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.     

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

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

Biogenic and abiogenic low-Mg calcite (bLMC and aLMC): Evaluation of seawater-REE composition,water masses and carbonate diagenesis

The ΣREE and shale-normalized (PAAS) REE_SN values of modern brachiopods (biogenic low-Mg calcite: bLMC) represented by several species from high- to low latitudes, from shallow- to deep waters and from warm- and cold-water environments, define three distinct average ‘seawater’ trends. The warm- and cold-water brachiopods define two indistinguishable (p < 0.050) groups that mimic open-ocean seawater REE chemistry, exhibiting the typical LREE enrichment with a slightly positive to negative Ce anomaly followed by an otherwise invariant series. Other recent brachiopods from an essentially siliciclastic seabed environment are distinct in both ΣREE and REE_SN trends from the previous two populations, showing a slight enrichment in the MREEs and an increasing trend in the HREEs. Other groups of modern brachiopods are characterized by elevated REE_SN trends relative to the ‘normal’ groups as well as by complexity of the series trends. The most characteristic feature is the decrease in the HREEs in these brachiopods from areas of unusual productivity (i.e., such as upwelling currents, fluvial input and aerosol dust deposition). Preserved brachiopods from the Eocene and Silurian exhibit REE_SN trends and Ce anomalies similar to that of the ‘open-ocean’ modern brachiopods, although, their enriched ΣREE concentrations suggest precipitation of bLMC influenced by extrinsic environmental conditions.Preservation of the bLMC was tested by comparing the ΣREE and REE_SN trends of preserved Eocene brachiopods to those of Oligocene brachiopods that were altered in an open diagenetic system in the presence of phreatic meteoric-water. The altered bLMC is enriched by approximately one order of magnitude in both ΣREE and REE_SN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REE_SN of preserved Silurian brachiopod bLMC were compared to those of their enclosing altered lime mudstone, which exhibits features of partly closed system, phreatic meteoric-water diagenesis. Despite these differences in the diagenetic alteration systems and processes, the ΣREEs and REE_SN trends of the bLMC of altered brachiopods and of originally mixed mineralogy lime mudstones (now diagenetic low-Mg calcite) are enriched by about one order of magnitude relative to those observed in the coeval and preserved bLMC.In contrast to the changes in ΣREE and REE_SN of carbonates exposed to phreatic meteoric-water diagenesis, are the REE compositions of late burial calcite cements precipitated in diagenetically open systems from burial fluids. The ΣREE and REE_SN trends of the burial cements mimic those of their host lime mudstone, with all showing slight LREE enrichment and slight HREE depletion, exhibiting a ‘chevron’ pattern of the REE_SN trends. The overall enrichment or depletion of the cement REE_SN trends relative to that of their respective host rock material reflects not only the openness of the diagenetic system, but also strong differences in the elemental and REE compositions of the burial fluids. Evaluation of the (Ce/Ce*)_SN and La = (Pr/Pr*)_SN anomalies suggests precipitation of the burial calcite cements essentially in equilibrium with their source fluids.     

Nitrogen isotope chemostratigraphy across the Permian–Triassic boundary at Chaotian,Sichuan, South China

