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.     

New constraints for the source characteristics,deposition and age of the 2.1–1.9 Ga metasedimentary cover at the western margin of the Karelian Province

The Paleoproterozoic cover sequence at the 100–150 km wide western margin of the Archean Karelian Province is dominated by deep water Lower and Upper Kaleva metasediments. We present here an interpretation of Sm–Nd isotope and geochemical data on 36 samples, TIMS multi-grain U–Pb zircon analyses on nine samples, and ca. 100 SIMS analysis of detrital zircon grains from four Upper Kaleva and one Lower Kaleva samples.The Lower Kaleva is characterized by autochthonous–parautochthonous, lithologically heterogeneous metaturbidites showing common enrichment in quartz. All the analysed detrital zircons are of a local Neoarchean source but t_DM variation up to 2.4 Ga combined with geochemical data indicate abundant mixing of Paleoproterozoic mafic material, presumably from 2.1 Ga plateau lavas and dykes, in most of the Lower Kaleva samples.The Upper Kaleva is dominantly allochthonous with tectonically enclosed fragments of ophiolite bodies, and it is characterized by lithological and geochemical-isotopic homogeneity. Geochemical, isotopic and detrital zircon data favour material derived from an orogenic domain, comprising both Archean and Proterozoic units, followed by effective mixing during the transport. The Archean zircon grains (25%) are mostly Neoarchean. The Paleoproterozoic grains lack zircons at 2.5–2.2 Ga and plot dominantly (92%) between 1.92 and 2.05 Ga. The indicated maximum deposition ages vary from 1.95–1.94 Ga to 1.92 Ga. The main source area proposed is the Himalaya-type Lapland-Kola orogen (now) in the northeast, which experienced mountain building and erosion at 1.95–1.91 Ga.The western margin of the Karelian Province shows evidence of rifting and lithosphere thinning from 2.1 to 1.95 Ga but it is still under debate whether the craton breakup occurred at 2.06 Ga in a volcanic or later at 1.95 Ga in a non-volcanic margin setting. One hypothesis is that the onset of collision in the northeast changed plate motion and lead to a new spreading within the pre-existing passive margin at 1.97–1.95 Ga. Thus, both a volcanic margin at 2.06 Ga and a non-volcanic margin at ca. 1.95 Ga could have been operated at the western margin of the Karelian Province.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

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

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

In situ zircon U–Pb dating and O isotopes of the Neoarchean Hongtoushan VMS Cu–Zn deposit in the North China Craton: Implication for the ore genesis

The Hongtoushan volcanogenic massive sulfide (VMS) deposit is the largest Archean Cu–Zn deposit in China, located in the Qingyuan greenstone belt on the northern margin of the North China Craton. The Cu–Zn mineralization was stratigraphically controlled by the interbeds (~ 100 m in thickness) of mafic–felsic volcanic sets and overlain by banded iron layers. However, the relationship between VMS deposits and associated volcanics has not been examined. This study ultimately clarifies the times and sources of the volcanics and mineralization. Based on in situ zircon U–Pb and O isotope on VMS-hosting mafic, felsic volcanic rocks, banded and massive sulfide ores and postmineralization pegmatite vein, we considered that there were two main formation stages for the Qingyuan Cu–Zn deposits; one was exhalative-hydrothermal sedimentation and another was further Cu–Zn enriched by later hydrothermal processes. The timing of the first stage occurred at 2571 ± 6 Ma based on the magmatic zircons in the VMS-hosting mafic volcanic rocks, from which the inherited zircons also indicate the existence of 2.65–3.12 Ga ancient supercrustal rocks in the Qingyuan district. A modern mantle-like δ¹⁸Ozircon value of 5.5 ± 0.1‰ (2SD) for this volcanism was well preserved in the inherited core domains of ore samples. It suggests that the mafic volcanics was most likely sourced from partial melting of juvenile crust, e.g., TTG granites. A large-scale metamorphic or hydrothermal event is documented by the recrystallized zircons in sulfide ores. The timing is tightly constrained by the hydrothermal zircon U–Pb ages. They are 2508 ± 4 Ma for the banded ore, 2507 ± 4 Ma for the massive ore and 2508 ± 2 Ma for the postmineralization pegmatite vein. These indistinguishable ages indicate that the 2507 Ma hydrothermal systems played a significant role in the upgrading of the VMS Cu–Zn orebodies. The weighted δ¹⁸O values of hydrothermal zircons show a successively increasing trend from 6.0 ± 0.1‰ (2σ) for the banded ore, 6.6 ± 0.2‰ (2σ) for the massive ore to 7.3 ± 0.2‰ (2σ) for the later pegmatite vein. This variation might be induced by gradual inputting of the δ¹⁸O-rich oceanic crust and/or oceanic sediment during the hydrothermal cycling system. Considering its modern mantle-like oxygen isotope composition of 2571 Ma volcanism, a submarine volcanic hydrothermal system involving mantle plumes is a preferred setting for the Neoarchean VMS Cu–Zn deposits in the Qingyuan greenstone belt.     

