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This paper presents first U–Pb detrital zircon ages, major and trace element geochemical data and whole-rock Nd and Hf-in-zircon isotope data from sandstones of the Char and Zharma zones of eastern Kazakhstan. Petrographically the sandstones represent greywackes. The U–Pb ages of detrital zircons show unimodal distributions peaked at 345–340 and 330–325 Ma indicating post-Early Carboniferous deposition. The sandstones have high CIA values (60–68), suggesting moderate to weak chemical weathering. Their high ICV values (1.1–1.3) and relatively high MgO and low Y, Nb indicate an immature probably mafic–intermediate igneous source (low La/Th, medium Hf). Positive whole-rock eNd(t) and zircon eHf(t) indicate dominantly juvenile character of igneous rocks in the provenance. In total, the unimodal character of U–Pb detrital zircon age patterns, the chemical composition of sandstones similar to that of associated volcanic rocks and the positive values of eNd(t) and eHf(t) suggest their derivation from one or more intra-oceanic arcs. The data from eastern Kazakhstan fit those obtained from late Paleozoic greywacke sandstones of NW China. The new geochemical and geochronological data from sandstones and published data from oceanic and supra-subduction ophiolites of eastern Kazakhstan suggest an extended Pacific-type subduction system in the western Paleo-Asian Ocean in Devonian–early Carboniferous time.

The paper presents new original data on the Devonian felsic volcanism of the NW Rudny Altai (Russia) in the west of Central Asian Orogenic Belt (CAOB) – the front part of the Altai convergent margin of the Siberian continent. Two geochemical types of subvolcanic rhyolites were emplaced synchronously with the bimodal rhyolite-basalt association, which began to form in the end-Emsian, and clearly manifested on the border of the Givetian and the Frasnian. The rhyolites yield zircon U-Pb ages of ca. 390 Ma (R1-type) and 380 Ma (R2- and R3-types), reflecting two peaks of the volcanic activity. Most of these rocks have extreme petrochemical characteristics of high SiO2 contents and have contrast Na/K ratios. Their compositions are transition between calc-alkaline and tholeiite series: (La/Yb)n ~ 2–7, Zr/Y ~ 4 (Zr 350 ppm), Zr (>250 ppm), and high Ga/Al (>2.6) values. The island-arc-like R1-rhyolite formed immediately after the beginning of rifting due to widespread crustal melting under reduced conditions. The generation of rift-like R2- and R3-rhyolites took place under non-equilibrium conditions, synchronously with the rise in the upper crust of Givetian-Frasnian basic magmas, as a result of the active lithospheric extension and high thermal input from the underlying hot mantle. We propose an extension regime in the transition area between the island-arc and back-arc basin for the origin of rhyolites. The study of the Devonian volcanism of the Rudny Altai gives important information about the processes that occurred at the initial stage of the formation of the Altai convergent margin.

The paper presents the results of geological, geochemical and isotope-geochronological studies of subvolcanic rhyolites of the Western Gorny Altai and Rudny Altai which have related to two large volcanic systems, the Altai-Minusinsk and Altai-Salair, respectively. The results of U-Pb isotopic dating of zircons revealed two groups of ages ~410-405 and 390-381 million years. Isotope-geochemical characteristics of rhyolites show relatively high values of εNd(T) = +2,7...6,0 with relatively young values of model ages T(DM) = 851-966 Ma in the Rudny Altai and more ancient - up to 1266 Ma in the West Gorny Altai. Geochemical characteristics indicate that its composition is consistent with transitional field between within-plate and island-arc felsic magmas. The results obtained correspond to the two-stage evolution of volcanism and its migration from the continent to the ocean.

