition of SiO₂ + Fe₂O₃^T (average value of 92.3 wt.%) of the BIF bands suggests their formation mainly through chemical precipitation. However, the widely varying contents of major elements such as Al₂O₃ (0.58–6.99 wt.%), MgO (1.00–3.86 wt.%), CaO (0.22–4.19 wt.%) and trace elements such as Rb (2.06–40.4 ppm), Sr (9.36–42.5 ppm), Zr (0.91–23.6 ppm), Hf (0.04–0.75 ppm), Cr (89.1–341 ppm), Co (2.94–30.4 ppm), and Ni (1.43–52.0 ppm) clearly indicate the incorporation of clastics, especially continental felsic clastics, as also confirmed by the presence of ancient detrital zircons in the BIF bands. When normalized against Post Archean Average Shale (PAAS), the seawater-like signatures of REE distribution patterns, such as LREE depletion, positive La and Y anomalies, and superchondritic Y/Ho ratios (average value of 36.3), support the deposition in seawater. Strong positive Eu anomalies (Eu/Eu*_PAAS = 1.14–2.86) also suggest the participation of hydrothermal fluids. In addition, the sympathetic correlation between Cr, Co and Ni as well as the Co + Ni + Cu vs. ∑ REE and the Al₂O₃ vs. SiO₂ relations further indicates that the iron and silica mainly originated from hydrothermal fluids. Combined with regional geological investigation and protolith restoration of the wallrocks, a continental rift environment is suggested for the Changyi BIF deposition. The appearance of negative Ce_PAAS anomalies might suggest the influence of the Great Oxidation Event at the time of deposition. The Changyi BIF witnessed the major Paleoproterozoic rifting–collision events in the NCC and their unique distribution in the NCC contrasts with other examples elsewhere in the world.     

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.     

Structural,textural, geochemical and isotopic signatures of synglaciogenic Neoproterozoic banded iron formations (BIFs) at Bafq mining district (BMD), Central Iran: The possible Ediacaran missing link of BIFs in Tethyan metallogeny

The Neoproterozoic magnetite–apatite–hematite–pyrolusite–jaspilite deposits in the Bafq mining district (BMD) contain more than 1.7 Gt ores with an average grade of 50 wt.% Fe and 0.01 to 7.78 wt.% P and were probably formed between 635 and 547 Ma in a riftogenic felsic submarine exhalative sequence of the Esfordi Formation. The ore zones occur in proximal zone of magnetite-rich albitized rhyolite (keratophyres), interdistal zone of rhyolitic tuff–tuffaceous sediments and distal zone of pyrolusite–jaspilite. These sequences are covered by the diamictites and cap carbonates. The BIFs are linked to the altered rhyolites–rhyodacites, jaspilites and diamictites and contain magnetite, hematite and apatite. The presence of Spriggina, Dickinsonia, Medusites and Persimedusites chahgazensis (Sennewald and Krüger, 1979; Hahn and, Pflug; McCall, 2006) in the Kushk shale member of the Esfordi Formation conforms to the Australian fauna of the Ediacaran period (635–540). This relative age is supported by some reliable Pb isotopic data (635–547 Ma) on galena, monazite and apatite (Huckriede et al., 1962; Torab, 2008; Stosch et al., 2011). The most frequent structures–textures in the ore zones include felsic autobrecciation, massive, colloidal, banded, detrital and glaciogenic. The BIFs are highlighted by high values of LREE fractionation and no significant Eu and Ce anomalies. The ores show high values of Fe₂O₃ (14–60%), and SiO₂ (4–34%), and low contents of Al (3.32%), Cr (21.48 ppm), Co (42.82 ppm), Ni (125 ppm), V (868 ppm), and Ti (0.13%) similar to those of the Ediacaran–Rapitan BIFs. The cap carbonates show depletion in δ¹³C, with a range from − 0.43 to − 6.6 per mil and then return to near excursion of about + 2.97‰ in the Lower Cambrian carbonates. These are followed by δ¹⁸O values, which range from − 6.64 to − 11.86‰. The presence of jaspilites, diamictites, C and O isotopic signatures, REE patterns, and immobile element relationships highlights a glaciogenic BIF. Importantly, the glaciogenic structures–textures and jaspilites do not support the misconception of the previously proposed magmatic–carbonatitic and metasomatic–hydrothermal IOCG–Kiruna ore deposits.     

