Alteration of the Damiao anorthosite complex in the northern North China Craton: Implications for high-grade iron mineralization

The Damiao type iron deposit is hosted in a typical Proterozoic anorthosite complex in the northern North China Craton. The types of ores in Damiao mainly comprise massive Fe ores, massive Fe–P ores, and disseminated Fe and Fe–P ores. The disseminated Fe and Fe–P ores formed by fractional crystallization are generally hosted in oxide-apatite gabbronorite and account for 70% of the proven reserve of the Damiao type iron ore. The massive Fe and Fe–P ores account for 30% of the proven reserve of the Damiao type deposit iron ore and generally occur as irregular dykes or veins filling vertical fractures of the previously consolidated anorthosite, showing typical features of hydrothermal mineralization. The contact between the massive orebodies and wall rocks is sharp and straight. The anorthosite comprises white and dark varieties, with the former resulted by the alteration of the latter that occurs as relicts. Petrographic observation and electron microprobe analyses show abundant Fe–Ti oxide inclusions in plagioclase which impart the dark color to the rock. The similar spider diagram patterns between fresh and altered plagioclase and between dark- and white-colored anorthosite imply a genetic relationship between the dark and white types. During the alteration of anorthosite, CaO and MgO were slightly decreased, the SiO₂, Al₂O₃ and Na₂O were significantly increased, and the TFe₂O₃ and TiO₂ were significantly decreased. The TFe₂O₃ and TiO₂ in the dark-colored anorthosite have a range of 4.86–12.18 wt.% and 0.37–1.65 wt.%, respectively. However, The TFe₂O₃ and TiO₂ in the white-colored anorthosite have a range of 1.67–3.1 wt.% and 0.14–0.31 wt.%, respectively. These features suggest that the alteration of the anorthosite led the Fe element by leaching from the dark-colored anorthosite at highly oxidized condition, and then precipitated within the fractures of the anorthosite, thus forming the massive Fe and Fe–P orebodies. Because the estimated amount of transported Fe is much more abundant than the proven ore reserve, we infer that there should be huge potential for prospecting Damiao type iron ores.     

Geology,geochemistry and petrogenesis of post-collisional adakitic intrusions and related dikes in the Khoynarood area,NW Iran

The Khoynarood area is located in the northwest of Iran, lying at the northwestern end of the Urumieh–Dokhtar volcano-plutonic belt and being part of the Qaradagh–South Armenia domain. The main intrusive rocks outcropped in the area have compositions ranging from monzonite–quartz monzonite, through granodiorite, to diorite–hornblende diorite, accompanied by several dikes of diorite–quartz diorite and hornblende diorite compositions, which were geochemically studied in order to provide further data and evidence for the geodynamic setting of the region. The SiO₂, Al₂O₃ and MgO contents of these rocks are about 58.32–68.12%, 14.13–18.65% and 0.68–4.27%, respectively. They are characterized by the K₂O/Na₂O ratio of 0.26–0.58, Fe₂O₃ + MnO + MgO + TiO₂ content about 4.27–13.13%, low Y (8–17 ppm) and HREE (e.g., 1–2 ppm Yb) and high Sr contents (750–1330 ppm), as well as high ratios of Ba/La (13.51–50.96), (La/Yb)_N (7–22), Sr/Y (57.56–166.25), Rb/La (1.13–2.96) and La/Yb (10–33.63), which may testify to the adakitic nature of these intrusions. Their chemical composition corresponds to high-silica adakites, displaying enrichments of LREEs and LILEs and preferential depletion of HFSEs, (e.g., Ti, Ta and Nb). The REE differentiation pattern and the low HREE and Y contents might be resulted from the presence of garnet and amphibole in the solid residue of the source rock, while the high Sr content and the negative anomalies of Ti, Ta and Nb may indicate the absence of plagioclase and presence of Fe and Ti oxides in it. As a general scenario, it may be concluded that the adakitic rocks in the Khoynarood were most likely resulted from detachment of the subducting Neo-Tethyan eclogitic slab after subduction cessation between Arabian and Central Iranian plates during the upper Cretaceous–early Cenozoic and partial melting of the detached slab, followed by interactions with metasomatized mantle wedge peridotite and contamination with continental crust.     