The Ediacaran to Cambrian periods are characterized by the diversification and extinction of metazoans, carbon-cycle perturbation, and ocean oxygenation. Ocean nutrient cycles play a major role in the primary production and productivity-driven shallow water anoxia that was responsible for mass extinction in some Phanerozoic intervals. However, the relationships between these cycles and primary production and biological events during the Ediacaran to Cambrian periods have not previously been well-explored. This study presents stratigraphic profiles of nitrogen and organic carbon isotopes for sections belonging to the shelf and deep basin regions of the Yangtze Platform, South China. The nitrogen isotope profiles for these two regions share a similar trend, showing 1) relatively stable δ15N values of 5–6‰ in the early–middle Ediacaran (635 Ma–ca. 560 Ma) and 2) a shift towards lower δ15N values (3–4‰) since the Shuram δ13Ccarb Excursion. The δ15N values in the shelf section experienced a two-stage decrease from the late Ediacaran to Cambrian Stage 2 of the Terreneuvian series (down to −1‰) and then an increase from −1‰ to +4‰ across the Cambrian Stage 2/3 boundary (i.e., the Terreneuvian/Cambrian Series 2 boundary at 521 Ma). These data, in combination with previously reported nutrient profiles (δ15N, P, and Mo), allow the following new conclusions to be drawn. 1) The early–middle Ediacaran ocean was characterized by N Mo colimitation of primary production on a geological timescale that is different from the P limitation on long-term primary production in the modern ocean. 2) A shift in the ultimate limiting nutrient from N and Mo to P likely occurred in late Ediacaran–early Cambrian marine systems. This shift may have been a prerequisite for the extinction of small shelly fossils in response to the development of photic zone anoxia for several million years in Cambrian Stage 2, which was followed by the third and most prominent phase of metazoan diversification.

The paper reports the results of geological, geochemical, and isotope–geochronological studies of subvolcanic rhyolites of NW Gorny Altai and Rudny Altai, which belong to the large Hercynian volcanic systems: Altai-Minusa and Altai–Salair, respectively. U–Pb zircon dating revealed two age groups: ~410–405 and 390–381 Ma. The isotope–geochemical characteristics of the rhyolites demonstrate high eNd(Т) from +2.6 to 6.0 with relatively young model ages T(DM) = 851–966 Ma in Rudny Altai and older model ages, up to 1266 Ma, in NW Gorny Altai. The rhyolites show transitional geochemical signatures between within-plate and island-arc felsic magmas. The results obtained are consistent with two-stage evolution of volcanism and its migration from the continent to the ocean.

The article presents new geological, geochronological, mineralogical, geochemical, and isotopic data on the Early Cretaceous granitic rocks of the southern part of the Zhuravlevka Terrane (Sikhote-Alin). It is shown that four intrusive complexes containing significant amounts of granitic rocks were formed almost simultaneously in this area in the Early Cretaceous (about 100 Ma). These magmatic associations differ in rock set, their mineralogical characteristics, and chemical composition, varying from medium-potassium tonalites and granodiorites depleted in incompatible elements to shoshonitic monzonitic rocks enriched in HFSE and REE. The geochemical and isotopic characteristics of the granitic rocks indicate that the source of their melts was dominated by essentially juvenile metabasite crust with a limited contribution of the upper-crustal metasedimentary rocks. The diversity of geochemical types of the granitic rocks is explained by variable metabasite and metapelite contributions to their source, upper crustal contamination during magma ascent, as well as the variable contribution of the mantle source and different mechanisms of mantle–crust interaction.

