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.     

Polygenesis of mafic-ultramafic complexes: Isotope-geochronological and geochemical evidence from zircons of the Berezovka massif rocks (Sakhalin Island)

Results of comprehensive isotope-geochronological (U-Pb dating; SHRIMP II) and geochemical (LA-ICP-MS) studies of zircons from different rocks of the Berezovka polygenetic mafic-ultramafic massif of the East Sakhalin ophiolite association are presented. The massif includes three proximal but genetically autonomous structure-lithologic complexes of different ages: protrusion of ultramafic rocks of restite nature, gabbroid intrusion breaking through it, and contact reaction zone located along their boundaries. The isotopic age of zircons in the massif as a whole and in its individual rocks varies over a broad range of values. The zircons belong to several populations according to their age (Ma) and other features: relict and xenogenous (~ 3100-990, 70–410, and ~ 395-210) and syngenetic (~ 200-100, ~ 90-65, and ~ 30-20). They differ in grain size and morphology, optical and cathodoluminescence images, and trace-element patterns. By morphology, the grains are divided into short-prismatic crystals with well-developed faces and edges, long-prismatic crystals with well-developed faces and edges, prismatic crystals with slightly resorbed faces and edges, prismatic crystals with strongly resorbed faces and edges, and intensely resorbed grains totally or partly lacking faceting. The ages of zircons depend inversely on the contents of La, Ce, and Yb, total contents of REE, (Ce/Ce*)n, and (Eu/Eu*)n. Some grains are characterized by abnormal REE and trace-element patterns due to their epigenetic redistribution. The wide scatter of the intermediate ages of relict and xenogenous zircon grains, their resorption and disturbed optical and geochemical features are probably due to the nonuniform rejuvenation of their isotope systems and variations in other parameters, caused by the effect of younger mafic melt and its fluids, whose crystallization gave rise to a gabbroid intrusion dated at 170–150 Ma. The obtained data on the isotopic age and other properties of zircons from the rocks of the Berezovka massif agree with the geological model of its polygenesis.     

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.     

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.     

In situ U–Pb dating and trace element analysis of zircons in thin sections of eclogite: Refining constraints on the ultra high-pressure metamorphism of the Sulu terrane,China

In situ U–Pb dating and trace element analysis of zircons, combined with a textural relationship investigation in thin section, is a powerful tool to constrain the ultra high-pressure stage of high-grade metamorphism. Two types of zircon grains have been identified in thin sections of a retrograde eclogite from the main hole of the Chinese Continental Scientific Drill project in the Sulu UHP terrane. Type 1 zircon grains occur as inclusions in fresh garnet and omphacite, and Type 2 zircon grains were found in symplectite around omphacite. The fresh rims of Type 1 zircons and mantles of a few Type 2 zircons exhibit remarkably lower REE, Y, Nb and Ta contents than the inherited zircon cores, suggesting coeval growth with garnet, rutile and apatite during UHP metamorphism. These may have formed in the UHP metamorphism and survived retrograde metamorphism. The weighted average ²⁰⁶Pb/²³⁸U age of these zircon domains (230 ± 4 Ma, 2σ) agrees well with the published age of coesite-bearing zircon separates (230 ± 1 Ma, 2σ), suggesting that the peak UHP metamorphism in the Sulu terrane may have occurred at ~ 230 Ma.Zircon domains surrounded or cut across by symplectite could have been altered by retrograde metamorphism. Together, they provide a younger weighted average ²⁰⁶Pb/²³⁸U age of 209 ± 4 Ma (2σ). These retrograde zircon domains have similar REE compositions to the ~ 230 Ma UHP zircon domains. These observations imply that the ~ 209 Ma zircon domains could have formed by fluid activity-associated alterations in the amphibolite-facies metamorphism, which could have resulted in the complete loss of Pb but not REEs in these domains.     

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.     

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.     

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.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

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.     

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.     

Ediacaran Águas Belas pluton,Northeastern Brazil: Evidence on age,emplacement and magma sources during Gondwana amalgamation

