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.     

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

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

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.     

Delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex,North China Craton and its geological implications

Through detailed studies we have delineated a suite of banded TTG gneisses from the Zanhuang Complex. The protolith of the gneisses, predominantly tonalite, has undergone intensive metamorphism, deformation and anatexis and in a banded structure is intimately associated with melanocratic dioritic gneiss and leucocratic trondhjemitic veins. SHRIMP Zircon U–Pb data show that the tonalite was formed ca. 2692 ± 12 Ma ago. The tonalitic gneiss has the features of high SiO₂ (67.76–73.31%), high Al₂O₃ (14.38–15.83%), rich in Na₂O (4.48–5.07%) and poor in K₂O (0.77–1.93%). The gneiss is strongly fractioned in REE ((La/Yb)_N = 12.02–24.65) and shows a weak positive Eu anomaly (Eu/Eu^* = 1.05–1.64). It has high contents of Ba (199–588 ppm) and Sr (200–408 ppm), low contents of Yb (0.32–1.00 ppm) and Y (3.41–10.3 ppm) with high Sr/Y ratios (21.77–96.77) and depletion in HFSE Nb, Ta and Ti. These characteristics are similar to those of the high-Si adakitic rocks. The melanocratic dioritic gneiss has low SiO₂ (59.81%), high MgO (6.34%), high Al₂O₃ (14.02%) contents, rich in Na₂O (3.7%) and poor in K₂O (1.79%), with high Mg index (Mg^# = 67). REE and trace elements are on the whole similar to that of the tonalitic gneiss, but compatible element abundances V (116 ppm), Cr (249 ppm), Co (37 ppm) and Ni (179 ppm) are higher. The leucocratic felsic bands (approximating trondhjemite in composition) have major oxides similar to that of the TTG gneisses but the REE and compatible elements are extremely low, which are indicative of the products of anatexis. The tonalitic gneiss has positive ε_Nd(t) (2.37–3.29) and low initial Sr (0.69719–0.70068) values with depleted mantle Nd model age of ca. 2.8 Ga, suggesting its generation from partial melting of mantle-derived juvenile crust. The dioritic gneiss was also derived from subduction environment, but has undergone significant metasomatism of mantle wedge. The delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex further proves that the North China Craton experienced large-scale continental crustal accretion in early Neoarchean, and gives new constraints on the subdivision of the early blocks and greenstone belts of the craton.     

The petrogenesis and tectonic implications of the granitoid gneisses from Xingxingxia in the eastern segment of Central Tianshan

As part of Central Asian Orogenic Belt (CAOB), the Central Tianshan zone plays a crucial role in the reconstruction of the tectonic evolution of the CAOB. Furthermore, it is bordered by the Tarim Craton to the south, and the comparable evolutionary history between them enables the Central Tianshan zone to provide essential information on the crustal evolution of the Tarim Craton. The eastern segment of the Central Tianshan tectonic zone is characterized by the presence of numerous Precambrian metamorphic rocks, among which the Xingxingxia Group is the most representative one. The granitoids gneisses, intruded into the Xingxingxia Group, consist of two major lithological assemblages: (1) biotite-monzonitic gneisses and (2) biotite-plagioclase gneisses. These metamorphosed granitoid rocks are characterized by enrichment in SiO₂, Al₂O₃ and K₂O and depletion in MgO and FeO_T. The Rittmann index (σ) spreads between 1.44 and 2.21 and ACNK (Al₂O₃/(CaO + Na₂O + K₂O)) ranges from 1.03 to 1.08, indicating that these granitoid gneisses are high-K calc-alkaline and peraluminous. Trace element data indicate that the studied samples are enriched in LREE with moderate REE fractionated patterns ((La/Yb)_N = 10.5–75.3). The concentrations of HREE of the garnet-bearing gneisses are significantly higher than those of garnet-free gneisses. The former show pronounced negative Eu anomalies (Eu/Eu^* = 0.32–0.57), while the latter are characterized by negligible negative Eu anomalies to moderate positive Eu anomalies (Eu/Eu^* = 0.80–1.35). In addition, the enrichment of LILE (Rb, Th, K, Pb) and depletion of HFSE (Ta, Nb, P, Ti) of the examined granitoid gneisses are similar to typical volcanic-arc granites. Zircons U–Pb dating on the biotite monzonitic gneiss yields a weighted mean ²⁰⁶Pb/²³⁸U age of 942.4 ± 5.1 Ma, suggesting their protoliths were formed in the early Neoproterozoic, which is compatible with the time of the assembly of supercontinent Rodinia. The zircons have a large ε_Hf(t) variation from −5.6 to +3.2, suggesting that both old crust-derived magmas and mantle-derived juvenile materials contributed to the formation of their protoliths. Based on field observation, and petrological, geochemical and geochronological investigations, we infer that the granitoid gneisses from Xingxingxia were probably formed on a continental arc that resulted from the interaction of Australia and the Tarim Craton during the assembly of the Rodinia supercontinent, and that the Central Tianshan zone was a part of the Tarim Craton during that time. Besides, the Grenvillian orogenic events may have developed better in the Tarim Craton than previously expected.     