The metamorphic P–T conditions and processes of the mid-Archean Barberton Greenstone Belt (BGB), South Africa were examined with petrological and thermodynamic data from metamorphosed banded iron formation (BIF) and garnet amphibolite in the Inyoni shear zone (ISZ). Equilibrium mineral assemblages in these two rocks range from Grt + Cpx + Gru + Mag + Qz through Grt + Cpx + Gru + Amp + Mag + Qz to Amp + Gru + Mag + Qz, and from Grt + Cpx + Amp + Pl + Ep + Qz to Cpx + Amp + Pl + Ep + Qz, respectively. The metamorphic P–T conditions of these assemblages were estimated from thermodynamic calculations combined with their whole-rock and constituent mineral compositions. The results show that the metamorphosed BIF and garnet amphibolite samples record three and two different metamorphic P–T conditions, respectively, within a single period of metamorphism. The P–T conditions of the BIF changed from ca. 600–680 °C and >10 kbar through ca. 510–540 °C and 8–11 kbar to less than 500 °C and 4 kbar. The P–T conditions of the garnet amphibolite changed from ca. 9.5–10.5 kbar and 620–660 °C to less than 5 kbar and 500 °C. These new results combined with previously published data suggest that the geothermal gradients of the peak and retrograde metamorphisms were ca. 15–20 °C/km and 20–30 °C/km, respectively, and the possibility that the ISZ underwent slightly earlier prograde metamorphism than the high-pressure BGB. The difference between the gradients of 15–20 °C/km and 20–30 °C/km in the ISZ rocks was probably related to a shift from oceanic plate subduction to continental collision at ca. 3.23 Ga.

The Ediacaran–Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances. Based on geological evidence, it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life. Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species, this method is not necessarily applicable to all rocks. In the Earth system, the cycling of iron is of considerable interest owing to its sensitivity to redox conditions. Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of iron-bearing minerals. Unfortunately, only limited iron isotopic data exists for Ediacaran- to Cambrian-period oceans. To circumvent this deficiency, we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region, South China. We analyzed the iron isotope ratios (δ56/54Fe) of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry. The results demonstrate large variations in δ56/54Fe, from −1.6 to 1.6‰, and positive iron isotope ratios are observed in many successions. The presence of positive δ56/54Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized, suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods. However, aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zero δ56/54Fe values; this suggests that the ocean was transiently dominated by sulfidic conditions during these periods. Notably negative δ56/54Fe values, lower than −1‰, can be interpreted as a signature of DIR. The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.

We determined highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) concentrations and 187Os/188Os ratios for ultramafic rocks distributed over the Eoarchean gneiss complex of the Saglek-Hebron area in northern Labrador, Canada in order to constrain to what extent variations in HSE abundances are recorded in Early Archean mantle that have well-resolved 182W isotope anomalies relative to the present-day mantle (∼+11 ppm: Liu et al., 2016). The samples analysed here have been previously classified into two suites: mantle-derived peridotites occurring as tectonically-emplaced slivers of lithospheric mantle, and metakomatiites comprising mostly pyroxenitic layers in supracrustal units dominated by amphibolites. Although previous Sm-Nd and Pb-Pb isotope studies provided whole-rock isochrons indicative of ∼3.8 Ga protolith formation for both suites, our whole-rock Re-Os isotope data on a similar set of samples yield considerably younger errorchrons with ages of 3612 ± 130 Ma (MSWD = 40) and 3096 ± 170 Ma (MSWD = 10.2) for the metakomatiite and lithospheric mantle suites, respectively. The respective initial 187Os/188Os = 0.10200 ± 18 for metakomatiites and 0.1041 ± 18 for lithospheric mantle rocks are within the range of chondrites. Re-depletion Os model ages for unradiogenic samples from the two suites are consistent with the respective Re-Os errorchrons (metakomatiite TRD = 3.4–3.6 Ga; lithospheric mantle TRD = 2.8–3.3 Ga). These observations suggest that the two ultramafic suites are not coeval. However, the estimated mantle sources for the two ultramafics suites are similar in terms of their broadly chondritic evolution of 187Os/188Os and their relative HSE patterns. In detail, both mantle sources show a small excess of Ru/Ir similar to that in modern primitive mantle, but a ∼20% deficit in absolute HSE abundances relative to that in modern primitive mantle (metakomatiite 74 ± 18% of PUM; lithospheric mantle 82 ± 10% of PUM), consistent with the ∼3.8 Ga Isua mantle source and Neoarchean komatiite sources around the world (∼70–86% of PUM). This demonstrates that the lower HSE abundances are not unique to the sources of komatiites, but rather might be a ubiquitous feature of Archean convecting mantle. This tentatively suggests that chondritic late accretion components boosted the convecting mantle HSE inventory after core separation in the Hadean, and that the Eoarchean to Neoarchean convecting mantle was depleted in its HSE content relative to that of today. Further investigation of Archean mantle-derived rocks is required to explore this hypothesis.