Nitrogen isotopic compositions of upper Permian to lowermost Triassic rocks were analyzed at Chaotian in northern Sichuan, South China, in order to clarify changes in the oceanic nitrogen cycle around the Permian–Triassic boundary (P–TB) including the entire Changhsingian (Late Late Permian) prior to the extinction. The analyzed ca. 40 m thick interval across the P–TB at Chaotian consists of three stratigraphic units: the upper Wujiaping Formation, the Dalong Formation, and the lowermost Feixianguan Formation, in ascending order. The upper Wujiaping Formation, ca. 10 m thick, is mainly composed of dark gray limestone with diverse shallow-marine fossils such as calcareous algae and brachiopods, deposited on the shallow shelf. In contrast, the overlying Dalong Formation, ca. 25 m thick, is mainly composed of thinly bedded black mudstone and siliceous mudstone containing abundant radiolarians, deposited on the relatively deep slope/basin. Absence of bioturbation, substantially high total organic carbon contents (up to 15%), and abundant occurrence of pyrite framboids in the main part of the Dalong Formation indicate deposition under anoxic condition. The lowermost Feixianguan Formation, ca. 5 m thick, is composed of thinly bedded gray marl and micritic limestone with minor fossils such as ammonoids and conodonts, deposited on the relatively shallow slope. δ¹⁵N_TN values are in positive values around +1 to +2‰ in the upper Wujiaping Formation implying denitrification and/or anammox in the ocean. δ¹⁵N_TN values gradually decrease to −1‰ in the lower Dalong Formation and are consistently low (around 0‰) in the middle Dalong to lowermost Feixianguan Formation. No clear δ¹⁵N_TN shift is recognized across the extinction horizon. The consistently low δ¹⁵N_TN values suggest the enhanced nitrogen fixation in the ocean during the Changhsingian at Chaotian. Composite profiles based on previous and the present studies demonstrate the substantial δ¹⁵N variation on a global scale in the late Permian to earliest Triassic; a systematic δ¹⁵N difference by low and high latitudes is particularly clarified. Although the enhanced nitrogen fixation throughout the Changhsingian at Chaotian was likely a regional event in northwestern South China, the composite δ¹⁵N profiles imply that the sea area in which fixed nitrogen is depleted has gradually developed worldwide in the Changhsingian, possibly acting as a prolonged stress to shallow-marine biota.     

Paleogeographic forcing of the strontium isotopic cycle in the Neoproterozoic

The period spanning from 825 to 540 Ma is characterized by major changes in the surficial Earth system. This extraordinary interval starts with the breakup of the Rodinia supercontinent and eruption of a series of large igneous provinces and ends with the assembly of Gondwana, giving rise to the Pan-African orogenies. This paleogeographic reorganization is accompanied by a global climatic cooling, including the paroxysmal Cryogenian “snowball” glacial events. The ⁸⁷Sr/⁸⁶Sr of seawater displays a major long-term rise over this interval that is punctuated by episodic, smaller declines and inflections. We use a coupled deep time climate-carbon numerical model to explore the complex role of tectonics and climate on this distinct evolution in seawater ⁸⁷Sr/⁸⁶Sr. We show that the modulation of the weathering of the erupted large igneous provinces by continental drift explains the changes in seawater ⁸⁷Sr/⁸⁶Sr from 800 to 635 Ma. The subsequent sharp rise in seawater ⁸⁷Sr/⁸⁶Sr from 635 to 580 Ma is the result of erosion of radiogenic crust exposed in the Pan-African orogens. Coeval evolution of atmospheric CO₂ displays a decrease from about 80 times the pre-industrial level around 800 Ma to 5 times just before the beginning of the Phanerozoic.     

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

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

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ¹³C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier.Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.     

Precise dating of the Middle Permian: Zircon U–Pb geochronology from volcanic ash beds in the basal Gufeng Formation,Yangtze region,South China

Direct radiometric dating of the Lower/Middle Permian epochs has not been well accomplished. Shales and bedded cherts of the geologically well-documented Middle Permian Gufeng Formation are exposed in the Chaohu area, Anhui province, South China. Through detailed field examination and mapping of the Gufeng stratigraphic section, we found at least four volcanic ash beds within the basal shale strata. This new discovery indicates the existence of prominent volcanic activity during Gufeng sedimentation and provides the opportunity to precisely date the age of the Middle Permian. Zircon grains separated from two near-basal horizon yield LA‐ICP‐MS U–Pb ages of 272.0 ± 5.5 Ma (MSWD = 2.6) and 271.5 ± 3.3 Ma (MSWD = 1.7). As the first precise isotopic age (272 Ma) of the Middle Permian Gufeng Formation in South China, our data offer precise geochronological constraints for the division and correlation of Middle Permian not only in South China but also worldwide.     