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

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

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.     

Nd–Hf–Sr–Pb isotopes and trace element geochemistry of Proterozoic lamproites from southern India: Subducted komatiite in the source

The probable sources of some of the famous Indian diamonds are the 1.2 Ga old Krishna lamproites of Southern India, a rare Proterozoic occurrence of lamproites which are usually Cretaceous or younger in age. In this study we report Nd, Sr, Pb and Hf isotopes and multiple trace element concentrations of the Krishna lamproites. The goals are to evaluate mantle-processes and the petrogenesis of these ultrapotassic rocks of extreme chemical composition in light of these geochemical data, including their major element compositions.The Krishna lamproites show nearly uniform, parallel rare earth element (REE) distribution patterns with high concentrations and extreme light-REE enrichment (La/Yb_(N) = 41–88), high average concentrations of Ba (∼ 1200 ppm), Sr (∼ 1200 ppm), Zr (∼ 930 ppm), La (∼ 230 ppm), high U/Pb and Th/U ratios with notable absence of any Eu-anomaly. These rocks are typically porphyritic without any evidence of crystal accumulation, and have moderately high Mg-numbers (59–73) along with high Ni (average ∼ 301 ppm, highest 819 ppm) and Cr (average ∼ 183 ppm, highest 515 ppm) concentrations that show a positive correlation with MgO (wt.%), implying a role of olivine in the melt source. The low SiO₂ content (lowest 37.8%, average 49%) and high Nb (average 147 ppm), Zr, Sr, as well as Ni and Cr in these rocks indicate lack of upper continental crustal contribution in the genesis of these rocks. The initial Pb-isotopic composition of these lamproites is unusual in that in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb plot, these rocks plot to the left of the 1.2 Ga geochron (age of emplacement), unlike most mantle-derived rocks. This Pb-isotopic signature and the superchondritic Nb/Ta ratios (average 23.6) of these rocks rule out their derivation from a metasomatized sub-continental lithospheric mantle. The high ²⁰⁷Pb/²⁰⁴Pb at low ²⁰⁶Pb/²⁰⁴Pb indicates an Archean component in the source of these rocks. We argue that this Archean crustal component, which produced the low-SiO₂ lamproites along with the high Ni and Cr must have been ultrabasic, and we propose a model in which these lamproites formed by partial melting of metasomatized, subducted Archean komatiite in a peridotite mantle-source assemblage. In addition, these rocks display initial Hf isotopic compositions similar to Al-depleted komatiites, and high Nb/U, Nb/Th, and TiO₂ as well as low Al₂O₃/TiO₂ ratios (1.1–4.2) and average CaO/Al₂O₃ of ∼ 1.6 that are also similar to Archean komatiites. This is also supported by the initial Pb isotopic composition of the Krishna lamproites, requiring evolution in a variably high U/Pb, Th/Pb reservoir early in earth history, possibly resulting from preferential segregation of Pb relative to U and Th in the sulfides of the komatiite.The Al-depleted subducted komatiitic component was enriched by carbonate metasomatism in the peridotitic mantle. This metasomatism was responsible for the observed Nd–Hf isotope characteristics, specifically variable ε_Nd(T) at relatively constant ε_Hf(T) in the lamproites. This Nd–Hf-isotopic characteristic seems to be common in global lamproites of all ages. Our proposed model for the genesis of the Krishna lamproites involving a subducted komatiitic source may also be applicable for other global lamproites from cratonic settings, as older komatiite-bearing subducted crustal components were possibly ubiquitous in the architecture of ancient cratonic mantle.     