The early Cambrian Carinachitidae, a family in the subclass Conulata, are intriguing and important small shelly fossils. Their gently tapering, tube-shaped skeletons consist of convex faces separated from each other by broad, deep corner sulci, and they exhibit triradial, pentaradial, or predominantly tetraradial symmetry. However, the morphology of the aperture and the modes of growth of carinachitid skeletons as well as the anatomy of their soft parts are unknown. Examination of a single new, exceptionally well-preserved specimen of tetramerousCarinachites spinatusQian, 1977, collected from the lower Cambrian Kuanchuanpu Formation in South China, reveals: (1) that its aperture is connected to a small mass of relic soft tissue and (2) that the apertural end of each of the four faces is developed into a subtriangular lappet or oral lobe that is smoothly folded toward the long axis of the tube, partially closing the tube aperture. Similarities between thorn-like spines on the faces and the oral lobes indicate that the transverse ribs were periodically displaced from the perradial portion of the aperture during formation of new ribs. In addition, the tube walls may have undergone secondary thickening during growth. The growth pattern of the tube and the spatial relationships between the tube aperture and soft parts are analogous to those of co-occurring olivooids. These findings further strengthen the previously proposed hypothesis that coeval carinachitids, olivooids, hexangulaconulariids, and Paleozoic conulariids are closely related taxa within the subphylum Medusozoa. Finally, carinachitids most likely represent an evolutionary intermediate between olivooids and hexangulaconulariids.

Abundant microstructures have been discovered in small skeletal fossils (SSFs) and embryo-like fossils collected from the Lower Cambrian Kuanchuanpu Formation (ca. 535 Ma) in Xixiang County, Shaanxi Province, China. These involve two co-occurring structures: (1) long, unbranched cylindrical filaments, which are comparable to phosphatic casts of microborings constructed by euendolithic cyanobacteria (Endoconchia lata) in morphology and preservation pathway; and (2) meandering micro-tubes or grooves on fossil moulds (and steinkerns) of a wide range of sizes and morphological diversities, perceived as ambient inclusion trails (AITs). Herein, we also report a new occurrence of organic carbon spherules as AIT-propelled material, which is rare in comparable fossils. From direct comparison of endolith fossils and AITs, we propose a mechanism to account for their notably different preservation, and further attempt to offer an explanation for their co-occurrence. Their differential preservation suggests a chronological, taphonomic sequence of their formation. We interpret that E. lata microborings formed prior to phosphate sedimentation, whereas AITs are likely generated in a later phase of (or after) phosphorite precipitation but before calcareous re-cementation. Dissecting the sequence of formation of these structures, in conjunction with detailed morphological observations, assists in distinguishing true biologically produced endoliths from otherwise abiogenically produced microstructures.

