Geochemistry of the apulian allochthonous karst bauxite,Southern Italy: Distribution of critical elements and constraints on Late Cretaceous Peri-Tethyan palaeogeography

A comprehensive study of pebbles from the 'Salento-type' allochthnous bauxite deposit (Otranto, southern Italy), originally derived from a pristine Campanian bauxite, has been performed for evaluating: 1) the chemical fractionation and inter-elemental relationships, especially for critical elements, 2) the climatic conditions that promoted bauxite formation, and 3) the provenance of the protolith(s) using zircon age data and conservative elemental proxies. The study confirms the capability of bauxite to concentrate many elements defined as critical by the European Union report on critical raw materials. Sc, Co, Ga, and especially Cr, are enriched when compared with the UCC composition and assuming Nb is immobile. Other critical elements such as the REEs, with the exception of La, are moderately depleted. R-mode factor analysis suggests that most of the variance in our chemical dataset is explained by a factor with significant weightings for TiO₂, Al₂O₃, Fe₂O₃, Sc, V, Nb, REEs, Pb and Th. This arises from climate effects affecting the distribution of the more abundant oxides and some trace elements, including the critical metals Nb and REEs. The texture of the pebbles is typical for Apulian karst bauxites and consists of sub-spheroidal ooids composed of boehmite and dispersed in a fine-grained matrix. The growth of the ooids, which formed under dry climate, was described in terms of fractal geometry. The average fractal dimension value of the ooids in the pebbles is close to that of the diffusion-limited aggregation models suggesting the ooid growth can be modelled using a molecular diffusion pattern, based on Fick's first law. The calculated time required for growth of the boehmite concretions is ~ 45 ÷ 310 ka. This finding is consistent with an intra-Campanian emersion event (74–76 Ma) that occurred during a dry and warm climatic stage. Since most of the karst bauxites worldwide have an ooidic texture, evaluation of the composition of concretions and the time required for their growth represents a powerful tool in reconstructing the palaeoenvironment. The zircon grains collected from the pebbles of the Salento-type karst bauxite define several concordant age populations. The youngest cluster, Early Cretaceous in age (99 ÷ 127.5 Ma), suggests that windborne particles from Cretaceous volcanics, possibly originating in the Carpatho-Balkan orogenic belts, provided material for further bauxitisation. The largest cluster (623 ÷ 689 Ma) is of Neoproterozoic age, predominately from the Late Ediacaran and Cryogenian p.p.. The 900–540 Ma Pan-African orogenic cycle was followed by continental-scale uplift and erosion, leading to the deposition of thick Cambrian–Ordovician siliciclastic sequences that represent the most widespread detrital sequence ever deposited on continental crust and that now cover large parts of North Africa. These Cambrian–Ordovician sandstones contain a large population of Neoproterozoic zircons of Cryogenian age. Neoproterozoic zircons also occur in the youngest (Silurian–Mesozoic) sandstones of the Saharan Metacraton. These sandstones also contain 1.0 Ga detrital zircons, suggesting as the oldest zircons found in the Salento-type bauxite pebbles (866 Ma and 941 Ma in age) are younger representatives of the zircon cluster present in this sandstone unit.These zircon age determinations suggest that the source material for the Salento-type bauxite pebbles was a combination of magmatic material from a distant source and clastic material derived from a continental margin (North Africa). This result concurs with the Eu/Eu* vs. Sm/Nd binary diagram, on which bauxite pebbles fall close to a mixing curve with andesite and cratonic sandstone end-members. As our results indicate that material was sourced from the North African continental margin, we suggest that a continental bridge separated oceanic domains in the Late Cretaceous of the Peri-Tethyan domain.     

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.     