Adakite-like signature of porphyry granitoid stocks in the Meiduk and Parkam porphyry copper deposits,NE of Shahr-e-Babak,Kerman, Iran: Constrains on geochemistry

The Middle Miocene porphyry granitoid stocks of Meiduk and Parkam porphyry copper deposits are intruded in the north-western part of the Dehaj-Sarduiyeh volcano-sedimentary belt in the south-eastern extension of the Urumieh-Dukhtar Magmatic Arc (UDMA) in Iran. The porphyritic to microgranular granitoids are mainly consist of quartz diorite, granodiorite and diorite. The whole rock geochemical analyses of these rocks reveals sub-alkaline, calc-alkaline, meta-peraluminous and I-type characteristics. Their geochemical characteristics such as Al₂O₃ content of 13.51–17.05 wt%, high Sr concentration (mostly >400 ppm), low Yb (an average of 0.74 ppm) and Y (an average of 9.02 ppm) contents, strongly differentiated REE patterns (La/Yb ≥ 20), lack of Eu anomaly (Eu/Eu¹ ≥ 1) are indicative of adakitic signature. Their enrichment in low field strength elements (LFSE) and conspicuous negative anomalies for Nb, Ta and Ti are typical of subduction related magmas. Detailed petrological studies and geochemical data indicated that Meiduk and Parkam porphyry granitoids were derived from amphibole fractionation of hydrous melts at a depth of >40 km in a post-collisional tectonic setting.     

Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti,REE) deposit (Amazonas,Brazil)

The Morro dos Seis Lagos niobium deposit (2897.9 Mt at 2.81 wt% Nb₂O₅) is associated with laterites formed by the weathering of siderite carbonatite. This iron-rich lateritic profile (>100 m in thickness) is divided into six textural and compositional types, which from the top to the base of the sequence is: (1) pisolitic laterite, (2) fragmented laterite, (3) mottled laterite, (4) purple laterite, (5) manganiferous laterite, and (6) brown laterite. All the laterites are composed mainly of goethite (predominant in the lower and upper varieties) and hematite (predominant in the intermediate types, formed from goethite dehydroxylation). The upper laterites were reworked, resulting in goethite formation. In the manganiferous laterite (10 m thick), the manganese oxides (mainly hollandite, with associated cerianite) occur as veins or irregular masses, formed in a late event during the development of the lateritic profile, precipitated from a solution with higher oxidation potential than that for Fe oxides, closer to the water table. Siderite is the source for the Mn. The main Nb ore mineral is Nb-rich rutile (with 11.26–22.23 wt% Nb₂O₅), which occurs in all of the laterites and formed at expense of a former secondary pyrochlore, together with Ce-pyrochlore (last pyrochore before final breakdown), Nb-rich goethite and minor cerianite. The paragenesis results of lateritization have been extremely intense. Minor Nb-rich brookite formed from Nb-rich rutile occurs as broken spherules with an “oolitic” (or Liesegang ring structure). Nb-rich rutile and Nb-rich brookite incorporate Nb following the [Fe³⁺ + (Nb, Ta) for 2Ti] substitution and both contain up to 2 wt% WO₃. The laterites have an average Nb₂O₅ content of 2.91 wt% and average TiO₂ 5.00 wt% in the upper parts of the sequence. Average CeO₂ concentration increases with increasing depth, from 0.12 wt% in the pisolitic type to 3.50 wt% in the brown laterite. HREE concentration is very low.     

A mafic intrusion of “arc affinity” in a post-orogenic extensional setting: A case study from Ganluogou gabbro in the northern Yidun Arc Belt,eastern Tibetan Plateau