The Archean continental crusts account for ca. 20% of the present volume, but the thermal history of the Earths' mantle suggests much more continental crusts were formed in the early Archean. Because the Archean continental crust underwent severe metamorphism, it is important to avoid influence by the later thermal events. We carried out a comprehensive geochronological work of Cathodoluminescence (CL) observation and U-Pb dating of zircons from orthogneisses and supracrustal rocks over the Saglek Block to obtain their protolith ages. The zircons were classified into three domains of core, mantle and rims, and the cores were further classified into three groups of inherited, altered and zoned cores based on the zonation on the CL images. We estimated the protolith ages from Pb-Pb ages of the zoned-cores of zircons with low U contents. We made a detailed sketch of a small outcrop in St. John's Harbour South (SJHS) area, and classified the orthogneisses and mafic enclaves into seven generations based on the geologic occurrence. The first and second generations comprise mafic rocks and lack magmatic zircons. We conducted CL imaging and U-Pb dating of zircons from the third, sixth and seventh generation of the orthogneisses to estimate the protolith ages at 3902 ± 25, 3892 ± 33 and 3897 ± 33 Ma for each, supporting the presence of the over 3.9 Ga Iqaluk Gneiss. The geological occurrence that the mafic rocks occur as enclaves within the 3.9 Ga Iqaluk Gneiss indicates that they are the oldest supracrustal rocks in the world. Our geochronological and geological studies show the Uivak Gneiss is quite varied in lithology and age from 3.6 to >3.9 Ga, and tentatively classified into six groups based on their ages. The oldest Uivak Gneiss components including the Iqaluk Gneiss are present around the SJHS area, and the orthogneisses become young as it is away. The lines of evidence of overprinting of younger granitoid on older granitoid in small outcrops and geological-map scale as well as presence of inherited zircons even in the oldest suite suggests that crustal reworking played an important role on erasing the ancient crusts.

The earliest fossil record of animal biomineralization occurs in the latest Ediacaran Period (c. 550 Ma).CloudinaandSinotubulitesare two important tubular taxa among these earliest skeletal fossils. The evolutionary fate ofCloudina-type fossils across the Ediacaran–Cambrian transition, however, remains poorly understood. Here we report a multi-layered tubular microfossilFeiyanella manicagen. et sp. nov. from a phosphorite interval of the lowest Cambrian Kuanchuanpu Formation, southern Shaanxi Province, South China. This newly discovered fossil is a conical tube with a ‘funnel-in-funnel’ construction, showing profound morphological similarities toCloudinaandConotubus. On the other hand, the outer few layers, and particularly the outermost layer, ofFeiyanellatubes are regularly to irregularly corrugated, a feature strikingly similar to the variably folded/wrinkled tube walls ofSinotubulites. TheFeiyanellatubes additionally exhibit two orders of dichotomous branching, similar to branching structures reported occasionally inCloudinaand possibly indicative of asexual reproduction. Owing to broad similarities in tube morphology, tube wall construction and features presumably indicative of asexual reproduction,Cloudina, Conotubus, Sinotubulitesand the here describedFeiyanellamay thus constitute a monophyletic group traversing the Ediacaran–Cambrian boundary. The tube construction and palaeoecological strategy ofFeiyanellaputatively indicate evolutionary continuity in morphology and palaeoecology of benthic metazoan communities across the Ediacaran–Cambrian transition.

The Acasta Gneiss Complex, located in the western part of the Slave Province, Canada, is widely recognized as the oldest Eoarchean terrane. In addition to felsic gneisses with the ages of 3.6–4.0 Ga, minor mafic rocks occur as rounded to elliptical enclaves and inclusions within the felsic gneisses. Despite serving as potential sources of geochemical information on the Hadean mantle, the mafic rocks have received less attention in previous studies. Thus, we conducted a comprehensive geological petrological and geochemical investigation on the Acasta mafic rocks to constrain their petrogenesis and geodynamic setting. The mafic rocks comprise massive to weakly foliated amphibolite, garnet amphibolite and hornblendite, with variable abundances of hornblende, plagioclase, chlorite and quartz and subordinate clinopyroxene, garnet and cummingtonite. They commonly underwent high-grade metamorphic recrystallization under amphibolite to upper-amphibolite facies conditions. The observed variations in mineral assemblages, abundances and compositions reflect large differences in whole-rock compositions, likely caused by crustal anatexis during the Eoarchean thermal events responsible for the generation of the surrounding felsic gneisses. Infiltration or extraction of felsic melts formed due to partial melting of precursor rocks can account for an overall negative correlation between Al 2 O 3 and MgO contents and variable enrichments in the incompatible elements. Despite the widespread influence of anatexis on the geochemistry of Acasta mafic rocks, we identified the precursor compositions of the least-modified amphibolites as basaltic magmas. They are characterized by intermediate Al 2 O 3 and MgO contents on the observed array and by near chondritic patterns for incompatible trace elements, except for slightly negative Nb and Ta anomalies. We considered two scenarios to explain the origin of Eoarchean basaltic rocks with Nb–Ta anomalies: (1) generation of Nb–Ta deficient basaltic magma in a suprasubduction setting, analogous to modern arcs-derived magmas, and (2) generation of Nb–Ta deficient basaltic magma from the melting of a Nb–Ta deficient primitive mantle, possible if the core contains significant proportions of the Earth’s Nb and Ta budget. Although the operation of plate tectonics and the presence of subduction zones at the end of Hadean may be an attractive explanation for the observed Nb–Ta depletions, the chondritic relative proportions of other immobile trace elements for Acasta mafic rocks leave open the possibility of their formation from an Nb–Ta deficient primitive mantle.