Sampling oxygenated Archean hydrosphere: Implications from fractionations of Th/U and Ce/Ce* in hydrothermally altered volcanic sequences

Hydrothermally altered Archean igneous suites erupted in the submarine environment record variable excursions of Ce/Ce* and Th/U from primary magmatic values of 1 and ~ 4 respectively. Rhyolites of the 2.96 Ga bimodal basalt–rhyolite sequence of the Murchison Domain, Yilgarn Craton, Western Australia, hosting the Golden Grove VMS deposit, are enriched in MnO up to ten fold over primary values. Th/U ratios span 2.6–4.7, Ce/Ce* = 2.5–16, and Eu/Eu* = 1.3–3. The 2.8 Ga Lady Alma ultramafic–mafic subvolcanic complex of the same domain features highly dispersed MREE and LREE due to intense hydrothermal alteration. Th/U ratios span 0.005–0.16 from preferential addition of U, with Ce/Ce* = 0.6–2.2, and Eu/Eu* = 1–1.4. The eastern Dharwar Craton, India, includes greenstone terranes dominantly 2.7–2.6 Ga. Adakites of the Gadwal terrane preserve near primary magmatic Th/U, Ce/Ce*, and Eu/Eu*. In contrast, igneous lithologies of the Hutti greenstone terrane are characterized by total ranges of Th/U = 2–5.8, Ce/Ce* = 1.01–1.28, and Eu/Eu* = 0.82–1.26, and counterparts of the Sandur terrane have Th/U = 0.4–6.0, Ce/Ce* = 0.9–1.25, and Eu/Eu* = 0.8–1.8. Coexistence of Ce and Eu anomalies may reflect a two-stage process: low-temperature hydrothermal alteration at high water–rock ratios by oxidizing fluids, with evolution of the hydrothermal systems to high temperature, low water–rock ratios, under reducing conditions. Uranium is dominantly added to these lithologies over Th in common with Recent altered ocean crust. Iron-rich shales in the Sandur terrane record U-enrichment where Th/U = 2–4. Three shales record true negative Ce anomalies and Eu/Eu* = 0.8–2.4: true negative Ce anomalies, present in some other Archean iron formations, are interpreted as a signature of precipitates from the ocean water column whereas Eu anomalies are hydrothermal in origin. Volcanic flows of the 2.7 Ga Blake River Group, Abitibi greenstone terrane, Canada, preserve Th/U = 1.5–8.5, the conjunction of low Th/U values with Ce/Ce* = 1.4 in two samples, and Eu/Eu* = 0.15–1.3. Mobility of U and Ce in these hydrothermally altered Archean lithologies is in common with their mobility in Phanerozoic counterparts by oxygenated fluids.     

Content and mode of occurrences of rare earth elements in the Zagrad karstic bauxite deposit (Nikšić area,Montenegro)

Three vertical sections through the Zagrad deposit of Jurassic karst bauxite in central Montenegro have provided knowledge of the vertical distribution of major and some selected trace elements, including rare earth elements (REE). Variations in the mineralogy, particularly those hosting REE, have been studied. This has revealed the presence of authigenic mineral phases such as xenotime, mottramite and monazite (best proved using Raman microprobe analysis) as well as residual phases such as zircon, titanite and monazite. The mobility of the elements during bauxitization processes has been studied to show that the REE minerals ensure progressive concentration of these elements during removal of major elements through weathering. The similarity of normalized REE in the bauxite to the typical Post-Archean Australian Shales (PAAS) and Upper Continental Crust (UCC) profile, and the preserved Eu anomaly, are evidence that the bauxite was not derived from carbonates and represents alteration of shale, marly limestone and volcanogenic or proximal igneous sourced detritus that accumulated in the original karst landform. Mass change during bauxitization, using Ti as “index” element and compared to PAAS composition, revealed almost 100% depletion of Si and weak enrichment in Al. Deeper parts of the deposit with authigenic minerals exhibit very strong enrichment in all REE. The bauxite ores have high ΣREE contents (693.5–6953.4 ppm), especially ΣLREE contents (582.8–4882.9 ppm), while ΣHREE contents (106.6–2070.5 ppm) are much lower.     