Ediacaran syenogranites from the Águas Belas pluton, Borborema Province, Northeastern Brazil were investigated in this work. The studied granitoids show high SiO₂, Fe# [FeO / (FeO + MgO)], total alkalis (K₂O + Na₂O) and BaO contents and medium Sr and low Nb contents. They show gentle fractionated rare earth patterns with discrete Eu negative anomalies. Major and trace element data point to chemical features of transitional high-K calc-alkaline to alkaline post-collisional magmatism. Structural data coupled with geochronological data suggest that NNE–SSW-trending sinistral movements at shear zones were initiated at ca. 590 Ma and have activated E–W pre-existing structures at the current crustal level. The synchronism of these shear zones allowed the dilation to generate the necessary space for the emplacement of the Águas Belas pluton.U–Pb SHRIMP zircon data show a cluster of ages around 588 ± 4 Ma which is interpreted as the crystallization age. Some zircon grain cores yielded ages within 2060–1860 Ma and 1670–1570 Ma intervals. Oxygen isotope compositions of zircon grains with distinct ages were measured using SHRIMP techniques. Twenty three analyses in the same zircon spots previously analyzed for U–Pb show δ¹⁸O values ranging from 5.79‰ to 10.30‰ SMOW. This large range of values results from variations both between grains and within grains (core–mantle/rim), and is interpreted as the result of mixing of components with distinct oxygen isotope compositions. The U–Pb zircon ages and the δ¹⁸O values associated with Paleoproterozoic Nd T_DM model ages suggest that the protolith of these granitoids involved a mantle component (Paleoproterozoic lithospheric mantle), Paleoproterozoic and Mesoproterozoic igneous rocks. Interactions with Mesoproterozoic or Neoproterozoic supracrustal rocks, may have occurred during the intrusion. The resulting magma evolved through biotite and K-feldspar fractionation.     

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%).     

Age and geochemistry of contrasting peridotite types in the Dabie UHP belt,eastern China: Petrogenetic and geodynamic implications

The Dabie ultrahigh-pressure (UHP) metamorphic belt, central China, contains two contrasting types of ultramafic–mafic complex. The Bixiling peridotite in the southern Dabie terrane contains abundant garnet (21–32 vol.%) and thus has high CaO +Al₂O₃ (9.94–15.3 wt.%). The peridotite also has high REE contents with flat REE patterns, high contents of S and other incompatible trace elements, together with low-Mg^# olivine and pyroxene and low Ni and PGE contents. Zircons from this peridotite mostly have low Th/U ratios, interpreted to reflect a metamorphic origin, and give dominantly Triassic ages (ca. 210 Ma). Other zircons with high Th/U ratios give upper intercept ages of 745 Ma. Most zircons have positive ?_Hf (+- 3.6 ～ +- 8.1) values with depleted-mantle model ages (T_DM) of 0.6–1.0 Ga (mean 0.8 Ga) and crustal model ages (T_crust) of 0.8–1.4 Ga (mean 1.1 Ga). We interpret that the Bixiling complex was formed as cumulates in a Neoproterozoic asthenosphere-derived magma chamber in the continental crust, and was later carried to garnet-stable depths (ca. ～ 4.4 GPa) during the subduction of the Yangtze Craton in the Triassic. In contrast, the Raobazhai peridotite in the northern Dabie terrane was metamorphosed at lower P/T conditions (i.e. 15 Kb and 1000 °C). All zircon grains from the peridotite yield Triassic ages (ca. 212 Ma) and have negative ?_Hf values (? 16.6 ～ ? 3.2), Mesoproterozoic model ages (T_DM = 1.0–1.5 Ga) and Paleoproterozoic crustal model ages (T_crust = 1.5–2.3 Ga). The peridotite is enriched in LREE ((La/Yb)_n ≈ 3.5), has high-Mg^# olivine and pyroxene, high Ni and PGEs but low Pd/Ir (mean 3.0). It represents a highly refractory residue of partial melting (up to 18%) of primitive mantle, and is similar to the cratonic mantle xenoliths in Phanerozoic igneous rocks from the eastern North China Craton (e.g. Mengyin and Hebi areas). Negative Ce, Eu and HFSE anomalies in the peridotites suggest that their protolith was derived from the shallow part of the mantle wedge (e.g. plagioclase-stable field) of the North China Craton, and was pulled to a deeper level (e.g. spinel-stable field) during the subduction of the Yangtze Craton. The mantle wedge, like peridotitic xenoliths in the Jurassic Xinyang diatremes at the southern edge of the North China Craton, was metasomatised by fluids/melts released from the subducted continental crust. The fragments of this modified mantle wedge were incorporated into the Yangtze crust during its subduction.     