Petrography and geochemistry of the Mesoarchean Bikoula banded iron formation in the Ntem complex (Congo craton), Southern Cameroon: Implications for its origin

Precambrian banded iron formations (BIFs) represent an important source of mineable iron, as well as an archive recording secular changes in the chemistry of the Earth’s early oceans. Here we report petrographic and geochemical characteristics of unweathered drill core samples from the Bikoula BIF, a virtually uncharacterized oxide facies iron formation, hosted in the Mesoarchean Ntem complex, southern Cameroon. The BIF is cross-cut with syenitic veins. The entire succession is highly deformed and metamorphosed under granulite facies conditions. The BIF is characterized by alternating micro-bands of magnetite, quartz and pyroxene. Sulfides (pyrite, pyrrhotite, and chalcopyrite), oligoclase, ferro-pargasite, biotite and ilmenite occur as minor phases. The presence of pyroxene, ferro-pargasite and oligoclase, relatively high contents of major elements such as Al₂O₃ (0.76–7.52 wt.%), CaO (1.95–4.90 wt.%), MgO (3.78–5.59 wt.%), as well as positive correlations among Al₂O₃, TiO₂, HFSEs, LILEs and transition metals (V, Cr, Ni, Cu and Zn), suggest that the BIF protolith included a significant amount of clastic material. Several samples have preserved seawater-like PAAS-normalized REE-Y patterns, including LREE depletion, and positive La and Y anomalies. Positive Eu anomalies observed in some of the analyzed samples indicate influx of hydrothermal fluids (possibly including Fe and Si) within the basin where the BIF precipitated. However, few samples show unusual negative Eu anomalies that likely result from a large proportion of clastic contamination. The lack of Ce anomalies suggests that the Bikoula BIF was deposited in a basin that was (at least partly) anoxic or suboxic, where it was possible to transport and concentrate dissolved Fe²⁺.     

Mineralogical and microfabric characteristics of magnetite in the Wuyang Precambrian BIFs,southern North China Craton: Implications for genesis and depositional processes of the associated BIFs

Precambrian Banded Iron Formations (BIFs) are widely distributed in the North China Craton (NCC). Among them, the Wuyang BIFs located in the southern margin of NCC occur in the Late Archaean Tieshanmiao Formation and can be subdivided in two different sub-types: (i) quartz–magnetite BIFs (QMB), consisting of magnetite, fine-microcrystalline quartz and minor calcite and (ii) pyroxene–magnetite BIFs (PMB), composed of pyroxene, fine-microcrystalline quartz and subordinate feldspars. Both sub-types display apparent discrepancies in terms of petrography and mineral composition.As shown in Electron BackScattered Diffraction (EBSD) images and micrographs, magnetite grains from the QMB range in size from tens up to hundreds of μm, whereas magnetite crystals from the PMB can be up to a few tens of μm across. The X-ray diffraction (XRD) structural data indicate that magnetite from both BIF sub-types is equiaxed (cubic) and was generated by sedimentary metamorphic processes. The cell parameters of magnetite in the QMB are a = b = c = 8.396 Å and Z = 8, which deviate slightly from these of magnetite in the PMB: a = b = c = 8.394 Å and Z = 8. The analytical results of Raman spectroscopy analysis revealed micro-structural signatures of both magnetite (Raman shifts near 552 cm⁻¹ and 673 cm⁻¹) and hematite (Raman shifts near 227 cm⁻¹, 295 cm⁻¹ and 413 cm⁻¹). In magnetite from both QMB and PMB, the crystallinity degree is similar for magnetite micro-structures but varies significantly for hematite micro-structures. Oxygen fugacity (fO₂) conditions fluctuated during the recrystallization of magnetite in the QMB, whereas no evident variation of fO₂ occurred during the formation of magnetite in the PMB. Analytical results of laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) show that the Si, Al and Mg abundances are higher in magnetite from the QMB, whereas the Ti and Mn contents are more elevated in magnetite from the PMB. Magnetite composition also denotes that both BIF sub-types are sedimentary-metamorphic origin, whereas the deposition of PMB was also affected by volcanic activities. Overall data indicate that the differences in the depositional environment of each BIF sub-type are due to the involvement of volcanic eruption processes in the genesis of the PMB. Thus, this paper indicated that the QMB was deposited by chemical deposition at the long-term interval of volcanic eruptions, and the PMB were the product of chemical deposition affected by the volcanic eruption.     

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.     