Formation and evolution of Precambrian continental lithosphere in South China

An overview is presented for the formation and evolution of Precambrian continental lithosphere in South China. This is primarily based on an integrated study of zircon U–Pb ages and Lu–Hf isotopes in crustal rocks, with additional constraints from Re–Os isotopes in mantle-derived rocks. Available Re–Os isotope data on xenolith peridotites suggest that the oldest subcontinental lithospheric mantle beneath South China is primarily of Paleoproterozoic age. The zircon U–Pb ages and Lu–Hf isotope studies reveal growth and reworking of the juvenile crust at different ages. Both the Yangtze and Cathaysia terranes contain crustal materials of Archean U–Pb ages. Nevertheless, zircon U–Pb ages exhibit two peaks at 2.9–3.0 Ga and ~ 2.5 Ga in Yangtze but only one peak at ~ 2.5 Ga in Cathaysia. Both massive rocks and crustal remnants (i.e., zircon) of Archean U–Pb ages occur in Yangtze, but only crustal remnants of Archean U–Pb ages occur in Cathaysia. Zircon U–Pb and Lu–Hf isotopes in the Kongling complex of Yangtze suggest the earliest episode of crustal growth in the Paleoarchean and two episodes of crustal reworking at 3.1–3.3 Ga and 2.8–3.0 Ga. Both negative and positive ε_Hf(t) values are associated with Archean U–Pb ages of zircon in South China, indicating both the growth of juvenile crust and the reworking of ancient crust in the Archean. Paleoproterozoic rocks in Yangtze exhibit four groups of U–Pb ages at 2.1 Ga, 1.9–2.0 Ga, ~ 1.85 Ga and ~ 1.7 Ga, respectively. They are associated not only with reworking of the ancient Archean crust in the interior of Yangtze, but also with the growth of the contemporaneous juvenile crust in the periphery of Yangtze. In contrast, Paleoproterozoic rocks in Cathaysia were primarily derived from reworking of Archean crust at 1.8–1.9 Ga. The exposure of Mesoproterozoic rocks are very limited in South China, but zircon Hf model ages suggest the growth of juvenile crust in this period due to island arc magmatism of the Grenvillian oceanic subduction. Magmatic rocks of middle Neoproterozoic U–Pb ages are widespread in South China, exhibiting two peaks at about 830–800 Ma and 780–740 Ma, respectively. Both negative and positive ε_Hf(t) values are associated with the middle Neoproterozoic U–Pb ages of zircon, suggesting not only growth and reworking of the juvenile Mesoproterozoic crust but also reworking of the ancient Archean and Paleoproterozoic crust in the middle Neoproterozoic. The tectonic setting for this period of magmatism would be transformed from arc–continent collision to continental rifting with reference to the plate tectonic regime in South China.     