Dielectric loss in ore-forming chromium spinel at temperatures from 20 to 800 °C

Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe₂O₃)^? : (FeO/Fe₂O₃)^??, where (FeO/Fe₂O₃)^? and (FeO/Fe₂O₃)^?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe₂O₃ ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr₂O₃) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr₂O₃), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N², with an error of σ = 0.19 (N = T · 10^?2, T is temperature in °C).     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Geochemistry and magmatic history of eclogites and ultramafic rocks from the Chinese continental scientific drill hole: Subduction and ultrahigh-pressure metamorphism of lower crustal cumulates

Three distinct groups of eclogites (low-Mg–Ti eclogites, high-Ti eclogites and Mg-rich eclogites) and ultramafic rocks from the depth interval of 100–680 m of the Chinese Continental Scientific Drill Hole were studied. The low Mg#s (= 100^?molar Mg/(Mg + Fe)) (81–84%) and low Ni (1150–1220 ppm) and high Fe₂O₃^total (13–15 wt.%) contents of ultramafic rocks suggest a cumulate origin. Mg-rich eclogites show middle and heavy REE enrichments, which could not be produced by metamorphic growth of garnet. Instead, if the rocks formed from a light REE enriched magma, there may be an igneous precursor for some garnets in their protolith. Alternatively, perhaps they formed from a light REE depleted magma without garnet. The high-Ti eclogites are characterized by unusually high Fe₂O₃^total contents (up to 24.5 wt.%) and decoupling of high TiO₂ from low Nb and Ta contents. These features cannot be produced by concentration of rutile during UHP metamorphism (even for samples with TiO₂ > 4 wt.%) of high-Ti basalts, but could be attributed to crystal fractionation of titanomagnetite (for those with TiO₂ < ～ 4 wt.%) or titanomagnetite + ilmenite (for those with TiO₂ > ～ 4 wt.%). Thus, we suggest that protoliths of the high-Ti eclogites were titanomagnetite/ilmenite-rich gabbroic cumulates. As a whole, the low-Mg–Ti eclogites are geochemically complementary to the high-Ti eclogites, Mg-rich eclogites and ultramafic rocks, and could be metamorphic products of gabbroic/dioritic cumulates formed by high degree crystal fractionation. All these observations suggest that parental materials of the ultramafic rock-eclogite assemblage could represent a complete sequence of fractional crystallization of tholeiitic or picritic magmas at intermediate to high pressure, which were later carried to ultrahigh-pressure conditions during a continental collision event.     

Enriched crustal and mantle components and the role of the lithosphere in generating Paleoproterozoic dyke swarms of the Ungava Peninsula,Canada