Recurrent rare earth element mineralization in the northwestern Okcheon Metamorphic Belt,Korea: SHRIMP U–Th–Pb geochronology,Nd isotope geochemistry,and tectonic implications

Rare earth element (REE) mineralization is hosted within Neoproterozoic alkaline metaigneous rocks in the northwestern part of the Okcheon Metamorphic Belt (OMB), a polymetamorphosed fold-and-thrust belt transecting the Paleoproterozoic Gyeonggi and Yeongnam Massifs in the southern Korean Peninsula. The principal carrier phase of REEs is allanite. Allanite grains can be subdivided into several types based on the texture and mineral assemblage including quartz, K-feldspar, biotite, britholite, apatite, fergusonite, andradite, magnetite, zircon, titanite and fluorite. Electron microprobe analysis of allanite clearly distinguishes sample-to-sample variations in total REEs, Ca, Al, Fe and Y but the textural varieties from each rock sample do not show marked differences in those elements. Sensitive high-resolution ion microprobe dating of allanite and zircon reveals a complex history of multistage mineralization. Allanite grains from REE ores yielded Late Ordovician (444.6 ± 8.0 Ma), Permian to Triassic (ca. 300–220 Ma) and Early Jurassic (199–183 Ma) ²⁰⁸Pb/²³²Th ages. These multiple age components often coexist in single grains showing slight differences in backscattered electron brightness. The Ordovician components have distinctly higher Th/U than the younger domains in the same rock sample. The cores and rims of zircon from a syenite hosting REE ore bodies yielded Neoproterozoic (858.2 ± 6.3 Ma) and Early Jurassic (ca. 190 Ma) ²⁰⁶Pb/²³⁸U ages, respectively. The Early Jurassic ages (194–187 Ma) also obtained from zircon grains from granites taken from dykes occurring close to the ores and a drill core indicate the correspondence between granitic magmatism and REE mineralization. The Neoproterozoic zircon inheritance (weighted mean = 853.9 ± 3.8 Ma) in these granites is in sharp contrast to the dominant Paleoproterozoic inherited zircon from the widespread earliest Middle Jurassic granites enclosing the mineralized zone. The geotectonic significance of the Late Ordovician event recorded in the allanite, as well as in detrital zircon from the OMB, is still unclear but its temporal coincidence with intraplate volcanism and arc-related igneous activity, respectively, reported from the southwestern edge of the adjacent Taebaeksan Basin and the southwestern Gyeonggi Massif is noteworthy. The following Permian–Triassic and Early Jurassic mineralization events are probably linked to the continental suturing between the North and South China blocks and subsequent post-orogenic magmatism, and arc magmatism resulting from the paleo-Pacific plate subduction, respectively. Sub-grain Sm–Nd isotopic analyses of allanite by laser ablation multiple collector ICPMS yielded initial ε_Nd values plotting along the Nd isotopic evolution path of the Neoproterozoic metaigneous rocks, indicating that REEs originating from the host rock have been recycled during multistage mineralization events. The profound differences in inherited zircon ages and Nd isotopic compositions between the Early and Middle Jurassic granites may reflect the presence of a major thrust-bounded crustal structure beneath the OMB.     

Crustally-derived granites in the Panzhihua region,SW China: Implications for felsic magmatism in the Emeishan large igneous province

In the Panxi region of the Late Permian (~ 260 Ma) Emeishan large igneous province (ELIP) there is a bimodal assemblage of mafic and felsic plutonic rocks. Most Emeishan granitic rocks were derived by differentiation of basaltic magmas (i.e. mantle-derived) or by mixing between crustal melts and primary basaltic magmas (i.e. hybrid). The Yingpanliangzi granitic pluton within the city of Panzhihua intrudes Sinian (~ 600 Ma) marbles and is unlike the mantle-derived or hybrid granitic rocks. The SHRIMP zircon U–Pb ages of the Yingpanliangzi pluton range from 259 ± 8 Ma to 882 ± 22 Ma. Younger ages are found on the zircon rims whereas older ages are found within the cores. Field relationships and petrography indicate that the Yingpanliangzi pluton must be < 600 Ma, therefore the older zircons are interpreted to represent the protolith age whereas the younger analyses represent zircon re-crystallization during emplacement. The Yingpanliangzi granites are metaluminous and have negative Ta–Nb_PM anomalies, low εNd_{(260 Ma)} values (? 3.9 to ? 4.4), and high I_Sr (0.71074 to 0.71507) consistent with a crustal origin. The recognition of a crustally-derived pluton along with mantle-derived and mantle–crust hybrid plutons within the Panxi region of the ELIP is evidence for a complete spectrum of sources. As a consequence, the types of Panxi granitoids can be distinguished according to their ASI, Eu/Eu*, εNd_(T), εHf_(T), T_Zr(°C) and Nb–Ta_PM values. The diverse granitic magmatism during the evolution of the ELIP from ~ 260 Ma to ~ 252 Ma demonstrates the complexity of crustal growth associated with LIPs.     

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.     