Genesis of the Jinding Zn-Pb deposit,northwest Yunnan Province,China: Constraints from rare earth elements and noble gas isotopes

The giant sediment-hosted Jinding zinc-lead deposit is located in the Lanping Basin, northwestern Yunnan Province, China. The genesis of the deposit has long been debated and the sources of the ore-forming fluids and metals are controversial. This study presents rare earth element (REE) and noble gas isotope data that constrain the origins of the ore fluids and the heat source driving the hydrothermal circulation. The early-stage sulfides are enriched in light REEs and have high ∑REE values (30.8–94.8 ppm) and weakly negative Eu (δEu 0.85–0.89) and Ce anomalies (δCe 0.84–0.95), suggesting that the fluids were likely derived from dissolution of Upper Triassic marine carbonates with input of REEs from aluminosilicate rocks in the basin. In contrast, the late-stage sulfides have irregular REE patterns, generally low ∑REE values (0.24–10.8 ppm) and positive Eu (δEu 1.22–10.9) and weakly negative Ce anomalies (δCe 0.53–0.90), which suggest that the ore-forming fluids interacted with evaporite minerals. The ³He/⁴He (0.01–0.04 R_a) and ⁴⁰Ar/³⁶Ar values (301–340) of the ore-forming fluids indicate crustal and atmospheric origins for these noble gases. These findings are in agreement with the published fluid inclusion microthermometry data and the results of H, O, C, S, Pb and Sr isotope studies. Our data, in combination with published results, support a two-stage hydrothermal mineralization model, involving early-stage basinal brines and late-stage meteoric water that acquired metals and heat from crustal sources.     

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.     

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau,East Sea

We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)_UCC, (La/Yb)_UCC, and (Ce/Ce^*)_UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce^*)_UCC ratios in the extractable fraction at depth.     

Genesis of REE minerals in the karstic bauxite in western Guangxi,China, and its constraints on the deposit formation conditions

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce^3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce^4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce^3 + was oxidized into Ce^4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.     

Molybdenite Re–Os and U–Pb zircon dating and genesis of the Dayana W-Mo deposit in eastern Ujumchin,Inner Mongolia

The Dayana W-Mo deposit in eastern Ujumchin of Inner Mongolia is a quartz-vein type deposit in the mid-western part of the Central Asian Orogenic Belt (CAOB). Biotite monzogranite, quartz porphyry and hornfels host W-Mo in quartz veins. Based on spatial relationships, molybdenite was deposited first followed by wolframite. This contribution presents precise laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) U–Pb zircon dating and geochemical analysis of the biotite monzogranite. The U–Pb dating shows that the monzogranite is 134 ± 1 Ma. Major and trace element geochemistry shows that the monzogranite is characterized by high SiO₂ and K₂O contents, a “Right-inclined” shape of the chondrite normalized REE patterns, enrichment of large ion lithophile elements (LILEs), and depletion of high field strength elements (HFSEs) such as Nb, P, Ba. The monzogranite is high-K calc-alkaline, has a strong negative Eu anomaly (Eu/Eu* = 0.04–0.45), low P₂O₅ content, high A/CNK of > 1.2, enriched in large-ion lithophile elements (LILEs; such as Rb, Th, U, Nd, and Hf), and notably depleted in Ba, Sr, P, Ti, and Nb. These characteristics define the Dayana monzogranite as a highly fractionated peraluminous granite. Re–Os isotopic analysis of seven molybdenite samples from the deposit yield an isochron age of 133 ± 3 Ma (MSWD = 2.2), which indicates that the monzogranite and ore have the same age within error, are probably genetically related, and related to a major Early Cretaceous mineralizing event in China known as the Yanshanian.     

Origin of Archean tonalite–trondhjemite–granodiorite (TTG) suites and granites in the Fiskenæsset region,southern West Greenland: Implications for continental growth