Paleoproterozoic mafic dyke swarms (2.5–2.0 Ga) of the Ungava Peninsula can be divided in three chemical groups. The main group has a wide range of Fe (10–18 wt.% Fe₂O₃) and Ti (0.8–2.0 wt.% TiO₂) contents, and the most magnesian samples have compositions consistent with melting of a fertile lherzolitic mantle at ~ 1.5 GPa. Dykes of a low-LREE (light rare earth element) subgroup (La/Yb ≤ 4) display decreasing Zr/Nb with increasing La/Yb ratios and positive εNd_2.0 Ga values (+ 3.9 to + 0.2) that trend from primitive mantle towards the composition of Paleoproterozoic alkaline rocks. In contrast, dykes of a high-LREE subgroup (La/Yb ≥4) display increasing Zr/Nb ratios and negative εNd_2.0 Ga values (? 2.3 to ? 6.4) that trend towards the composition of Archean crust. A low Fe–Ti group has low Fe (< 11 wt.% Fe₂O₃), Ti (< 0.8 wt.% TiO₂), high field strength elements (HFSE; < 6 ppm Nb) and heavy rare earth elements (HREE; < 2 ppm Yb) contents, but are enriched in large ion lithophile elements (LILE; K/Ti = 0.7–3) and LREE (La/Yb > 4). These dykes are interpreted as melts of a depleted harzburgitic mantle that has experienced metasomatic enrichment. A positive correlation of Zr/Nb ratio and La/Yb ratio, negative εNd_2.0 Ga values (? 14 to ? 6), and the presence of inherited Archean zircons further suggest the incorporation of a crustal component. A high Fe–Ti group has high Fe (> 14 wt.% Fe₂O₃) and Ti (> 1.4 wt.% TiO₂) contents, along with higher Na contents relative to the main group dykes. Dykes of a high-Al subgroup (> 12 wt.% Al₂O₃) share Fe contents, εNd_2.0 Ga values (? 2.3 to ? 3.4), La/Yb and Th/Nb ratios with Archean ferropicrites, and may represent evolved ferropicrite melts. A low-Al subgroup (< 12 wt.% Al₂O₃) has relatively lower Yb contents (< 2 ppm) and fractionated HREE patterns that indicate the presence of garnet in their melting residue. A comparison with ~ 5 GPa experimentally-derived melts suggests that these dykes may be derived from garnet-bearing pyroxenite or peridotite. The εNd_2.0 Ga values (? 0.3 to ? 2.0) of these dykes lie between the compositions of Archean granitoids and Paleoproterozoic alkaline rocks, signifying their petrogenesis involved both crustal and mantle components.Paleoproterozoic dykes containing a crustal component occur within, or close to, an isotopically enriched Archean terrane (T_DM 4.3–3.1 Ga), whereas dykes without this component occur in an isotopically juvenile terrane (T_DM < 3.1 Ga). The lack of a crustal component and the positive εNd_2.0 Ga values of dykes intruding the latter suggest that the crust they intruded was either too cold to be assimilated, or that its lower crust and/or lithosphere were Paleoproterozoic in age. In contrast, the ubiquitous presence of a crustal component and the diversity of mantle sources for dykes intruding the enriched terrane (lherzolite, harzburgite, pyroxenite) suggest a warmer crust with underlying heterogeneous lithospheric mantle.     

Mineralogical and geochemical investigations of the Mombi bauxite deposit,Zagros Mountains,Iran

The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al₂O₃, SiO₂, Fe₂O₃ and TiO₂ are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce³⁺ to Ce⁴⁺), ionic potential, and complexation of Ce⁴⁺ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation.     

Evidence of Mid-ocean ridge and shallow subduction forearc magmatism in the Nagaland-Manipur ophiolites,northeast India: constraints from mineralogy and geochemistry of gabbros and associated mafic dykes

We discuss here the mineralogical and geochemical characteristics of mafic intrusive rocks from the Nagaland-Manipur Ophiolites (NMO) of Indo-Myanmar Orogenic Belt, northeast India to define their mantle source and tectonic environment. Mafic intrusive sequence in the NMO is characterized by hornblende-free (type-I) and hornblende-bearing (type-II) rocks. The type-I is further categorized as mafic dykes (type-Ia) of tholeiitic N-MORB composition, having TiO₂ (0.72–1.93 wt.%) and flat REE patterns (La_N/Yb_N = 0.76–1.51) and as massive gabbros (type-Ib) that show alkaline E-MORB affinity, having moderate to high Ti content (TiO₂ = 1.18 to 1.45 wt.%) with strong LREE-HREE fractionations (La_N/Yb_N = 4.54–7.47). Such geochemical enrichment from N-MORB to E-MORB composition indicates mixing of melts derived from a depleted mantle and a fertile mantle/plume source at the spreading center. On the other hand, type-II mafic intrusives are hornblende bearing gabbros of SSZ-type tholeiitic composition with low Ti content (TiO₂ = 0.54 wt.%–0.86 wt.%) and depleted LREE pattern with respect to HREE (La_N/Yb_N = 0.37–0.49). They also have high Ba/Zr (1.13–2.82), Ba/Nb (45.56–151.66) and Ba/Th (84.58–744.19) and U/Th ratios (0.37–0.67) relative to the primitive mantle, which strongly represents the melt composition generated by partial melting of depleted lithospheric mantle wedge contaminated by hydrous fluids derived from subducting oceanic lithosphere in a forearc setting. Their subduction related origin is also supported by presence of calcium-rich plagioclase (An_16.6–32.3). Geothermometry calculation shows that the hornblende bearing (type-II) mafic rocks crystallized at temperature in range of 565°–625 °C ± 50 (at 10 kbar). Based on these available mineralogical and geochemical evidences, we conclude that mid ocean ridge (MOR) type mafic intrusive rocks from the NMO represent the section of older oceanic crust which was generated during the divergent process of the Indian plate from the Australian plate during Cretaceous period. Conversely, the hornblende-bearing gabbros (type-II) represent the younger oceanic crust which was formed at the forearc region by partial melting of the depleted mantle wedge slightly modified by the hydrous fluids released from the subducting oceanic slab during the initial stage of subduction of Indian plate beneath the Myanmar plate.     