Coal-derived rates of atmospheric dust deposition during the Permian

Despite widespread evidence for atmospheric dust deposition prior to the Quaternary, quantitative rate data remains sparse. As dust influences both climate and biological productivity, the absence of quantitative dust data limits the comprehensiveness of models of pre-Quaternary climate and biogeochemical cycles. Here, we propose that inorganic matter contained in coal primarily records atmospheric dust deposition. To test this, we use the average concentration of inorganic matter in Permian coal to map global patterns and deposition rates of atmospheric dust over Pangea. The dust accumulation rate is calculated assuming Permian peat carbon accumulation rates in temperate climates were similar to Holocene rates and accounting for the loss of carbon during coalification. Coal-derived rates vary from 0.02 to 25 g m^− 2 year^− 1, values that fall within the present-day global range. A well-constrained East–West pattern of dust deposition corresponding to expected palaeoclimate gradients extends across Gondwana with maximum dust deposition rates occurring close to arid regions. A similar pattern is partially defined over the northern hemisphere. Patterns are consistent with the presence of two large global dust plumes centred on the tropics. The spatial patterns of dust deposition were also compared to dust cycle simulations for the Permian made with the Community Climate System Model version 3 (CCSM3). Key differences between the simulations and the coal data are the lack of evidence for an Antarctic dust source, higher than expected dust deposition over N and S China and greater dust deposition rates over Western Gondwana. This new coal-based dust accumulation rate data expands the pre-Neogene quantitative record of atmospheric dust and can help to inform and validate models of global circulation and biogeochemical cycles over the past 350 Myr.     

Chronological link between deep-seated processes in magma chambers and eruptions: Permo-Carboniferous magmatism in the core of Pangaea (Southern Pyrenees)

In the Southern Pyrenees there are Upper Carboniferous–Lower Permian sedimentary basins with a significant volume of volcanic material derived from explosive eruptions (rhyolitic ignimbrites and andesitic flows). These basins are spatially associated with granodiorites and dacitic dykes emplaced in Variscan basement rocks. U–Pb SHRIMP dating of zircons extracted from three granodiorites, an andesitic flow, a dacitic dyke and six ignimbrites, revealed that magmatism occurred over an extended period of thirty eight million years, from ca. 304 Ma to ca. 266 Ma (Upper Carboniferous–Middle Permian). A scattering of zircon ages in each sample shows that the history of melt crystallization was complex, with more than one zircon-forming event in each magma chamber. The prolonged crystallization history was transferred to the product of the eruptions. A chronological link between the deep-seated magma chambers and processes in eruptions was identified on the basis of four overlapping intervals at: ca. 309–307 Ma (Upper Carboniferous), ca. 304–296 Ma (Upper Carboniferous–Lower Permian), ca. 294–282 Ma (Lower Permian), and ca. 276 Ma (Lower Permian). The variation of zircon U/Th ratios exposes a tendency for an increase in mafic sources as crystallization advances in the Permian. Zircons probably crystallized from melt phases related to both a felsic-intermediate metaluminous source from ca. 310–293 Ma (mostly 0.1 < Th/U < 0.6) to ca. 289–273 Ma (especially in the range 0.6 < Th/U < 1) and a mafic source (mostly 1.2 < Th/U < 1) at ca. 266–265 Ma. U–Pb zircon ages from volcanic and plutonic rocks of the Southern Pyrenees are consistent with the ages of the post-Variscan magmatism of Iberia associated with orocline generation and subduction of the Paleotethys Ocean (ca. 304–283 Ma), and in addition reveal a later magmatic event at ca. 276–266 Ma (Lower–Middle Permian). The location of the Iberian orocline in the core of Pangaea and near the western end of the subduction zone of the Paleotethys Ocean leads to the hypothesis that this later magmatic activity of the Southern Pyrenees could provide the missing link between the Variscan and Cimmerian cycles that acted sequentially in Permo-Carboniferous times.     

U–Pb ages of detrital zircons within the Inthanon Zone of the Paleo-Tethyan subduction zone,northern Thailand: New constraints on accretionary age and arc activity