Mesoarchean to Neoarchean orthogneisses (2.95–2.79 Ga) in the Fiskenæsset region, southern West Greenland, are composed of an older suite of metamorphosed tonalites, trondhjemites, and granodiorites (TTGs), and a younger suite of high-K granites. The TTGs are characterized by high Al₂O₃ (14.2–18.6 wt.%), Na₂O (3.4–5.13 wt.%), and Sr (205–777 ppm), and low Y (0.7–17.4 ppm) contents. On chondrite- and N-MORB-normalized trace element diagrams, the TTGs have the following geochemical characteristics: (1) highly fractionated REE patterns (La/Yb_cn = 14–664; La/Sm_cn = 4.3–11.0; Gd/Yb_cn = 1.5–19.7); (2) strong positive anomalies of Sr (Sr/Sr* = 1.0–15.9) and Pb (Pb/Pb* = 1.4–34.9); and (3) large negative anomalies of Nb (Nb/Nb* = 0.01–0.34) and Ti (Ti/Ti* = 0.1–0.6). The geochemical characteristics of the TTGs and trace element modeling suggest that they were generated by partial melting of hydrous basalts (amphibolites) at the base of a thickened magmatic arc, leaving a rutile-bearing eclogite residue. Field observations suggest that spatially and temporarily associated tholeiitic basalts (now amphibolites) in the Fiskenæsset region might have been the sources of TTG melts. The high-K granites have steep REE patterns (La/Yb_cn = 3.8–506; La/Sm_cn = 2.7–18.9; Gd/Yb_cn = 0.92–12.1) and display variably negative Eu anomalies (Eu/Eu* = 0.37–0.96) and moderate Sr (84–539 ppm) contents. Four outlier granite samples have variably positive Eu (Eu/Eu* = 1.0–12) anomalies. Given that the granodiorites have higher K₂O/Na₂O than the tonalites and trondhjemites, it is suggested that the granites were derived from partial melting of the granodiorites. It is speculated that the dense eclogitic residues, left after TTG melt extraction, were foundered into the sub-arc mantle, leading to basaltic underplating beneath the lower rust. Melting of the granodiorites in response to the basaltic underplating resulted in the production of high-K granitic melts. Formation of the Fiskenæsset TTGs, the foundering of the eclogitic residues into the mantle, and the emplacement of the high-K granites led to the growth of Archean continental crust in the Fiskenæsset region.     

Mineralogical evidence for crystallization conditions and petrogenesis of ilmenite-series I-type granitoids at the Baogutu reduced porphyry Cu deposit (Western Junggar,NW China): Mössbauer spectroscopy,EPM and LA-(MC)-ICPMS analyses

Primary ore-forming minerals retain geochemical signatures of magmatic crystallization information and can reveal the petrochemical conditions prevalent at the time of their formation. The Baogutu deposit is a typical reduced porphyry Cu deposit. Amphibole and biotite Fe³⁺/ΣFe ratios, minerals (feldspar, biotite, amphibole, zircon and apatite), in situ elemental and apatite Nd isotopic compositions were determined by Mössbauer spectroscopy, electron probe microanalysis, and laser ablation multiple-collection inductively coupled plasma mass spectrometry, respectively, to investigate the magma oxidation state, petrogenesis, source features, and to constrain the carbon species at magmatic stages for the intrusive phases. The results show that the primary plagioclase and amphibole in the mineralized diorite to granodiorite porphyry and post ore hornblende diorite porphyry are distinct (An_26-55 versus An_60-69; Mg-hornblende versus tschermakite). In particular, the amphibole shows distinct major and trace element compositions with light rare earth element enrichments and negative Eu anomalies in Mg-hornblende and light rare earth element depletions and no Eu anomalies in tschermakite. All the analyzed biotites are primary igneous phases with a biotite phenocryst profile showing significant variations of Zn, Cr, Sc and Sr from core to rim. These results may indicate the occurrence of mixing between two distinct magmas during mineral formation. Titanium in zircon and Si¹ in amphibole thermometries indicate that magma crystallized at >900 °C and continued to ∼650 °C. In situ apatite Nd isotope (εNd(t) = 5.6–7.6, T_DM2 = 620–460 Ma), indicate absence of significant reduced sedimentary contamination and the source of juvenile lower crust. Slightly decreasing Fe³⁺/ΣFe ratios from biotite and amphibole to whole rock indicate decreasing oxygen fugacity during magma crystallization. Recalculated biotite compositions according to Fe³⁺/ΣFe ratios indicate fO₂ values of less than Ni-NiO buffer (NNO) which show slightly lower values than that estimated according to zircon/melt distribution coefficients Ce anomalies (∼ΔNNO + 0.6). These values are consistent with the features of reduced porphyry Cu deposits. Crystallization of other mineral phases significantly affects the reliability of oxybarometer of zircon/melt distribution coefficients Eu anomalies and Mn contents in apatite. This oxidation state suggests that only CO₂ was present at the magmatic stage, and implies that CH₄ formed during CO₂ reduction occurring later hydrothermal alteration. The alteration of primary amphibole to actinolite released Ti, Al, Fe, Mn, Na and K to the fluid with later precipitation of titanite, albite and minor ilmenite and magnetite during actinolite alteration.     