Geochemical features of the Matomb alluvial rutile from the Neoproterozoic Pan-African belt,Southern Cameroon

The Matomb region constitutes an important deposit of detrital rutile. The rutile grains are essentially coarse (> 3 mm), tabular and elongated, due to the short sorting of highly weathered detritus. This study reports the major, trace, and rare-earth element distribution in the bulk and rutile concentrated fractions. The bulk sediments contain minor TiO₂ concentrations (1–2 wt%), high SiO₂ contents (∼77–95 wt%) and variable contents in Al₂O₃, Fe₂O₃, Zr, Y, Ba, Nb, Cr, V, and Zn. The total REE content is low to moderate (86–372 ppm) marked by high LREE-enrichment (LREE/HREE ∼5–25.72) and negative Eu anomalies (Eu/Eu^* ∼0.51–0.69). The chemical index of alteration (CIA) shows that the source rocks are highly weathered, characteristic of humid tropical zone with the development of ferrallitic soils. In the concentrated fractions, TiO₂ abundances exceed 94 wt%. Trace elements with high contents include V, Nb, Cr, Sn, and W. These data associated with several binary diagrams show that rutile is the main carrier of Ti, V, Nb, Cr, Sn, and W in the alluvia. The REE content is very low (1–9 ppm) in spite of the LREE-abundance (LREE/HREE ∼4–40). The rutile concentrated fractions exhibit anomalies in Ce (Ce/Ce^* ∼0.58 to 0.83; ∼1.41–2.50) and Eu (Eu/Eu^* ∼0.42; 1.20–1.64). The high (La/Sm)_N, (La/Yb)_N and (Gd/Yb)_N ratios indicate high REE fractionation.     

A Cretaceous dike swarm provides evidence of a spreading axis in the back-arc basin of the Kohistan paleo-island arc,northwestern Himalaya,Pakistan

A 100–4000 m wide and 15 km long dike swarm, consisting of basalt and dolerite, occurs at the base of the Thelichi Formation in the Kohistan paleo-island arc terrane, north Pakistan. The dikes contain hornblende (altered from diopsidic-augite), diopsidic-augite (relics; ophitic to subophitic texture), chlorite, epidote, sphene, apatite, zircon, ilmenite, titanomagnetite and magnetite. The geochemistry reveals two groups of dikes: (1) Higher TiO₂ (2.74–3.50 wt%), Na₂O, Fe₂O₃ and lower Al₂O₃ (12.65–14.16 wt%) and MgO (3.73–5.04 wt%); (2) Lower TiO₂ (1.24–2.05 wt%), Na₂O, Fe₂O₃ and higher Al₂O₃ (14.02–16.52 wt%) and MgO (3.98–7.52 wt%). The MgO contents (3.73–7.52-wt%) show a variation in the dikes from relatively primitive to more evolved compositions. The dikes contain high amounts of both LILE and HFSE. The major, trace and rare-earth elements data confirm the MORB affinity and the back-arc basin origin of the dike swarm. The NW–SE orientation of the dike swarm and its 134 ± 3 Ma K–Ar age suggest the spreading axis of the back-arc basin in the Early Cretaceous.     