Cap Carbonates overlie the Marinoan Snowball Earth-related glacial diamictite, and possibly record the drastic surface environmental change and biological evolution after the Snowball Earth. We conducted on-land drilling from the Liantuo Formation, through the Nantuo, to the lower Doushantuo Formation in the Three Gorges area of South China to collect fresh, continuous samples in the Three Gorges area. We obtained high-resolution chemostratigraphies of δ 13 C and δ 18 O values of carbonates from the topmost part of the Nantuo Formation to the Cap Carbonate, in order to decode the detailed surface environmental change in the shallow marine setting. The δ 13 C chemostratigraphy possesses some unique characteristics: (1) stable δ 13 C values as a whole, but ubiquitous low δ 13 C anomalies through the Cap Carbonate, (2) increase of the δ 13 C values from −3 to +5‰ across the C2/C3 boundary, (3) no δ 13 C anomaly between the C1 and C2 boundary, and (4) presence of an anomalous high δ 13 C value (+2.3‰) and a faint positive correlation between δ 13 C and δ 18 O values in the C1 unit. Evidence of quite low δ 13 C anomalies (with a nadir of −41‰), ubiquitous negative δ 13 C anomalies through the Cap Carbonate, and a high δ 13 C anomaly accompanied with a faint positive correlation between δ 13 C and δ 18 O values in the C1 unit supports decomposition and formation of methane hydrate during Cap Carbonate formation. The drastic increase of δ 13 C values from the upper C2 to C3 units indicates enhancement of primary productivity and organic carbon burial, possibly due to high continental fluxes after the Snowball Earth event, evidenced by high Sr isotope values. The increase is restricted to the proximal side of the inner shelf in South China, and the timing of the increase of δ 13 C values of carbonates is earlier at Three Gorges area than any other area, suggesting that the enhancement of primary productivity started in the proximal environment because of higher continental influxes. The increase in oxygen contents of seawater due to the enhanced primary productivity possibly resulted in the emergence of multicellular animals soon after Cap Carbonate deposition.