Generally, arc-related or subduction-related mafic magmas are formed during or slightly postdate subduction, and characterized by depletion in high field strength elements (HFSEs) relative to the large ion lithophile elements (LILEs) and light rare-earth elements (LREEs). Combining with mineral chemistry and Sr–Nd isotopes, these geochemical characteristics were usually used to define an arc setting, especially for some ancient arcs that had been strongly modified by later tectonic activities. However, we report an exceptional case from the northern part of the Triassic Yidun Arc Belt, eastern Tibetan Plateau. The Ganluogou gabbro (∼152 Ma) occurs as several intrusive bodies. Its mineral assemblage is olivine (chrysolite), plagioclase (anorthite), clinopyroxene (diopside), amphibole (edenite and pargasite) and phlogopite. Whole rock geochemistry shows low SiO₂ (42.87–46.99 wt.%), total rear earth elements (ΣREE = 22.8–28.4 ppm), Na₂O + K₂O (0.92–1.34 wt.%), and high Al₂O₃, MgO and FeO contents. It has small variations of initial ⁸⁷Sr/⁸⁶Sr ((⁸⁷Sr/⁸⁶Sr)_i = 0.7053–0.7055) and ε_Nd(t) values (−4.8 to −1.8). All the samples exhibit enrichment in LILEs including Th and U, but strongly depleted in HFSEs, including Nb, Ta, Zr and Hf. For the mineral chemistry, there are two type amphiboles. Amp(I) show higher V, Sc, Cr, Sr, Nb and Zr contents, but lower Th and U contents than those of Amp(II). Their REE patterns range from convex shape without Eu anomaly to LREE-enriched pattern with weak positive Eu anomaly. We suggest that Amp(I) was crystallized from a liquid that was mainly buffered by olivine, clinopyroxene and plagioclase, while Amp(II) crystallized from later melt that was mainly buffered by olivine. Based on clinopyroxene chemistry, compositions of coexisting olivine and plagioclase, and whole rock Sr–Nd isotopes, the parental magma of the Ganluogou gabbro is interpreted as a tholeiitic arc-affinity magma, which might be derived from an N-MORB mantle that had been metasomatised by slab-derived melts in the late Triassic (237–206 Ma). Thus, the Ganluogou gabbro provides an example that magmas exhibiting arc-affinity could in fact be formed in a post-orogenic extensional setting.     

Dehydration and melting during continental collision: Constraints from element and isotope geochemistry of low-T/UHP granitic gneiss in the Dabie orogen

A combined study of petrography, whole-rock major and trace elements as well as Rb?Sr and Sm?Nd isotopes, and mineral oxygen isotopes was carried out for two groups of low-T/UHP granitic gneiss in the Dabie orogen. The results demonstrate that metamorphic dehydration and partial melting occurred during exhumation of deeply subducted continent. Zircon δ¹⁸O values of ? 2.8 to + 4.7‰ for the gneiss are all lower than normal mantle values of 5.3 ± 0.3‰, consistent with ¹⁸O depletion of protolith due to high-T meteoric-hydrothermal alteration at mid-Neoproterozoic. Most samples have extremely low ⁸⁷Sr/⁸⁶Sr ratios at t₁ = 780 Ma, but very high ⁸⁷Sr/⁸⁶Sr ratios at t₂ = 230 Ma. This suggests intensive fluid disturbance due to the hydrothermal alteration of protoliths during Neoproterozoic magma emplacement and the metamorphic dehydration during Triassic continental collision. Rb–Sr isotopes, Th/Ta vs. La/Ta and Th/Hf vs. La/Nb relationships suggest that Group I gneiss experienced lower degrees of hydrothermal alteration, but higher degrees of dehydration, than Group II gneiss. The two groups of gneiss have similar patterns of REE and trace element partition. Group I gneiss displays good correlations between Nb and LREEs but no correlations between Nb and LILEs (Rb, Ba, Pb, Th and U), indicating differential mobilities of LILEs during the dehydration. Thus the correlation between Nb and LREEs is inherited from protolith rather than caused by metamorphic modification. Relative to Group I gneiss, Group II gneiss has stronger negative Eu anomaly, lower contents of Sr and Ba but higher contents of Rb, Th and U. In particular, Nb correlates with LILEs (e.g., Rb, Sr, Ba, Th and U), but not with LREEs (La and Ce). This may indicate decoupling between the dehydration and LILEs transport during continental collision. Furthermore, dehydration melting may have occurred due to breakdown of muscovite during “hot” exhumation. Group II gneiss has extremely low contents of FeO + MgO + TiO₂ (1.04 to 2.08 wt.%), high SiO₂ contents of 75.33 to 78.23 wt%, and high total alkali (Na₂O + K₂O) contents (7.52 to 8.92 wt.%), comparable with compositions predicted from partial melting of felsic rocks by experimental studies. Almost no UHP metamorphic minerals survived; felsic veins of fine-grain minerals occurs locally between coarse-grain minerals, resulting in a kind of metatexite migmatites due to dehydration melting without considerable escape of felsic melts from the host gneiss. In contrast, Group I gneiss only shows metamorphic dehydration. Therefore, the two groups of gneiss show contrasting behaviors of fluid–rock interaction during the continental collision.     