Manufactured metal and metal-oxide nanoparticles: Properties and perturbing mechanisms of their biological activity in ecosystems

The inorganic manufactured nanoparticles as TiO₂, Ag°, the iron oxides and CeO₂ are more and more present in various manufactured products and in the aqueous media (TiO₂). Their dispersion in the ecosystems during their life cycle will be associated with interactions with biota (plants, bacteria, fishes). The present work shows strong relations between particular physical chemical properties of very small nanoparticles (size < 30 nm) and biological activity perturbations. It is shown that Ag° and CeO₂ act at very low concentrations. TiO₂ act via the ROS production due to their photo-reactivity.     

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.     

Geochemistry of the Apulian karst bauxites (southern Italy): Chemical fractionation and parental affinities

This study focuses on a late Cretaceous karst bauxite deposit in the Murge area of the Apulia district, southern Italy. The first analysis of the vertical distributions of a wide range of elements (including REEs and selected trace elements) throughout the deposit was shown in order to identify the processes determining element fractionation during the evolution of the bauxite.The studied karst bauxite deposit exhibits an ooidal texture, is mineralogically homogeneous, and contains higher abundances of boehmite than of hematite, kaolinite, and anatase. The major element composition of the bauxite is dominated by elevated concentrations of SiO₂, TiO₂, Al₂O₃, and Fe₂O₃, and analyses of element mobility within the bauxite indicate that all elements except for Nb and Ni, and to a lesser extent Cr, are depleted relative to the immobile element Ti. R-mode factor analysis revealed a number of key findings: (i) some low-solubility elements (e.g., Zr, Th, Ti, V, Ga) were concentrated in detrital zircon and monazite (Zr, Th), in anatase (Ti, V), and possibly in boehmite and hematite (Ga) during the later stages of bauxitisation; (ii) Fe and Cr were concentrated during wet conditions, whereas Al and Co accumulated during dry conditions; (iii) distributions of the light REEs (LREEs) and the heavy REEs (HREEs) are controlled by the same processes, suggesting that little LREE/HREE fractionation occurred during bauxite formation; and (iv) the behaviour of cerium is different from that of the other REEs, and highly variable cerium anomalies are observed across the deposit, with three characteristic Ce/Ce* maxima with values of > 2. Parisite was the only authigenic cerium mineral detected during this study. Thus, we propose a three-step model to explain the distribution of Ce: cerianite is dissolved by cerium reduction, is transported by downward-moving meteoric water (per descensum), and finally parisite is precipitated. This cycle was repeated several times in the Apulian karst bauxite in response to Eh decreases under alkaline conditions, promoted by fluctuations in the groundwater level. Finally, we used the value of the Eu anomaly to discuss the parental affinity or protolith of the bauxite. The value of the Eu anomaly (min. Eu/Eu* = 0.76, max. Eu/Eu* = 0.89) indicates that the bauxite was not derived from carbonates, but rather, that the majority of the bauxite was influenced by intermediate to mafic magmatic sources. Eu/Eu* vs Sm/Nd diagram suggests that the parental material for the bauxite was derived from a combination of a distant magmatic source and clastic material derived from a continental margin (northern Africa) to the south.     

Geological setting and fluid inclusion characteristics of a lead-copper-barium occurrence hosted in a Neoproterozoic mafic sill at Kiatak,Northumberland Island,Northwestern Greenland