U–Pb dating of detrital zircons was performed on mélange-hosted lithic and basaltic sandstones from the Inthanon Zone in northern Thailand to determine the timing of accretion and arc activity associated with Paleo-Tethys subduction. The detrital zircons have peak ages at 3400–3200, 2600–2400, 1000–700, 600–400, and 300–250 Ma, similar to the peaks ages of detrital zircons associated with other circum-Paleo-Tethys subduction zones. We identified two types of sandstone in the study area based on the youngest detrital zircon ages: Type 1 sandstones have Late Carboniferous youngest zircon U–Pb ages of 308 ± 14 and 300 ± 16 Ma, older than associated radiolarian chert blocks within the same outcrop. In contrast, Type 2 sandstones have youngest zircon U–Pb ages of 238 ± 10 and 236 ± 15 Ma, suggesting a Middle Triassic maximum depositional age. The youngest detrital zircons in Type 1 sandstones were derived from a Late Carboniferous–Early Permian ‘missing’ arc, suggesting that the Sukhothai Arc was active during sedimentation. The data presented within this study provide information on the development of the Sukhothai Arc, and further suggest that subduction of the Paleo-Tethyan oceanic plate beneath the Indochina Block had already commenced by the Late Carboniferous. Significant Middle Triassic arc magmatism, following the Late Carboniferous–Early Permian arc activity, is inferred from the presence of conspicuous detrital zircon U–Pb age peaks in Type 2 sandstones and the igneous rock record of the Sukhothai Arc. In contrast, only minimal arc activity occurred during the Middle Permian–earliest Triassic. Type 1 sandstones were deposited between the Late Permian and the earliest Triassic, after the deposition of associated Middle–Late Permian cherts that occur in the same mélanges and during a hiatus in Sukhothai Arc magmatism. In contrast, Type 2 sandstones were deposited during the Middle Triassic, coincident with the timing of maximum magmatism in the Sukhothai Arc, as evidenced by the presence of abundant Middle Triassic detrital zircons. These two types of sandstone were probably derived from discrete accretionary units in an original accretionary prism that was located along the western margin of the Sukhothai Arc.     

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

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

30 million years of Permian volcanism recorded in the Choiyoi igneous province (W Argentina) and their source for younger ash fall deposits in the Paraná Basin: SHRIMP U–Pb zircon geochronology evidence

We present four SHRIMP U–Pb zircon ages for the Choiyoi igneous province from the San Rafael Block, central–western Argentina. Dated samples come from the Yacimiento Los Reyunos Formation (281.4 ± 2.5 Ma) of the Cochicó Group (Lower Choiyoi section: andesitic breccias, dacitic to rhyolitic ignimbrites and continental conglomerates), Agua de los Burros Formation (264.8 ± 2.3 Ma and 264.5 ± 3.0 Ma) and Cerro Carrizalito Formation (251.9 ± 2.7 Ma Upper Choiyoi section: rhyolitic ignimbrites and pyroclastic flows) spanning the entire Permian succession of the Choiyoi igneous province. A single zircon from the El Imperial Formation, that is overlain unconformably by the Choiyoi succession, yielded an early Permian age (297.2 ± 5.3 Ma), while the main detrital zircon population indicated an Ordovician age (453.7 ± 8.1 Ma). The new data establishes a more precise Permian age (Artinskian–Lopingian) for the section studied spanning 30 Ma of volcanic activity. Volcanological observations for the Choiyoi succession support the occurrence of explosive eruptions of plinian to ultraplinian magnitudes, capable of injecting enormous volumes of tephra in the troposphere–stratosphere. The new SHRIMP ages indicate contemporaneity between the Choyoi succession and the upper part of the Paraná Basin late Paleozoic section, from the Irati up to the Rio do Rasto formations, encompassing about 24 Ma. Geochemical data show a general congruence in compositional and tectonic settings between the volcanics and Paraná Basin Permian ash fall derived layers of bentonites. Thickness and granulometry of ash fall layers broadly fit into the depletion curve versus distance from the remote source vent of ultraplinian eruptions. Thus, we consider that the Choiyoi igneous province was the source of ash fall deposits in the upper Permian section of the Paraná Basin. Data presented here allow a more consistent correlation between tectono-volcanic Permian events along the paleo-Pacific margin of southwestern Gondwana and the geological evolution of neighboring Paleozoic foreland basins in South America and Africa.     

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.     

Significant Li isotope fractionation in geochemically evolved rare element-bearing pegmatites from the Little Nahanni Pegmatite Group,NWT, Canada

Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ⁷Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ⁷Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H₂O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.     