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

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

Crustal growth of the central-eastern Paleoproterozoic domain,SW Amazonian craton: Juvenile accretion vs. reworking

The Trans-Amazonian cycle was an important rock-forming event in South America, generating voluminous juvenile and reworked fractions of continental crust. The Bacajá domain, in the southern sector of the Maroni-Itacaiúnas Province in the Amazonian craton, is an example of the Trans-Amazonian terranes adjacent to the Archean Carajás block. Zircon Pb-evaporation and whole-rock Sm–Nd analyses were carried out on representative samples of six lithological units, and allowed the proposal of a comprehensive tectonic-magmatic evolutionary sequence for the central and eastern parts of this domain, from the Neoarchean to the Rhyacian. Gneisses with ages of ca. 2.67 and 2.44 Ga are the oldest rocks recorded in the region, and probably represent remnants of island and continental arcs. The Três Palmeiras succession, emplaced between 2.36 and 2.34 Ga, hosts gold deposits and represents the first record of Siderian supracrustal rocks in the Amazonian craton. It was probably part of an island arc/ocean floor accreted to a craton margin. Rhyacian granitogenesis lasted for ca. 140 My (2.22–2.08 Ga), marking different stages of the Trans-Amazonian cycle. The first stage is represented by continental arc granitoids formed by melting of Archean crust at 2.22–2.18 Ga. The second is characterized by the production of juvenile material between 2.16 and 2.13 Ga. The third and final stage at ca. 2.08 Ga is represented by a large volume of granitoids originated from either juvenile material or reworked crust during compressive stresses. Nd isotopes reveal that juvenile rocks dominated in the northern part of the domain, whereas those formed from reworked crust predominate in the south. The present-day configuration of the Bacajá domain results from collision against the Archean Carajás block at the end of the Trans-Amazonian cycle.     

Modification of a Palaeoproterozoic porphyry-like system: Integration of structural,geochemical, petrographic,and fluid inclusion data from the Aitik Cu–Au–Ag deposit,northern Sweden

The Aitik Cu–Au–Ag deposit in the Gällivare area in northern Sweden is Sweden's largest sulphide mine with an annual production of 35 Mt of ore, and the biggest open pit operation in northern Europe. It is proposed in the present study that the Aitik deposit represents a Palaeoproterozoic, strongly metamorphosed porphyry copper deposit that was affected ca. 100 Ma later by a regional IOCG-type hydrothermal event. Consequently, the Aitik deposit might represent a mixed ore system where an early copper mineralisation of porphyry type has been overprinted by later regional IOCG mineralisation.Several attempts have previously been made to genetically classify the Aitik Cu–Au–Ag deposit as a distinct ore type. New geochemical, petrographic, structural, and fluid inclusion results combined with published data have provided the opportunity to present new ideas on the genesis and evolution of the Aitik Cu–Au–Ag deposit. The emplacement of a ca. 1.9 Ga quartz monzodiorite that host the ore at Aitik was related to subduction processes and volcanic arc formation, and synchronous with quartz vein stockwork formation and porphyry copper mineralisation. Highly saline aqueous (38 wt.% NaCl) fluid inclusions in the stockwork veins suggest entrapment at 300 °C and a pressure of nearly 3 kbar, a high pressure for a typical porphyry copper ore, but consistent with conditions at associated deep root zones of intrusion-related magmatic–hydrothermal systems. The highly saline fluid formed disseminated and vein-type ore of mainly chalcopyrite and pyrite within comagmatic volcaniclastic rocks, and caused potassic alteration (biotite, microcline) of the host rocks. The early porphyry copper mineralising event was followed, and largely overprinted, by CO₂ and aqueous medium- to high-salinity (16–57 wt.% salts) fluids related to a ca. 1.8 Ga tectonic and metamorphic event (peak conditions 500–600 °C and 4–5 kbar). Extensive deformation of rocks and redistribution of metals occurred. Magnetite enrichment locally found within late veins, and late amphibole–scapolite and K feldspar alterations within the deposit, are some of the features at Aitik implying that aqueous fluids responsible for IOCG-mineralisation (200–500 °C and ~ 1 kbar) and extensive Na–Ca alteration in the region during the 1.8 Ga tectonic event also affected the Aitik rocks, possibly leading to addition of copper ± gold.     