We describe a Pb-Cu-Ba occurrence in Northumberland Island, Northwestern Greenland. Mineralization occupies the brecciated upper contact domain of a Neoproterozoic diabase sill belonging to the Franklin-Thule dike swarm (720–716 Ma), with pyrite-bearing black shales of the Dundas Group, upper Thule Supergroup. The host tholeiitic diabase sill is of different composition (low TiO₂ and P₂O₅) than the locally crosscutting dikes (high TiO₂ and P₂O₅). Chloritization, carbonatization and silicification are intense in proximity to sulfides. Coarse grained, open space-filling galena and minor chalcopyrite are accompanied by 2 generations of calcite and 2 of barite. Galena contains significant amounts of Ag (av. 400 ppm), Sb (av. 700 ppm), Se (av. 20 ppm), traces of Bi, Cd, and Sn. Fluid inclusions in the gangue of the Kiatak occurrence indicate two fluid types. Prior to galena precipitation, a CaCl₂-NaCl-rich aqueous brine (~ 20 wt.% eq NaCl) cooled from temperatures > 300 °C and was trapped first in early calcite, and with further cooling, in barite together with solid bitumen inclusions. Following galena crystallization, secondary inclusions containing a similar brine, but of lower salinity, higher Ca:Na ratio, and lower temperature, were trapped in calcite. Corrosion of galena was followed by precipitation of lower temperature (~ 100 °C) barite from a second fluid, comprising immiscible water and CH₄. Despite its location in the contact between shale and large mafic sill, the low-temperature mineralization postdates the cooling of the sill, and may be related to basinal fluid circulation controlled by regional extensional faults parallel to diabase dikes. Although uneconomic, the Kiatak occurrence may be witness to a larger metallogenic process that could have formed significant SEDEX type metal concentrations in strata within the Thule Supergroup.     

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.     

Geology and fluid characteristics of the Ulu Sokor gold deposit,Kelantan, Malaysia: Implications for ore genesis and classification of the deposit

The Ulu Sokor gold deposit is one of the most famous and largest gold deposits in Malaysia and is located in the Central Gold Belt. This deposit consists of three major orebodies that are related to NS- and NE-striking fractures within fault zones in Permian-Triassic meta-sedimentary and volcanic rocks of the East Malaya Block. The faulting events represent different episodes that are related to each orebody and are correlated well with the mineralogy and paragenesis. The gold mineralization consists of quartz-dominant vein systems with sulfides and carbonates. The hydrothermal alteration and mineralization occurred during three stages that were characterized by (I) silicification and brecciation; (II) carbonatization, sericitization, and chloritization; and (III) quartz–carbonate veins.Fluid inclusions in the hydrothermal quartz and calcite of the three stages were studied. The primary CO₂–CH₄–H₂O–NaCl fluid inclusions in stage I are mostly related to gold mineralization and display homogenization temperatures of 269–389 °C, salinities of 2.77–11.89 wt.% NaCl equivalent, variable CO₂ contents (typically 5–29 mol%), and up to 15 mol% CH₄. In stage II, gold was deposited at 235–398 °C from a CO₂ ± CH₄–H₂O–NaCl fluid with a salinity of 0.83–9.28 wt.% NaCl equivalent, variable CO₂ contents (typically 5–63 mol%), and up to 4 mol% CH₄. The δ¹⁸O_H2O and δD values of the ore-forming fluids from the stage II quartz veins are 4.5 to 4.8‰ and − 44 to − 42‰, respectively, and indicate a metamorphic–hydrothermal origin. Oxygen fugacities calculated for the entire range of T-P-X_CO2 conditions yielded log f_O2 values between − 28.95 and − 36.73 for stage I and between − 28.32 and − 39.18 for stage II. These values indicate reduced conditions for these fluids, which are consistent with the mineral paragenesis, fluid inclusion compositions, and isotope values.The presence of daughter mineral-bearing aqueous inclusions is interpreted to be a magmatic signature of stage IIIa. Combined with the oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 6.8 to 11.9‰, δD = − 77 to − 62‰), these inclusions indicate that the initial fluid was likely derived from a magmatic source. In stage IIIb, the gold was deposited at 263° to 347 °C from a CO₂–CH₄–H₂O–NaCl fluid with a salinity of 5.33 to 11.05 wt.% NaCl equivalent, variable CO₂ contents (typically 9–15 mol%), and little CH₄. The oxygen and hydrogen isotopic compositions of this fluid (δ¹⁸O_H2O = 8.1 to 8.8‰, δD = − 44 to − 32‰) indicate that it was mainly derived from a metamorphic–hydrothermal source. The CO₂–H₂O ± CH₄–NaCl fluids that were responsible for gold deposition in the stage IIIc veins had a wide range of temperatures (214–483 °C), salinities of 1.02 to 21.34 wt.% NaCl equivalent, variable CO₂ contents (typically 4–53 mol%), and up to 7 mol% CH₄. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 8.5 to 9.8‰, δD = − 70 to − 58‰) were probably acquired at the site of deposition by mixing of the metamorphic–hydrothermal fluid with deep-seated magmatic water and then evolved by degassing at the site of deposition during mineralization. The log f_O2 values from − 28.26 to − 35.51 also indicate reduced conditions for this fluid in stage IIIc. Moreover, this fluid had a near-neutral pH and δ³⁴S values of H₂S of − 2.32 to 0.83‰, which may reflect the derivation of sulfur from the subducted oceanic lithospheric materials.The three orebodies represent different gold transportation and precipitation models, and the conditions of ore formation are related to distinct events of hydrothermal alteration and gold mineralization. The gold mineralization of the Ulu Sokor deposit occurred in response to complex and concurrent processes involving fluid immiscibility, fluid–rock reactions, and fluid mixing. However, fluid immiscibility was the most important mechanism for gold deposition and occurred in these orebodies, which have corresponding fluid properties, structural controls, geologic characteristics, tectonic settings, and origins of the ore-forming matter. These characteristics of the Ulu Sokor deposit are consistent with its classification as an orogenic gold deposit, while some of the veins are genetically related to intrusions.     