Petrogenesis of Carboniferous adakites and Nb-enriched arc basalts in the Alataw area,northern Tianshan Range (western China): Implications for Phanerozoic crustal growth in the Central Asia orogenic belt

Carboniferous volcanic rocks in the Alataw area, Northern Tianshan Range (Xinjiang), consist of early Carboniferous (ca. 320 Ma) adakites and Nb-enriched arc basalts and basaltic andesites (NEBs), and late Carboniferous (ca. 306–310 Ma) mainly high-K calc-alkaline andesites, dacites and rhyolites. The adakites are calc-alkaline, and characterized by high Na₂O/K₂O (1.52–3.32) ratios, negligible to positive Eu anomalies, strong depletion of heavy rare earth elements (e.g., Yb = 0.74–1.47 ppm) and Y (6.7–14.9 ppm), positive Sr and Ba but negative Nb and Ti anomalies, and relatively constant ε_Nd(T) values (+ 3.4–+ 6.6) and (⁸⁷Sr/⁸⁶Sr)_i ratios (0.7035–0.7042). Some andesitic and dacitic adakite samples exhibit high MgO contents similar to magnesian andesites. The NEBs are sodium-rich (Na₂O/K₂O = 2.03–8.06), and differ from the vast majority of arc basalts in their higher Nb, Zr, TiO₂ and P₂O₅ contents and Nb/Th, Nb/La and Nb/U ratios, and minor negative to positive anomalies in Ba, Nb, Sr, Zr and Ti. They have the highest ε_Nd(T) values (+ 6.4–+ 11.6) but varying (⁸⁷Sr/⁸⁶Sr)_i ratios (0.7007–0.7063). The high-K calc-alkaline suite is similar to typical ‘normal’ arc volcanic rocks in terms of moderately fractionated rare earth abundance and distinctly negative Eu, Nb, Sr and Ti anomalies. They have ε_Nd(T) values (+ 1.2–+ 6.4) and (⁸⁷Sr/⁸⁶Sr)_i ratios (0.7018–0.7059). Geochemically, they are similar to coeval I-type granitoids in the Alataw area. Given the presence of early Carboniferous ophiolites in the Northern Tianshan Range, and the isotopically inappropriate compositions of Proterozoic metamorphic basement in the Alataw area, we argue that the Alataw adakites were most probably related to the melting of young subducted crust of the Northern Tianshan Ocean. The NEBs likely originated from mantle wedge peridotites metasomatized by adakites and minor slab-derived fluids. The later high-K calc alkaline suite was generated by AFC processes that acted on melts derived from a mantle wedge metasomatized by hydrous fluids. The larger range of isotopic compositions exhibited by both the NEB and high-K suite, relative to the adakites, suggests that the mantle wedge was heterogeneous prior to slab- or fluid-mediated metasomatism.Continental crustal growth of the Central Asian orogenic belt was dominated by contributions of the juvenile materials from the depleted mantle prior to 270 Ma and possibly afterwards. The results of this study suggest that other Carboniferous Nb-enriched basalts in the Tianshan Range were generated by subduction processes rather than by intraplate tectonics as previously proposed.     

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.     

Mafic xenoliths in Proterozoic kimberlites from Eastern Dharwar Craton,India: Mineralogy and P–T regime

Mafic xenoliths of garnet pyroxenite and eclogite from the Wajrakarur, Narayanpet and Raichur kimberlite fields in the Archaean Eastern Dharwar Craton (EDC) of southern India have been studied. The composition of clinopyroxene shows transition from omphacite (3–6 wt% Na₂O) in eclogites to Ca pyroxene (<3 wt% Na₂O) in garnet pyroxenites. Some of the xenoliths have additional phases such as kyanite, enstatite, chromian spinel or rutile as discrete grains. Clinopyroxene in a rutile eclogite has an X_Mg value of 0.70, which is unusually low compared to the X_Mg range of 0.91–0.97 for all other samples. Garnet in the rutile eclogite is also highly iron-rich with an end member composition of Prp_26.5Alm_52.5Grs_14.7Adr_5.1TiAdr_0.3Sps_1.0Uv_0.1. Garnets in several xenoliths are Cr-rich with up to 8 mol% knorringite component. Geothermobarometric calculations in Cr-rich xenoliths yield different P–T ranges for eclogites and garnet pyroxenites with average P–T conditions of 36 kbar and 1080 °C, and 27 kbar and 830 °C, respectively. The calculated P–T ranges approximate to a 45 mW m^?2 model geotherm, which is on the higher side of the typical range of xenolith/xenocryst geotherms (35–45 mW m^?2) for several Archaean cratons in the world. This indicates that the EDC was hotter than many other shield regions of the world in the mid-Proterozoic period when kimberlites intruded the craton. Textural and mineral chemical characteristics of the mafic xenoliths favour a magmatic cumulate process for their origin as opposed to subducted and metamorphosed oceanic crust.     