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.     

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.     

Rare earth element signatures of economic and sub-economic porphyry copper systems in Urumieh–Dokhtar Magmatic Arc (UDMA), Iran

A wide variety of porphyry copper deposits have been reported along the Cenozoic Urumieh–Dokhtar magmatic arc in Iran. The formation of these deposits is attributed to closure of Neo-Tethys and the subsequent collisional tectonic regime during the Tertiary. This study presents whole-rock rare earth element (REE) data for the giant to small (Sarcheshmeh, Meiduk, Sungun, Darreh-Zerreshk, Dalli, Iju, Parkam and Ali-Abad) with sub-economic (Daraloo and Reagan) porphyry copper systems. The data indicate a temporal and geochemical evolution from sub-economic porphyry systems to economic deposits. All the economic and sub-economic porphyry copper systems exhibit LREE enrichment relative to HREE, whereas the economic deposits exhibit a relatively steep downward LREE to HREE profile, reflecting higher LREE abundance. The Eu anomalies vary from distinct negative in sub-economic deposits (Eu/Eu* = 0.28–0.70) to either markedly less negative or positive anomalies (Eu/Eu* = 0.45–1.67) in economic deposit. The economic porphyry deposits are characterized by relatively high La/Sm and Sm/Yb values, representing high crustal assimilation in a relatively thickened crust and provide insight into fractionation of hornblende with minor garnet in deep crustal parts (MASH zone). Compared with sub-economic deposits, the steep downward LREE to MREE and flatter to slightly upward MREE to HREE in economic deposits indicate hornblende involvement (magma evolution toward more volatile content). It seems that in an ongoing process of closure of Neo-Tethys, during compression and crustal shortening, the early Eocene–Oligocene sub-economic intrusions are followed by adakite-like hydrous Miocene (and younger) economic Cu-bearing intrusions.     

Extreme positive Ce-anomalies in a 3.0 Ga submarine volcanic sequence,Murchison Province: Oxygenated marine bottom waters

Systematic positive anomalies of Ce, where Ce/Ce* spans 2.1 to 11.4, are present in basalts and rhyolites of a 2.96 Ga submarine volcanic sequence of the Murchison Province, Western Australia. This volcanic sequence is host to a stratabound Cu–Zn deposit that formed on the seafloor from a seawater hydrothermal system. These are true Ce anomalies as Pr/Pr* < 1. In modern oxygenated marine water Ce is sequestered by Mn-oxides and hydroxides, which coprecipitate with Fe-oxides and hydroxides as nodules and crusts on the ocean floor, as well as Fe–Mn chemical sediments from hydrothermal systems at ocean spreading centers. Fe–Mn sediments have positive Ce anomalies and marine water complementary negative anomalies. Such Ce anomalies have not formerly been reported for Archean hydrothermally altered volcanic rocks. These extreme anomalies are attributed to Mn-transport in shallow-circulating oxygenated marine bottom waters peripheral to the deeper, hotter, hydrothermal system from which the Cu–Zn deposit formed, and record an oxygenated marine environment ~ 500 Ma before the so-called great oxidation event at ~ 2.4 Ga. Results for positive Ce anomalies in the Golden Grove volcanic sequence are complementary to negative anomalies in Archean BIF, collectively stemming from particulate scavenging of Ce^+ 3 in an oxic water column.     