Kinetics of nickel leaching from spent catalyst in sulphuric acid solution

The kinetics of spent nickel oxide catalyst (NiO/Al₂O₃) leaching in sulphuric acid solutions was investigated. The effects of sulphuric acid concentration, temperature, stirring speed, and particle size on the rate of nickel leaching were studied. In addition, the reaction residues at various levels of nickel extraction were examined by SEM, X-ray diffraction, electron microprobe, and chemical analysis. The results of the kinetic analysis of the leaching data for various experimental conditions indicated that the reaction is controlled by diffusion through the catalyst network with the activation energy of 16.6 ± 0.9 kJ/mol. A linear relationship between the rate constant and the inverse square of the initial particle diameter is also characteristic for a diffusion-controlled process.     

Iron isotope fractionation during skarn-type alteration: Implications for metal source in the Han-Xing iron skarn deposit

The Han-Xing iron mineralization in the central North China Craton is a typical Fe skarn deposit associated with altered diorites. Here we report the Fe isotopic compositions of whole rocks and mineral separates from this deposit with a view to evaluate the Fe isotope fractionation during the formation of Fe skarn deposit, and to constrain the metal source. The Fe isotopes show a large variation both in whole rocks and mineral separates. Altered diorites show a wide range in δ⁵⁶Fe values (− 0.07‰ to + 0.21‰ relative to the Fe isotope standard IRMM-014) which positively correlate with their TFe₂O₃/TiO₂ ratios (Fe₂O₃ and FeO calculated as TFe₂O₃). The positive correlation indicates that heavy Fe isotopes were preferentially leached from diorites during the skarn-type alteration. Among the metallic minerals, pyrite and pyrrhotite are isotopically heavier (+ 0.12‰ to + 0.48‰) than the magnetite (+ 0.07‰ to + 0.21‰). Fe isotope fractionation between mineral pairs demonstrates that magnetite did not attain Fe isotopic equilibrium with pyrite and pyrrhotite, whereas pyrite and pyrrhotite might have attained isotopic equilibrium. Petrological observations and major element data also suggest that iron was leached from the diorites during the skarn-type alteration. If the leached iron provides the main Fe budget of the Han-Xing Fe skarn deposit, magnetite in ores would be isotopically heavier than the unaltered diorite. However, our results are in contrast with the magnetite being isotopically lighter than the unaltered diorite. This suggests that the major Fe source of the Han-Xing Fe skarn deposit is not from the leaching of diorites, and might be from magmatic fluid which is isotopically lighter than the silicate melt. Our data demonstrate that Fe isotopes can be used as important tracers in deciphering the metal source of Fe skarn deposits.