Combined U-Pb,Lu-Hf,Sm-Nd and Ar-Ar multichronometric dating on the Bailang eclogite constrains the closure timing of the Paleo-Tethys Ocean in the Lhasa terrane,Tibet

The Lhasa terrane, the main tectonic component of the Himalayan–Tibetan orogen, has received much attention as it records the entire history of the orogeny. The occurrence of Permian to Triassic high-pressure eclogites has a significant bearing on the understanding of the Paleo-Tethys subduction and plate suturing processes in this area. An eclogite from the Bailang, eastern Lhasa terrane, was investigated with a combined metamorphic P–T and U–Pb, Lu–Hf, Sm–Nd and Ar–Ar multichronometric approach. Pseudosection modeling combined with thermobarometric calculations indicate that the Bailang eclogite equilibrated at peak P–T conditions of ~ 2.6 GPa and 465–503 °C, which is much lower than those of Sumdo and Jilang eclogites in this area. Garnet–whole rock–omphacite Lu–Hf and Sm–Nd ages of 238.1 ± 3.6 Ma and 230.0 ± 4.7 Ma were obtained on the same sample, which are largely consistent with the corresponding U–Pb age of 227.4 ± 6.4 Ma for the metamorphic zircons within uncertainty. The peak metamorphic temperature of the sample is lower than the Lu–Hf and Sm–Nd closure temperatures in garnet. This, combined with the core-to-rim decrease in Mn and HREE concentrations, the slightly U-shaped Sm zonation across garnet and the exclusive occurrence of omphacite inclusion in garnet rim, are consistent with the Lu–Hf system skewing to the age of the garnet core and the Sm–Nd system favoring the rim age. The Sm–Nd age was thus interpreted as the age of eclogite-facies metamorphism and the Lu–Hf age likely pre-dated the eclogite-facies metamorphism. ⁴⁰Ar/³⁹Ar dating of hornblende from the eclogite yielded ages about 200 Ma, which is interpreted as a cooling age and is probably indicative of the time of exhumation to the middle crust. The difference of peak eclogite-facies metamorphic conditions and the distinct metamorphic ages for the Bailang eclogite (~ 2.6 GPa and ~ 480 °C; ca. 230 Ma), the Sumdo eclogite (~ 3.4 GPa and ~ 650 °C; ca. 262 Ma) and Jiang eclogite (~ 3.6 GPa and ~ 750 °C; ca. 261 Ma) in the same (ultra)-high-pressure belt indicate that this region likely comprises different slices that had distinct P–T histories and underwent (U)HP metamorphism at different times. The initiation of the opening the Paleo-Tethys Ocean in the Lhasa terrane could trace back to the early Permian. The ultimate closure of the Paleo-Tethys Ocean in the Lhasa terrane was no earlier than ca. 230 Ma.     

Current perspectives on the Permian–Triassic boundary and end-Permian mass extinction: Preface

The end-Permian mass extinction is now robustly dated at 252.6 ± 0.2 Ma (U–Pb) and the Permian–Triassic (P–T) GSSP level is dated by interpolation at 252.5 Ma. An isotopic geochronological timescale for the Late Permian–Early Triassic, based on recent accurate high-precision U–Pb single zircon dating of volcanic ashes, together with calibrated conodont zonation schemes, is presented. The duration of the Early Triassic (Induan + Olenekian stages) is estimated at only 5.5 million years. The duration of the Induan Stage (Griesbachian + Dienerian sub-stages) is estimated at ca. one million years and the early Olenekian (Smithian sub-stage) at 0.7 million years duration. Considering this timescale, the “delayed” recovery following the end-Permian mass extinction may not in fact have been particularly protracted, in the light of the severity of the extinction. Conodonts evolved rapidly in the first 1 million years following the mass extinction leading to recognition of high-resolution conodont zones. Continued episodic global environmental and climatic stress following the extinction is recognized by multiple carbon isotope excursions, further faunal turnover and peculiar sedimentary and biotic facies (e.g. microbialites). The end-Permian mass extinction is interpreted to be synchronous globally and between marine and non-marine environments. The nature of the double-phased Late Permian extinction (at the Guadalupian–Lopingian boundary and the P–T boundary), linked to large igneous provinces, suggests a primary role for superplume activity that involved geomagnetic polarity change and massive volcanism.     