Importance of hydrogeological conditions during formation of the karstic bauxite deposits,Central Guizhou Province,Southwest China: A case study at Lindai deposit

Karstic bauxite deposits are widespread in Central Guizhou Province, SW China, and high-grade ores are frequently sandwiched with overlying coal and underlying iron-rich layers and form a special “coal–bauxite–iron” structure. The Lindai deposit, which is one of the most representative karstic bauxite deposits in Central Guizhou Province, was selected as a case study. Based on textural features and iron abundances, bauxite ores in the Lindai deposit are divided into three types of ores, i.e., clastic, compact, and high-iron. The bauxite ores primarily comprise diaspore, boehmite, kaolinite, illite, and hematite with minor quartz, smectite, pyrite, zircon, rutile, anatase, and feldspar. The Al₂O₃ (53–76.8 wt.%) is the main chemical contents of the bauxite ore samples in the Lindai district, followed by SiO₂, Fe₂O₃, TiO₂, CaO, MgO, S, and P etc. Our geological data on the Lindai deposit indicated that the ore-bearing rock series and its underlying stratum have similar rare earth elements distribution pattern and similar Y/Ho, Zr/Hf, and Eu/Eu¹ values; additionally, all ore-bearing rock samples are rich in MgO (range from 0.16 wt.% to 0.68 wt.%), and the plots of the dolomites and laterites lie almost on or close to the weathering line fit by the Al-bearing rocks in Zr vs. Hf and Nb vs. Ta diagrams; suggesting that the underlying Middle Cambrian Shilengshui Formation dolomite is the parent rock of bauxite resources in the Lindai district.Simulated weathering experiments on the modern laterite from the Shilengshui Formation dolomite in the Lindai bauxite deposit show that hydrogeological conditions are important for karstic bauxite formation: Si is most likely to migrate, its migration rate is several magnitudes higher than those of Al and Fe under natural conditions; the reducing inorganic acid condition is the most conducive to Al enrichment and Si removal; Fe does not migrate easily in groundwater, Al enrichment and Fe removal can occur only in acidic and reducing conditions with the presence of organic matter.The geological and experimental studies show that “coal–bauxite–iron” structure in Lindai deposit is formed under certain hydrogeological conditions, i.e., since lateritic bauxite or Al-rich laterite deposited upon the semi-closed karst depressions, Si can be continuously removed out under neutral/acidic groundwater conditions; the coal/carbonaceous rock overlying the bauxitic materials were easily oxidized to produce acidic (H₂S, H₂SO₄, etc.) and reductant groundwater with organic materials that percolated downward, resulting in enrichment of Al in underlying bauxite; it also reduced Fe³⁺ to its easily migrating form Fe²⁺, moving downward to near the basal carbonate culminated in precipitating of ferruginous (FeS₂, FeCO₃, etc.) strata of the “coal–bauxite–iron” structure. Thus, the bauxitic materials experienced Al enrichment and Si and Fe removal under above certain hydrogeological conditions forming the high-quality bauxite.     

Nanhuan manganese deposits within restricted basins of the southeastern Yangtze Platform,China: Constraints from geological and geochemical evidence

The Nanhuan manganese deposits in the southeastern Yangtze Platform occur in the black shale series in the lower part of the Datangpo Formation. In order to constrain the genesis of the deposits, a detailed study was undertaken that involved field observations, major and trace element analyses, organic carbon analyses, and isotope analyses (C, O, S). The major findings are as follows. (1) The ore-bearing rock series, morphology of the ore bodies, and characteristics of ores in several deposits are similar. The ore minerals are rhodochrosite and manganocalcite. The gangue minerals are mainly quartz, feldspar, dolomite, and illite. Minor apatite and bastnaesite occur in the manganese ores. (2) The ores are enriched in Ca and Mg, whereas they are depleted in Si, Al, K, and Ti compared to wall rocks. The ores normalized to average Post-Archean Australian shale (PAAS) are enriched in Co, Mo, and Sr. The chondrite-normalized rare earth element (REE) patterns for ores and wall rocks are between those of typical hydrogenous and hydrothermal type manganese deposits. Additionally, the ores have positive Ce anomalies with an average Ce/Ce* of 1.23 and positive Eu anomalies with an average Eu/Eu* of 1.18 (normalized to PAAS). (3) The average content of organic carbon is 2.21% in the samples, and the average organic carbon isotopic value (δ¹³C_V-PDB) is − 33.44‰. The average inorganic carbon isotopic value (δ¹³C_V-PDB) of carbonates in Gucheng is − 3.07‰, while the values are similar in the other deposits with an average of − 8.36‰. The oxygen isotopic compositions (δ¹⁸O_V-PDB) are similar in different deposits with an average of − 7.72‰. (4) The sulfur isotopic values (δ³⁴S_V-CDT) of pyrite are very high and range from + 37.9‰ to + 62.6‰ (average of 52.7‰), which suggests that the pyrite was formed in restricted basins where sulfate replenishment was limited. The sulfate concentrations in the restricted basins were extremely low and enriched in δ³⁴S, which resulted in the very high δ³⁴S values for the pyrite that formed in the manganese deposits. Therefore, a terrigenous weathering origin for manganese can be excluded; otherwise, the sulfate would have been introduced into the basins together with terrigenous manganese, which would have decreased the δ³⁴S values of pyrites. The manganese, which originated from hydrothermal processes, was enriched in the restricted and anoxic basins, and then, it was oxidized to manganese oxyhydroxide in the overlying oxic waters whereby the products precipitated into the sediments. The manganese oxyhydroxide in the sediment was then reduced to Mn^2 + and released to the pore waters during the process of diagenesis. Some organic carbon was oxidized to CO₃^2 −, which made the depletion of ¹³C in manganese carbonates. Therefore, we suggest that the Nanhuan manganese deposits are hydrothermal–sedimentary/diagenetic type deposits.     