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

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

Geochemistry of pillow basalts from Bompoka,Andaman–Nicobar islands,Bay of Bengal,India

Pillow lavas in Bompoka island of the Andaman–Nicobar islands, forming a part of Sunda–Burmese forearc, are composed of plagioclase and clinopyroxene microphenocrysts in a fine-grained ferruginous groundmass along with glass. They are also characterized by several quench plagioclase and clinopyroxene morphologies. Zr/TiO₂ versus Nb/Y relationship of these pillow lavas show that these are tholeiitic basalts in composition. These basalts have low MgO (5.19–6.12 wt%), Ni (84–118 ppm), and Cr (144–175 ppm) abundance and high FeO^(T)/MgO (1.71–1.92) ratios, reflecting their fractionated nature. In Th/Yb versus Nb/Yb and Ti/Yb versus Nb/Yb binary diagrams, they show N-MORB affinity. However, La/Nb–Y and Ce/Nb–Th/Nb relationships along with a slight LREE depleted (La_N/Yb_N = 0.75–0.82) pattern and high Ba/Zr (0.28–0.40) ratios and LILE (K, Rb, Ba, Sr and Th) enrichment relative to N-MORB, suggest their back-arc basin basalt affinity. It is inferred that these pillow basalts have been derived from a metasomatised N-MORB-like mantle source in a trench-distal (wider) back-arc basin, probably near the leading edge of the Eurasian continent during Early to Late Cretaceous times, prior to the currently active Andaman–Java subduction system.     

Petrogenesis and geochemical characteristics of plagiogranites from Naga Ophiolite Belt,northeast India: Fractional crystallization of MORB-type magma

The Naga Ophiolite Belt is a part of the Naga-Arakan-Yoma flysch trough that occurs along the Indo-Myanmar border. It is represented by peridotites, mafic-ultramafic cumulates, mafic volcanics, mafic dykes, plagiogranites, pelagic sediments and minor felsic to intermediate intrusives. Minor plagiogranites, gabbros and thin serpentinite bands occur juxtaposed near Luthur, with the slate-phyllite-metagreywacke sequence (Phokpur Formation) adjacent to the contact. The development of tonalites, trondhjemites and diorites in the oceanic crust, which is grouped as plagiogranites, offers an opportunity to study the process of formation of silicic melts from mafic crust. Plagiogranites from Naga Ophiolite Belt contains moderate SiO₂ (51.81–56.71 wt.%), low K₂O (0.08–1.65 wt.%) and high Na₂O (4.3–5.03 wt.%). The Naga Ophiolite Belt plagiogranites like ocean-ridge granites contain low K₂O, high Na₂O and CaO. The rocks investigated from Naga Ophiolite Belt contain TiO₂ concentrations above the lower limit for fractionated Mid Oceanic Ridge Basalt which is above 1 wt% of TiO₂ and the ternary plots of A (Na₂O + K₂O) F(FeO^T) M(MgO) and TiO₂-K₂O-SiO₂/50 indicate that the plagiogranite are tholeiitic in character and gabbro samples are calc-alkaline in nature. The plagiogranites are enriched in Rb, Ba, Th, U, Nb and Sm against chondrite with negative anomalies on Sr and Zr whereas Y and Yb are depleted to Mid Oceanic Ridge Basalt. The chondrite normalized REE patterns of the plagiogranite display enrichments in LREE (La_N/Sm_N: 2.37–3.62) and flat HREE (Eu/Eu*: 0.90–1.06). The Mid Oceanic Ridge Basalt normalization of gabbro is characterized by strong enrichment of LILE like Ba and Th. The REE pattern is about 50–100 times chondrite with slight enrichment of LREE (La_N/Sm_N = 2.21–3.13) and flat HREE (Eu/Eu*: 0.94–1.19). The major-element and trace element data of the NOB plagiogranites and their intrusive nature with host gabbroic rock suggest that the plagiogranites were produced by fractional crystallization of basaltic parental magmas at Mid Oceanic Ridge.     