Magma sources and petrogenesis of the early–middle Paleozoic backarc granitoids from the central part of the Qilian block,NW China

The petrology, geochemistry, geochronology, and Sr–Nd–Hf isotopes of the backarc granitoids from the central part of the Qilian block are studied in the present work. Both S- and I-type granitoids are present. In petrographic classification, they are granite, alkali feldspar granite, felsic granite, diorite, quartz diorite, granodiorite, and albite syenite. The SHRIMP ages are 402–447 Ma for the S-type and 419–451 Ma for the I-type granitoids. They are mostly high-K calc-alkaline granitoids. The S-type granitoids are weakly to strongly peraluminous and are characterized by negative Eu anomalies (Eu/Eu* = 0.18–0.79). The I-type granitoids are metaluminous to weakly peraluminous and are characterized mostly by small negative to small positive Eu anomalies (Eu/Eu* = 0.71–1.16). The initial (⁸⁷Sr/⁸⁶Sr) values are 0.708848–0.713651 for the S-type and 0.704230–0.718108 for the I-type granitoids. The ε_Nd(450 Ma) values are − 8.9–−4.1 and − 9.7–+ 1.9 for the S-type and I-type granitoids, respectively. The T_DM values are 1.5–2.4 Ga for the S-type and 1.0–2.3 Ga for the I-type granitoids. For the Qilian block, the backarc granitoid magmatism took place approximately 60 million years after the onset of the southward subduction of the north Qilian oceanic lithosphere and lasted approximately 50 million years. Partial melting of the source rocks consisting of the Neoproterozoic metasedimentary rocks of the Huangyuan Group and the intruding lower Paleozoic basaltic rocks could produce the S-type granitoid magmas. Partial melting of basaltic rocks mixed with lower continental crustal materials could produce the I-type granitoid magmas. Major crustal growth occurred in the late Archean and Meso-Paleoproterozoic time for the Qilian block. The magma generation was primarily remelting of the crustal rocks with only little addition of the mantle materials after 1.0 Ga for the Qilian block.     

Constraints of Sr isotopic compositions of apatite and carbonates on the origin of Fe and Cu mineralizing fluids in the Lala Fe-Cu-(Mo,LREE) deposit,SW China

Numerous Fe-Cu deposits with mineralization styles similar to iron oxide-copper gold (IOCG) deposits form the Kangdian Fe-Cu metallogenic province, southwestern (SW) China. As one of the largest deposits in the region, the ~ 1.0 Ga Lala Fe-Cu deposit is hosted in a Paleoproterozoic volcanic-sedimentary succession named the Hekou Group which is alternately intruded by ~ 1.0 Ga doleritic plutons. This deposit has a paragenetic sequence evolving from Stage I of Na-alteration to Stage II of Fe mineralization, and finally to Stage III of Cu-(Mo, REE) mineralization, coeval with mafic-felsic intra-plate magmatism in the region. This study conducted in-situ Sr isotopic analyses on apatite and carbonate, aiming to resolve the long controversial issue regarding the origin of the Fe and Cu mineralizing fluids in the deposit. Apatite of Stage II has ⁸⁷Sr/⁸⁶Sr ratios varying from 0.71380 to 0.72733, much higher than those of synchronous igneous rocks in the region (0.7074 to 0.7091), but similar to the Paleoproterozoic host rocks (0.71368 to 0.71837 at ~ 1.0 Ga). This similarity indicates that radiogenic Sr of the Fe mineralizing fluid was dominantly sourced from the host rocks. Apatite and calcites of Stage III have ⁸⁷Sr/⁸⁶Sr ratios (0.75758–0.79293) much higher than apatite of Stage II and the host rocks but similar to the Archean basement rocks (as high as 0.80 at ~ 1.0 Ga) beneath the cover of the Yangtze Block, suggesting that the highly radiogenic Sr isotopic composition of the Cu mineralizing fluid was mainly inherited from the old basement rocks. In combination with previous C-O-S isotopic data indicating a magma-hydrothermal origin, it was suggested that the Fe mineralizing fluid was exsolved from a mafic magma that generated the ~ 1.0 Ga doleritic plutons, and inherited radiogenic Sr from the host rocks during fluid-rock interaction. By contrast, the Cu mineralizing fluid might have been sourced from another pulse of magmatic, Cu-Mo-REE- and CO₂-rich fluid which have once interacted with Archean basement rocks prior to mineralization. The source of such a Cu-Mo-REE-rich fluid was not well constrained in current study but was inferred to be exsolved from a hidden felsic magma. We propose that intrusions of the bimodal magmas in Kangdian are responsible for regional hydrothermal circulation which led to Fe-Cu-(Mo, REE) mineralization in the Kangdian province.     