Understanding Earth’s early evolution requires decoding the cryptic geological record that is preserved in a few extremely rare terrains on Earth. The Saglek–Hebron Block in the North Atlantic Craton is one of the oldest terrains in the world. To better understand the Eoarchean history of the Saglek–Hebron Block, we undertook a comprehensive geological and geochronological investigation of this terrain. The Saglek–Hebron locality contains orthogneisses and supracrustal rocks, which are classified into two groups of the Eoarchean and Mesoarchean suites based on field associations defined by intrusion of the Mesoarchean mafic Saglek dykes. The Eoarchean suites contain the Nulliak supracrustal rocks and Uivak Gneisses. In this paper, we report cathodoluminescence (CL) observations and U–Pb ages of zircons from the Eoarchean orthogneisses to constrain the evolution of the Saglek–Hebron Block. We made detailed sketch maps (1:20) of critical outcrops to establish relative chronological relationships between lithologies. At least seven generations of mafic and felsic units were recognized in an outcrop of the St John’s Harbour South area. The first and second generations are mafic supracrustal rocks whereas the third to seventh generations are tonalitic gneisses, which are intruded into the supracrustal units. We study CL observation, geochemistry and U–Pb dating of zircons from the oldest and youngest tonalitic gneisses. The CL observation of internal structures of the zircons showed they typically comprise three domains of core, mantle and rim. The cores have clear oscillatory zoning, whereas the mantles lack oscillatory zoning and exhibit dark CL emission and structureless CL images. The obvious correlation between the ages and chemical compositions of U contents and Th/U ratios indicates that the cores with low U contents and high Th/U ratios preserve the protolith age. The cores with clear oscillatory zoning, low U contents and high Th/U ratios of zircons from the oldest suite plot on a concordia line with ages ranging from 3953 to 3797 Ma. The oldest and average ages of the six oldest spots on the concordia line are 3953 ± 54 and 3920 ± 49 Ma, respectively. On the other hand, the average age of the four old spots of zircons from a younger generation of orthogneiss is 3869 ± 63 Ma. The geological and geochronological relationships between the third and seventh generation orthogneisses are consistent with each other, confirming an Eoarchean age of ca. 3.9 Ga for the oldest suite of the Uivak Gneisses. We name this oldest suite the Iqaluk Gneiss. As the protolith of the Iqaluk Gneiss was clearly intruded into the Nulliak supracrustal rocks, the Nulliak supracrustals must have a minimum age of ca. 3.9 Ga, indicating that they are the oldest supracrustal rocks on Earth. But, further studies should be necessary to obtain more precise age of the Iqaluk Gneiss and Nulliak supracrustal rocks.

Du, W., Wang, X.L., Komiya, T., Zhao, R. & Wang, Y., April 2016. Dendroid multicellular thallophytes preserved in a Neoproterozoic black phosphorite in southern China. Alcheringa 40, xxx–xxx. ISSN 0311-5518.A new form of dendroid multicellular thallophyte is documented in the Ediacaran Doushantuo phosphorite at Weng’an, Guizhou Province, southern China. The dendroid thallophytes have variable forms, possibly owing to heteromorphic variation. Many lateral branches extend from the upper portions of the main axes; the lateral branches bear terminal vegetative vesicles, reproductive vesicles, monosporangium-like discoidal vesicles and urn-shaped pseudoparenchymatous structures. The vegetative vesicles give rise to clavate pseudoparenchymatous structures, characterized by differentiation of the thallus medulla/cortex, which might represent an early stage of thallus development. An oogamous conceptacle arising from one carpogonial vesicle forms a highly specialized goblet-shaped conceptacle. The discovery of th...