Significance of adakites in petrogenesis of early Silurian magmatism at the Yudai copper deposit in the Kalatag district,NW China

Yudai is a newly discovered copper deposit associated with a porphyritic quartz diorite, in the Kalatag district of the eastern Tianshan, China. SHRIMP U-Pb dating of zircons from the diorite yielded an age of 432 ± 3 Ma. The diorite is peraluminous (ASI = 0.98–1.10), calc-alkaline to tholeiitic with high Al₂O₃ of 16.6–17.7 wt% and Mg^# of 57.4–67.4. Trace element characteristics of the diorite show it is enriched in Ba, K and Sr, and depleted in Nb, Ta, Ti, with a positive Eu anomaly and high Sr/Y and La/Yb ratios. This diorite has positive ε_Nd(t) values ranging from 6.2 to 8.4 with low initial ⁸⁷Sr/⁸⁶Sr ratios of 0.704336 to 0.704450. These geochemical and isotopic characteristics indicate that the adakite-like diorite, associated with the copper mineralization, was emplaced in an island arc setting and resulted from partial melting of subducted oceanic plate in a mantle wedge.     

Petrogenesis of post-collisional A-type granitoids from the Urumieh–Dokhtar magmatic assemblage,Southwestern Kerman,Iran: Constraints on the Arabian–Eurasian continental collision

Three plutons (Deh-Siahan, Bande-Bagh and Baghe-Khoshk Sharghi, collectively referred to as the DBB hereafter) in southwestern Kerman, in the southeastern part of the Urumieh–Dokhtar magmatic assemblage (UDMA) of the Zagros orogenic belt differ from the typical calc-alkaline metaluminous, I-type intrusions of the region. The DBB intrusions have a distinct lithological assemblage varying from diorite through monzogranite and monzonite to alkali feldspar syenite and alkali granite. The DBB granitoids are metaluminous to slightly peraluminous, alkaline to shoshonitic in composition and have high total alkali contents with K₂O > Na₂O, high FeO_T/MgO values, and low CaO and MgO contents. They are enriched in some LILEs (such as Rb and Th) and HFSEs (such as Zr, Y and REEs except Eu) and depleted in Sr and Ba relative to primordial mantle, and have low concentrations of transitional metals. These features along with various geochemical discriminant diagrams suggest that the DBB granitoids are post-collisional A-type granitoids, which had not been recognized previously in the UDMA. The chondrite-normalized REE patterns of the DBB granitoids show slightly enriched light REEs [(La/Sm)_N = 2.26–4.13], negative Eu anomalies [(Eu/Eu*)_N = 0.19–0.74] and flat heavy REE patterns [(Gd/Yb)_N = 0.80–1.87]. The negative Eu anomaly indicates an important role for plagioclase and/or K-feldspar during fractional crystallization. Whole-rock Rb–Sr isotope analysis yields an isochron age of 33 ± 1 Ma with an initial ⁸⁷Sr/⁸⁶Sr value of 0.7049 ± 0.0001. Whole-rock Sm–Nd isotope analysis gives ε_Nd^t values from + 2.56 to + 3.62 at 33 Ma. The positive ε_Nd^t and low I_Sr values of the DBB granitoids together with their T_DM of 0.6–0.7 Ga suggest their formation from partial melting of a lithospheric mantle source, modified by fluids or melts from earlier subduction processes. Melting of lithospheric mantle occurred via a dehydration melting process at pressures below the garnet stability field, as a consequence of lithospheric mantle delamination or break-off of a subducted slab and melting of the lithospheric mantle by upwelling of hot asthenosphere. On the basis of Rb/Sr age dating and the post-collisional geochemical signatures of the DBB granitoids, along with extensive pre-collisional volcanic eruptions in Middle Eocene, we suggest Late Eocene for the time of collision between the Arabian and Central Iranian plates. This also implies that the calc-alkaline I-type intrusions in the southwestern Kerman and in other parts of the UDMA may have formed in a post-collisional context.