Geochemistry,provenance, and tectonic setting of Neoproterozoic metavolcanic and metasedimentary units,Werri area,Northern Ethiopia

Major, trace and rare earth element (REE) compositions of upper Proterozoic metavolcanic and metasedimentary rocks from the Tsaliet and Tembien Groups in the Werri district of northern Ethiopia were determined to examine their tectonic setting of eruption, provenance and source area weathering conditions. Tsaliet Group metavolcanic rocks in the Werri area have sub-alkaline chemistry characterized by low to intermediate SiO₂ contents, high Al₂O₃, low MgO and very low Cr and Ni. High field strength element (HFSE) abundances are highly variable. ∑REE abundances vary from 66.7 to 161.3 ppm, and chondrite-normalized REE patterns are moderately fractionated, with La_N/Yb_N values of between 3.1 and 9.0. Europium anomalies are variable (Eu/Eu* 0.80–1.21) but are generally positive (average Eu/Eu* 1.06). On tectonic discrimination diagrams, most samples have either volcanic-arc chemistry or fall in the overlap field with mid-oceanic ridge basalt (MORB). However, primitive mantle-normalized trace element abundances are comparable with sub-alkaline basalts from developed island arcs. ¹⁴⁷Sm/¹⁴⁴Nd ratios range from 0.1167 to 0.1269 (n = 3), yielding initial εNd_(800 Ma) of +3.8 to +4.9 and mean T_DM model age of 0.96 Ga, indicative of derivation from juvenile Neoproterozoic mantle. Metasediments from three locations (Werri1, Werri2 and Tsedia) in the Werri and Tsedia Slates have similar Al₂O₃, TiO₂ and HFSE contents but variable and low Na₂O, CaO and K₂O. Cr and Ni are slightly enriched in the Werri2 and Tsedia suites. SiO₂ is very variable, with average values of 70.75, 72.2 and 66.4 wt.% in the Werri1, Werri2 and Tsedia suites, respectively. ∑REE abundances in the metasediments (14.74–108.1) are lower than in the metavolcanics, and are slightly less fractionated, with La_N/Yb_N ratios of 0.8–5.9. Europium anomalies vary (Eu/Eu* 0.80–1.21) but are insignificant on average (Eu/Eu* 0.96). High values for the Chemical Index of Alteration (generally 70–90), and Plagioclase Index of Alteration (>75) in the Werri metasediments indicate moderate to severe chemical weathering in their source. Average major and trace element compositions of the metasediments and their REE patterns are comparable with the metavolcanics. ¹⁴⁷Sm/¹⁴⁴Nd ratios of the metasediments range from 0.1056 to 0.1398 (n = 4), with initial εNd_(800 Ma) of +3.4 to +5.0 and mean T_DM model age of 0.97 Ga, indicating derivation from juvenile Neoproterozoic crust similar to the underlying metavolcanics, with minimal (4–10%) contribution from older crust. The most sensitive tectonic setting discriminators indicate the Werri metasediments represent developed oceanic island arc sediments. The chemical similarity of the Werri metavolcanics to the nearby Adwa metavolcanics, Nakfa terrane in Eritrea, and volcanic units in central Saudi Arabia imply that juvenile Neoproterozoic Arabian Nubian Shield crust extended south at least as far as the Werri area of northern Ethiopia. The comparable geochemistry of the metasediments and their underlying lithologies attests to their derivation from this juvenile crustal material.     