Oldest volcanic-hosted submarine iron ores in South China: Evidence from zircon U–Pb geochronology and geochemistry of the Paleoproterozoic Dahongshan iron deposit

The Dahongshan iron deposit is hosted in the Paleoproterozoic submarine metavolcanic rocks of the Dahongshan Group in the Yangtze Block, South China. LA-ICP-MS dating of hydrothermal zircon grains from the genetically associated albitite and dolomite albitite show ca. 2008 Ma ages that are consistent with the zircon ages from the host metavolcanic rocks (ca. 2012 Ma), and postdated the post-ore diabase dike (ca. 1724 Ma), marking the Dahongshan iron deposit as the oldest submarine volcanic-hosted deposit so far as known. The ore-hosting metavolcanic rocks in the Dahongshan deposit have low Ni (9.1–77.4 ppm), Cr (1.0–63.0 ppm) and Co contents (5.6–62.9 ppm), suggesting the fractionation of olivine, clinopyroxene and plagioclase within the magma chamber. The major and trace element features of the alkaline to tholeiitic metavolcanic rocks are consistent with high-degree partial melting of the mantle wedge metasomatized by melts enriched in high field strength elements (HFSEs), which were derived from the subducted slab in volcanic arc setting. Based on an evaluation of the morphology of orebody, ore fabrics, petrology and melt-fluid inclusions, as well as the geochemical characteristics of the major ore mineral (magnetite), we correlate the iron mineralization in the Dahongshan deposit with hydrothermal process induced by the high-temperature, high-salinity and Fe-rich brines derived through magmatic exsolution. The similar characteristic of Ce and Eu anomalies of the Dahongshan iron deposit and banded iron formations (BIFs) suggest that the Dahongshan deposit was formed in reducing environment, although the two types of iron ores were generated through distinct processes with hydrothermal processes dominating for the submarine volcanic-hosted iron deposits whereas the BIFs were formed through chemical precipitation.     

冀东柞栏杖子BIF地球化学特征、形成时代及其地质意义

冀东地区柞栏杖子BIF出露于绿片岩相—低角闪岩相朱杖子岩群变质岩中。铁矿石主要由石英和磁铁矿组成,还含有少量透闪石和黑云母。主量元素主要为Si O2、Fe2O3和Fe O,其次为少量的Ca O和Mg O。较低的Al2O3含量、极低的Ti O2含量和高场强元素(HFSE)暗示,铁矿石中陆源碎屑物质含量很低。铁矿石的稀土元素含量较低,稀土元素配分模式特征为轻稀土元素相对亏损、重稀土元素相对富集。较明显的Eu正异常、轻微的Y正异常及较高的Y/Ho值的稀土元素特征,类似于高温热液和海水的混合热液,暗示成矿物质主要来自于海水和高温热液。对柞栏杖子BIF矿体夹层黑云斜长变粒岩进行SHRIMP锆石U-Pb定年,207Pb/206Pb年龄加权平均值为2572±8Ma(MSWD=5.8),可代表柞栏杖子BIF的形成年龄。综合前人研究,认为冀东地区变质级别不同的BIF物质来源相同、形成年代相近,BIF的变质可能和2500Ma左右华北克拉通东部陆块发生的地幔岩浆底侵事件有关。     

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%).     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Petrography and geochemical behaviour of trace element,REE and precious metal signatures of sulphidic banded iron formations from the Chikkasiddavanahalli area,Chitradurga schist belt,India

The ～1.2 km long and ～250 m wide Chikkasiddavanahalli (C.S. Halli) hill range consists of mixed sulphidic-oxide banded iron formations (BIFs) and Fe-rich phyllites (±carbonaceous), which overlie carbonated schistose and massive meta volcanics. In stratigraphic succession, the lithologies represent the Ingaldhal Formation and are an integral part of the Chitradurga schist belt in the Western Dharwar Craton. The general strike at C.S. Halli varies from N–S to 340° with vertical to steep dips towards east and west. The sulphides, oxides and silicates exhibit intergrowth replacement textures developed during regional greenschist- and amphibolites- facies metamorphism. The BIFs show mesobands of recrystallised cherts and iron sulphides such as pyrite, arsenopyrite, and silicates such as subordinate grunerite, hornblende, chlorite, muscovite, actinolite and minor carbonates such as ankerite, calcite and magnesian siderite. Chemical data indicate depletion in Ti, Mn, Co, Cu, Cr and Ni in these iron formations. Most chondrite normalized REE patterns of the iron formation show moderate LREE and HREE enrichment coupled with strong positive Eu anomaly; the mineralized portions exhibit characteristic negative Ce and Eu anomalies (Eu/Eu1 0.21 to 3.00). The total REE abundance varies, correlates well with the iron contents of the BIFs, and similar to those exhibited by hydrothermal plumes [Chown, E.H., Dah, E.N., Mueller, W.G., 2000. The relation between iron formation and low temperature alteration in a Archean volcanic environment. Precambrian Research 101, 263–275]. Trace and REE data suggest that primary mantle-derived hydrothermal solutions were added to the pore fluids of sediments of the Chitradurga basin and supplied chemical constituents such as FeO, SiO₂ and REE. Oxidation of FeO to Fe₂O₃ was caused by the photosynthesis of primitive stromatolite-building cyanobacteria. Geochemical data suggest a model involving epigenetic gold mineralisation in close association with shear zone deformation, quartz-calcite vein activity and sulphidation in the mixed sulphide oxide facies BIF and associated iron phyllites in the C.S. Halli area, Western Dharwar Craton, India.     