Isotopic ages for alkaline igneous rocks,including a 26 Ma ignimbrite,from the Peshawar plain of northern Pakistan and their tectonic implications

New isotopic ages on zircons from rocks of the Peshawar Plain Alkaline Igneous Province (PPAIP) reveal for the first time the occurrence of ignimbritic Cenozoic (Oligocene) volcanism in the Himalaya at 26.7 ± 0.8 Ma. Other new ages confirm that PPAIP rift-related igneous activity was Permian and lasted from ∼290 Ma to ∼250 Ma. Although PPAIP rocks are petrologically and geochemically typical of rifts and have been suggested to be linked to rifting on the Pangea continental margin at the initiation of the Neotethys Ocean, there are no documented rift-related structures mapped in Permian rocks of the Peshawar Plain. We suggest that Permian rift-related structures have been dismembered and/or reactivated during shortening associated with India–Asia collision. Shortening in the area between the Main Mantle Thrust (MMT) and the Main Boundary Thrust (MBT) may be indicative of the subsurface northern extension of the Salt Range evaporites. Late Cenozoic sedimentary rocks of the Peshawar Plain deposited during and after Himalayan thrusting occupy a piggy-back basin on top of the thrust belt. Those sedimentary rocks have buried surviving evidence of Permian rift-related structures. Igneous rocks of the PPAIP have been both metamorphosed and deformed during the Himalayan collision and Cenozoic igneous activity, apart from the newly recognized Gohati volcanism, has involved only the intrusion of small cross-cutting granitic bodies concentrated in areas such as Malakand that are close to the MMT. Measurements on Chingalai Gneiss zircons have confirmed the occurrence of 816 ± 70 Ma aged rocks in the Precambrian basement of the Peshawar Plain that are comparable in age to rocks in the Malani igneous province of the Rajasthan platform ∼1000 km to the south.     

Glacial/interglacial sea surface temperature changes in the Southwest Pacific ocean over the past 360 ka

The phase relationship between climate parameters during terminations gives insight into deglaciation mechanisms. By combining foraminiferal Mg/Ca and alkenone thermometers with planktonic and benthic foraminiferal δ¹⁸O, we determined the phase relationship between local sea surface temperature (SST) and global seawater δ¹⁸O changes in the Coral Sea in the Southwestern Pacific over the last 360 ka. The onset of the SST warming preceded the seawater δ¹⁸O change by several ka for Termination I, II and III. During Termination I, the SST warming started at 20 ka BP, earlier than atmospheric CO₂ rise suggesting that the greenhouse effect was not the main trigger of this early warming. Compilation of ¹⁴C-dated SST records from the whole Pacific during Termination I reveals that the onset of the warming is generally earlier in the Southern and the tropical Pacific than in the North Pacific. This spatio-temporal warming pattern suggests linkage between the southern ocean and tropical Pacific. The early tropical warming could provide heat and moisture to the northern high latitudes, modifying radiative balance and precipitation over ice sheets at the onset of deglaciation.     

Detrital zircon provenance of upper Cambrian-Permian strata and tectonic evolution of the Ellsworth Mountains,West Antarctica

Detrital zircons from the upper Cambrian-Devonian sandstones (Crashsite Group; n = 485) and Carboniferous tillite (Whiteout Conglomerate; n = 81) of the Ellsworth Mountains, Antarctica record a steady supply of Neoproterozoic (“Pan-African”) orogeny (~ 550–600 Ma), Grenville (~ 1000 Ma) and Neoarchean (~ 3000–3500 Ma) zircons into the northern marginal basin of Gondwana. The overlying Permian Glossopteris-bearing Polarstar Formation shales (n = 85) have the same zircon provenance as underlying units but also include a dominance of depositional-age (263 Ma) euhedral zircons which are interpreted to be of local, volcanic arc origin. Modeling of detrital zircon provenance suggests that source areas were present in Pan-African and Laurentian crust throughout the Paleozoic. We also report calcite twinning strain results (12 strain analyses; n = 398 twins) for the Cambrian Minaret Fm. in the Heritage range which is predominantly a layer-parallel shortening strain in the direction (WSW-ENE) of Permian Gondwanide orogen thrust transport. There is a secondary, sub-vertical twinning strain overprint. The initiation of localized lower-middle Cambrian rifting (Heritage Group deposition) in Grenville-aged crust as Gondwana amalgamated and the subsequent Jurassic counterclockwise rotation of the Ellsworth-Whitmore terrane out of the Permian Gondwanide belt into central Antarctica each remain tectonic curiosities.