Eocene potassic and ultrapotassic volcanism in south Tibet: New constraints on mantle source characteristics and geodynamic processes

In the Yangbajing area, southern Tibet, several monogenic volcanoes were conformably superimposed on the Linzizong calc-alkaline volcanic successions. According to their petrologic and geochemical characteristics, these monogenic volcanoes are composed of three rock varieties: tephritic phonolitic plugs and shoshonitic and trachytic lavas. Their geochemical systematics reveals that low-pressure evolutionary processes in the large voluminous Linzizong calc-alkaline magmas were not responsible for the generation of these potassic–ultrapotassic rocks, but the significant change in petrologic and geochemical characteristics from the Linzizong calc-alkaline to potassic–ultrapotassic magma is likely accounted for the change of metasomatic agents in the southern Tibetan lithospheric mantle source during the Paleocene to Eocene. The tephritic phonolites containing both leucite and plagioclase show primary ultrapotassic character similar to that of Mediterranean plagioleucititic magmas. Radiogenic Sr increases with SiO₂ in the xenolith-bearing trachytes strongly suggesting significant crustal assimilation in the shoshonitic magmas. The Yangbajing ultrapotassic rocks have high K₂O and Al₂O₃, and show depletion of high field strength elements (HFSEs) with respect to large ion lithophile elements. In primitive mantle-normalized element diagrams, all samples are characterized by positive spikes at Th (U) and Pb with negative anomalies at Ba, Nb–Ta and Ti, reflecting the orogenic nature of the ultrapotassic rocks. They are characterized by highly radiogenic ⁸⁷Sr/⁸⁶Sr_(i) ratios (0.7061–0.7063) and unradiogenic ¹⁴³Nd/¹⁴⁴Nd_(i) (0.5125), and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.688–18.733, ²⁰⁷Pb/²⁰⁴Pb = 15.613–15.637, and ²⁰⁸Pb/²⁰⁴Pb = 38.861–38.930) similar to the global subducting sediment. Strong enrichment of incompatible trace elements and high Th fractionation from the other HFSEs (such as Nb and U) clearly indicate that the Th-enriched sedimentary component in a network veined mantle source was mainly introduced by sediment-derived melts. In addition, the ultrapotassic rocks have significant Ce (Ce/Ce* = 0.77–0.84) and Eu (Eu/Eu* = 0.72–0.75) anomalies, suggesting a subduction sediment input into the southern Tibetan lithospheric mantle source. In contrast, high U/Th (> 0.20) and Ba/Th (> 32) and low Th/La (< 0.3) in the shoshonites indicate that the Eocene potassic magma originated from partial melting of the surrounding peridotite mantle pervasively affected by slab-related fluid addition from the dehydration of either the subducting oceanic crust or the sediment. Thus, at least two different subduction-related metasomatic agents re-fertilized the upper mantle. According to the radiometric ages and spatial distribution, the Gangdese magmatic association shows a temporal succession from the Linzizong calc-alkaline to ultrapotassic magmas. This indicates a late arrival of recycled sediments within the Tibetan lithospheric mantle wedge. The most diagnostic signatures for the involvement of continent-derived materials are the super-chondritic Zr/Hf (45.5–49.2) and elevated Hf/Sm values (0.81–0.91) in the ultrapotassic rocks. Therefore, the occurrence of orogenic magmatism in the Gangdese belt likely represents the volcanic expression of the onset of the India–Asia collision, preceding the 10 Ma Neo-Tethyan slab break-off process at 42–40 Ma. The absence of residual garnet in the mantle source for the ultrapotassic volcanism seems to imply that the southern Tibetan lithosphere was not been remarkably thickened until the Eocene (～ 50 Ma).     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.