SHRIMP zircon U–Pb ages of eclogite and orthogneiss from Sulu ultrahigh-pressure zone in Yangkou area,eastern China

We report SHRIMP U–Pb age of zircons in four samples of eclogite and one sample of orthogneiss from Sulu ultrahigh-pressure (UHP) zone in Yangkou area, eastern China. UHP rocks are distributed along the Sulu orogenic belt suturing North China Block with South China Block. In Yangkou area, UHP unit is well exposed for about 200 m along Yangkou beach section and consists mainly of blocks or lenses of ultramafic rocks and eclogite together with para- and orthogneiss which are highly sheared partly. Zircon grains examined in this study from eclogite show oscillatory zoning and overgrowth texture in CL images, and most of the grains have high Th/U ratio ranging from 0.8 to 2.1 indicating an igneous origin. The weighted mean ²⁰⁶Pb/²³⁸U ages of zircons from the four samples range from 690 to 734 Ma. These ages can be correlated to the magmatic stage of the protoliths. In rare cases, zircon grains possess a narrow rim with very low Th/U ratio (< 0.02). EPMA U–Th-total Pb dating of such rim yields younger ages that range from 240 to 405 Ma marking the metamorphic stage. On the other hand, zircons from the orthogneiss show irregular shape and zoning with inclusion-rich core and inclusion-free rim. These grains of zircon yield U–Pb discordia intercept ages of 226 ± 63 Ma and 714 ± 110 Ma (MSWD 0.78). Bulk of the areas of the rims rim of the zircons demonstrate younger ²⁰⁶Pb/²³⁸U ages close to the upper intercept, with low Th/U ratio (< 0.20) indicating their metamorphic origin. In contrast, the cores show older ²⁰⁶Pb/²³⁸U ages close to lower intercept and high Th/U ratio of (0.14–5.25) indicating their igneous origin. The upper intercept age is also commonly noted in zircons from eclogite. Our results suggest a bimodal igneous activity along this zone during the Neoproterozoic, probably related to the rifting of the Rodinia supercontinent.     

Early to Middle Devonian granitic and volcanic rocks from the central Gulf of Maine

Cashes Ledge igneous suite in the central Gulf of Maine is represented by 10 granitic and two felsic tuff samples collected from bedrock outcrops using the submersible Alvin in 1971–1972 and archived at the Woods Hole Oceanographic Institute. Laser ablation ICP-MS analyses of zircon grains yielded crystallization ages of 414.9 ± 1.1 Ma and 399.7 ± 1.5 Ma for two alkali feldspar granite samples, 407.0 ± 1.9 Ma for a syenogranite sample, and 384.4 ± 2.3 Ma and 383.9 ± 1.6 Ma for two felsic tuff samples. The samples contain iron-rich mafic minerals, including aegirine-augite, grunerite/ferroedenite, and annite. Most of the samples are alkaline to slightly peralkaline, with high concentrations of SiO₂, Y, Zr, Nb, and REE, strong negative Eu anomalies, and positive epsilon Nd values (1.8 to 3.7). The suite resembles part of a belt of similar Silurian–Devonian rocks with ages between 426 and 370 Ma now recognized in the central part of Avalonia in southeastern New England. They formed in a long-lived, likely extensional regime linked to subduction and subsequent complex transcurrent motions among Ganderia, Avalonia, and Meguma, culminating in the closure of the Rheic Ocean.     

Ti-in-zircon thermometry applied to contrasting Archean metamorphic and igneous systems

Ti-in-zircon thermometry with SHRIMP II multi-collector has been applied to two well-documented Archean igneous and metamorphic samples from southern West Greenland. Zircons from 2.71 Ga partial melt segregation G03/38 formed in a small (< 1 m³), closed system within a mafic rock under high pressure granulite facies conditions. Results of 14 Ti analyses present a mean apparent zircon crystallization temperature of 679 ± 11 °C, underestimating independent garnet-clinopyroxene thermometry by 20–50 °C but consistent with reduced a_TiO2 in this system. 36 spot analysis on 15 zircons from 3.81 Ga meta-tonalite G97/18, with an estimated magmatic temperature > 1000 °C, yield a low-temperature focused normal distribution with a mean of 683 ± 32 °C, further demonstrated by high resolution Ti mapping of two individual grains. This distribution is interpreted to represent the temperature of the residual magma at zircon saturation, late in the crystallization history of the tonalite. Hypothetically, Ti-in-zircon thermometry on Eoarchaean detrital zircons sourced from such a high temperature tonalite would present a low-temperature biased image of the host magma, which could be misconstrued as being a minimum melt granite. Multiple analyses from individual zircons can yield complex Ti distributions and associated apparent temperature patterns, reflecting cooling history and local chemical environments in large magma chambers. In addition to inclusions and crystal imperfections, which can yield apparent high temperature anomalies, zircon surfaces can also record extreme (> 1000 °C) apparent Ti temperatures. In our studies these were traced to ⁴⁹Ti (or a molecular isobaric interference) contamination derived from the double sided adhesive tape used in sample preparation, and should not be assigned geological significance.