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.     

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

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

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.     

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.     

Changes of Ge/Si,REE + Y and SmNd isotopes in alternating Fe- and Si-rich mesobands reveal source heterogeneity of the ~ 2.54 Ga Sijiaying banded iron formation in Eastern Hebei,China

The North China Craton (NCC) is one of the most important regions hosting abundant banded iron formations (BIFs). The ~ 2.54 Ga Sijiaying BIF, the best-preserved and most extensive deposit in Eastern Hebei, is intercalated and closely associated with meta-volcanic rocks of the Luanxian Group. In this context, major and trace element and SmNd isotopic analyses of individual mesobands of a Sijiaying BIF specimen were conducted to characterize the source and depositional environment over a transient period.Low Al₂O₃, TiO₂ and high field strength elements (HFSEs) concentrations show that the BIF is relatively detritus-free. Shale-normalized rare earth and yttrium distributions (REE + Y) of individual BIF mesobands exhibit positive La anomalies, enrichment in HREE relative to LREE and MREE and suprachondritic Y/Ho ratios, which are typical features of marine waters throughout the Archean and Proterozoic. The presence of consistently positive Eu anomalies indicates a significant high-T hydrothermal input, while the absence of true Ce anomalies suggests deposition from an anoxic water column. By comparison with other typical BIFs (e.g., the Isua BIF from Greenland; the Kuruman BIF from South Africa), the Sijiaying BIF is depleted in HREE, and appears to record variations in solute fluxes related to changing intensities of hydrothermal activity. These features, coupled with SmNd isotopic relations and Ge/Si distributional patterns, point to two decoupled sources controlling the depositional environment of the BIF and thus reveal source heterogeneity for silica and iron of the Sijiaying BIF. High Fe fluxes were associated with seafloor-vented hydrothermal fluids, which received their SmNd isotopic signature from alteration of depleted oceanic crust; whereas significant amounts of silica were associated with ambient seawater whose REE signature was controlled by solutes derived from weathering of nearby Mesoarchean continental landmasses. The old (up to ~ 3.0 Ga) Nd (T_DM) model ages of Si-rich mesobands of the BIF support such a scenario.     

Field and geochemical characteristics of Mesoarchean to Neoarchean volcanic rocks in the Storø greenstone belt,SW Greenland: Evidence for accretion of intra-oceanic volcanic arcs