In-situ LA-ICP-MS trace elemental analyses of magnetite and Re–Os dating of pyrite: The Tianhu hydrothermally remobilized sedimentary Fe deposit,NW China

The Tianhu Fe deposit (> 104 Mt at 42% TFe) in the Eastern Tianshan (NW China) is hosted in the schist, quartzite, marble, and amphibolite of the Neoproterozoic Tianhu Group. The deposit consists of disseminated, banded and massive ores. Metallic minerals are dominantly magnetite and pyrite, with minor titanite, pyrrhotite, chalcopyrite, and sphalerite. Gangue minerals include dolomite with minor forsterite, diopside, apatite, biotite, chlorite, tourmaline, tremolite, talc, calcite, and magnesite. Pyrite separates from ores have 10.7 to 54.7 ppb Re and 0.033 to 0.175 ppb common Os. Those from the massive ores have a model 1 isochron age of 535 ± 36 Ma (2σ), in agreement with the isochron age (528 ± 18 Ma) of pyrite from the banded ores by regression of seven Re–Os analyses. The Re–Os age of ~ 530 Ma reflects the timing of a hydrothermal event that remobilized the Tianhu deposit. Magnetite has Mg, Al, Ti, V, Mn, Zn, and Ga contents ranging from ~ 5 to 3500 ppm and Cr, Co, Ni, and Sn contents ranging from ~ 1 to 200 ppm. Most magnetite grains have Ca + Al + Mn and Ti + V contents similar to those of the banded iron formation (BIF). Some grains have elevated Ti and V contents, indicating that that magnetite was formed by sedimentary process and overprinted by hydrothermal activity. Pyrite has δ³⁴S_CDT values from − 9.23 to 10.96‰, indicating that the sulfur was reduced from the marine sulfates either by bacterial or thermochemical processes. Pyrite has relatively high Co (~ 346 to 3274 ppm) but low Ni (~ 5.6 to 35.4 ppm) with Co/Ni ratios ranging from ~ 10 to 270, indicating remobilization from a volcanic–hydrothermal fluid. Therefore, the Tianhu Fe deposit was originally a sedimentary type deposit but was overprinted by a hydrothermal event related to volcanic activity.     

鞍本地区大孤山条带状铁建造含铁矿物和相分带特征及形成环境分析

鞍山-本溪条带状铁建造(Banded Iron Formation,简称BIF)位于华北克拉通东北缘,是世界上典型BIF之一,也是我国最重要的铁矿资源基地。大孤山位于鞍山地区南部矿带,为新太古代典型的Algoma型BIF,与华北克拉通其它大多数BIF相比,具有较低变质程度(绿片岩相-低角闪岩相)和较完整的沉积相分布特征。因此,通过大孤山BIF的研究有利于追踪Algoma型BIF的原生矿物组成及其后期成岩-变质过程,进而通过分析原生矿物形成的物理化学条件探讨古海洋环境。依据原生矿物共生组合及产出特征,可将大孤山BIF沉积相划分为氧化物相(30%)、硅酸盐相(50%)和碳酸盐相(20%)。氧化物相主要分布于主矿体南部,主要矿物组成为磁铁矿和石英;硅酸盐相分布于主矿体中部,主要矿物组成除了石英和磁铁矿之外,还有黑硬绿泥石、绿泥石、镁铁闪石等;碳酸盐相分布于矿体北部,主要矿物组成为菱铁矿、磁铁矿和石英等。本文通过大孤山BIF岩相学观察和含铁矿物化学成分研究,推测原生沉积物的组成为无定形硅胶、三价铁氢氧化物和富铝粘土碎屑,在经历了成岩和低级变质作用后转变为具不同相带的条带状铁建造。通过分析磁铁矿、菱铁矿和黑硬绿泥石等矿物在不同P_(O_2)-P_(CO_2)和pH-Eh条件下的共生相图可知,这些矿物均是在较低氧逸度、中到弱碱性环境下形成。综合考虑矿物成分、共生组合及受变质作用较弱等信息,本文推测制约原生矿物形成的控制因素主要是古海水氧化还原状态、酸碱度、CO_2含量和硫逸度。     

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.