The Storø greenstone belt, southern West Greenland, consists of thrust-imbricated slices of Mesoarchean (>3060 Ma) and Neoarchean (ca. 2800 Ma) mafic to ultramafic volcanic rocks, volcaniclastic sediments, and gabbro–anorthosite associations. The belt underwent polyphase metamorphism at upper amphibolite facies conditions between 2650 and 2600 Ma. The contacts between the Mesoarchean and Neoarchean volcanic rocks, and surrounding Eoarchean to Neoarchean tonalite–trondhjemite–granodiorite (TTG) gneisses are tectonic and typically bounded by high-grade mylonites. Regardless of age, the volcanic rocks are dominated by mafic amphibolites with a tholeiitic basalt composition, near-flat to slightly enriched light rare earth element (LREE) patterns (La/Sm_cn = 0.91–1.48), relatively flat to slightly depleted heavy-REE (HREE) (Gd/Yb_cn = 1.0–1.28), and pronounced negative Nb–Ta anomalies (Nb/Nb* = 0.34–0.73) on chondrite- and primitive mantle-normalized diagrams. These geochemical characteristics are consistent with subduction zone geochemical signatures and partial melting of a shallow (<80 km) mantle source free of residual garnet. There is no geochemical evidence for contamination by older continental crust. The overall field and geochemical characteristics suggest that the thrust-imbricated basaltic rocks were erupted in intra-oceanic subduction zone settings. Sedimentary rocks are represented by garnet–biotite and quartzitic gneisses. They are characterized by relatively high contents of transition metal (Ni = 10–154 ppm; Cr = 7–166 ppm) and enriched LREE patterns (La/Sm_cn = 1.38–3.79). These geochemical characteristics suggest that the sedimentary rocks were derived from erosion of felsic to mafic igneous source rocks. Collectively, the structural and lithogeochemical characteristics of the Storø greenstone belt are consistent with collision (accretion) of unrelated Archean volcanic rocks formed in supra-subduction zone geodynamic settings. Accordingly, the Mesoarchean and Neoarchean rock record of the Storø greenstone belt may well be explained in terms of modern-style plate tectonic processes.     

Geochronology and thermochronology of gold mineralization in the Turmalina deposit,NE of the Quadrilátero Ferrífero Region,Brazil

The Turmalina gold deposit comprises three epigenetic domains whose development is related to the propagation/reactivation events of the NW–SE Pitangui Shear Zone (PSZ). The lodes are hosted in a Late Archaean sedimentary sequence on top of a strongly deformed (mafic-dominated) metavolcanic pile metamorphosed under 3.5–4 kbar and 540–610 °C; the association forms the upper part of a lithostratigraphic succession (Pitangui Group) that overlies an older TTG gneissic basement. According to field evidence and petrographic observations, the ore-forming process is polyphasic, starting at the time when the PSZ crossed the metamorphic quartz + staurolite + biotite + almadine + hornblende isograde; the main evolving stages, however, mostly took place throughout the metamorphic retrogression path. Fluid inclusion microthermometry also shows that metamorphogenic aqueous–carbonic solutions (initially with ≈ 16–20 eq. wt.% NaCl and circulating at approximately 4 kbar and 550 °C) were subjected to repeated boiling and mixing with cooler aqueous solutions at approximately 1–2 kb and 300–350 °C. These boiling events, which were triggered by depressurization, were contemporaneous with gold (and later sulfide) deposition, preceding a late stage of hydrothermal activity under lower PT conditions (< 1 kbar and ≈ 130–230 °C). To constrain both the mineralization age and the source/pathways of the ore-forming fluids in the Turmalina deposit, a multi-system isotope (Pb–Pb, Rb–Sr and Sm–Nd) study was carried out using various whole-rock and mineral samples. The main results are as follows: (i) the onset of the ore-forming process took place at ca. 2.2–2.1 Ga; (ii) the critical timing for gold formation was confined to ca. 2–1.9 Ga; and (iii) the late hydrothermal influxes occurred after 1.75 Ga. Therefore, the ore-forming process can be envisaged as a result of successive physical–chemical processes that took place during two major, long-lasting (≈ 250 Ma) periods under initial cooling rates of approximately 1 °C/Ma and, after ca. 2–1.9 Ga, approximately 2.5 °C/Ma. Moreover, the rejuvenation episodes at ca. 2–1.9 Ga and ca. 1.75 Ga probably indicate reactivation events in the PSZ, which triggered new fluid inflows into the system and revitalized the ore-forming process. That was the case for fluids that circulated deeply through both the older basement rocks and the mafic volcanic pile, allowing either metal enrichment from multistage leaching processes of various reservoirs or possible U/Th decoupling during ore remobilization. The Turmalina ore-system lifetime is consequently confined to the Rhyacian period (Paleoproterozoic), which is compatible with the age constraints presented by other studies regarding the fold-thrust belt's development (ca. 2.125 Ga) and orogenic collapse (ca. 2.095 Ga).     

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.