The Ongeluk Formation mainly consists of submarine volcanics (pillow lavas and sheet flows) composed of basaltic andesites that are between underlying and overlying glaciogenic deposits (i.e., the Makganyene diamictite and a dropstone layer at the base of the Hotazel Formation, respectively). The stratigraphic position of the Ongeluk Formation indicates that the Ongeluk volcanism occurred during a period of global glaciation. The Ongeluk volcanic rocks are host to subseafloor hydrothermal quartz deposits as drainage cavities and interpillow voids. The hydrothermal quartz contains many primary (Type 1) and secondary (Type 2) liquid–vapor fluid inclusions, as well as inclusions that are randomly distributed without a trace of secondary healed cracks (Type 3). All these fluid inclusions types were individually analyzed with microthermometry and particle-induced X-ray emission (PIXE) methods. The results show that Type 1 fluid inclusions are highly saline, whereas Type 2 fluid inclusions are relatively less saline. Type 3 fluid inclusions have bimodal peaks of salinity corresponding to those of Type 1 and Type 2 fluid inclusions and thus appear to represent mixtures between latter two inclusion types. Among the various fluid inclusion salinities of fluid inclusions, a wide range in Na/Ca values was identified in the high-salinity fluid inclusions (i.e., Type 1 and a subset of Type 3) which are thought to represent subseafloor fluids circulated by the Ongeluk submarine volcanism. The wide range in Na/Ca values can be explained by a mixing process between Na-rich and Ca-rich fluids associated with albitization of the host basaltic andesites. In the albitization process, Na is removed from the fluids and fixed by the host rocks; by contrast Ca is released from the host rocks into the fluids. PIXE analysis also showed two distinct trends (i.e., vertical and horizontal) on variation diagram of Ca/Cl versus Cu/Cl and positive correlations between Mn/Cl, Cu/Cl, Zn/Cl and Pb/Cl. These data are best explained by the presence of other mixing processes between; (1) a Na-rich, Ca- and Cu-poor fluid, (2) a Ca-rich, Na- and Cu-poor fluid, and (3) a Na- and Cu-rich, Ca-poor fluid. The Cu-, Mn-, Zn- and Pb-rich fluid likely represents a high-temperature hydrothermal fluid from a deep reaction zone in the Ongeluk subseafloor hydrothermal system. By contrast, the (1) Na- (and K-) rich, Ca- and Cu-poor endmember for the high-salinity primary inclusions is considered to represent the composition of 2.2 Ga Ongeluk seawater. We propose the estimation of 2.2 Ga Ongeluk seawater composition is >∼2237 mmol/kg of Na, 200–1000 mmol/kg of K

We present a new approach for recognizing the origin of accreted basaltic rocks based on ocean plate stratigraphy (OPS), and on the petrology and geochemistry of basalts from mid-oceanic ridges (MORB) and oceanic islands (OIB) using examples from four accretionary complexes (AC) in SW Japan: Akiyoshi, Mino–Tamba, Chichibu and Shimanto. The key to the problem is the model of OPS, which includes an association of igneous and sedimentary rocks that form on an oceanic plate during its travel from a mid-oceanic ridge to a subduction zone. We propose the reconstruction of the tectonic settings of basalts according to their relationships with associated OPS sediments, their petrogenesis and their geochemical features. Five types of OPS are recognized in the accretionary complexes of SW Japan: (1) sandstone/shale; (2) sandstone/shale and chert; (3) sandstone/shale, chert and MORB; (4) sandstone/shale, chert, MORB and gabbro (± peridotite); (5) seamount OPS including OIB, cap carbonates, slope clastics and basal shale/chert. The alkaline, tholeiitic or calc-alkaline composition of basaltic melts, which are typical of oceanic islands, mid-oceanic ridges and island-arcs, respectively, can be identified by the sequence in crystallization of their major phenocrysts, i.e. olivine (ol), clinopyroxene (cpx) and plagioclase (pl), and by their compositions. Alkaline and calc-alkaline mafic lavas are characterized by an ol → cpx → pl succession, whereas tholeiitic melts by their ol → pl ± cpx succession. Titanium-rich minerals, e.g., Ti–augite, kaersutite, Ti–biotite, are typical of alkaline lavas. The application of geochemistry-based tectonic discrimination diagrams is also a powerful tool, if not supported by geological and petrological data, may result in confusion due to magma contamination, post-magmatic alteration, and secular change of mantle thermal conditions. We propose that a direct comparison of normalized multi-element patterns and key binary plots from older volcanic rocks with their modern analogues provides a more viable and reliable method of basalt discrimination. Our OPS–petrology–geochemistry method allows us to confirm the above conclusions that the lavas of the Akiyoshi, Mino–Tamba and Southern Chichibu AC formed in oceanic islands, because they are associated with seamount OPS sediments, crystallized from ol to cpx and pl, contain Ti–augite and kaersutite and are enriched in TiO2, LREE and Nb. In this paper we present geochemical data from the Inuyama basalts of the Mino–Tamba AC and from the Toba complex in the huge Mikabu greenstone belt of the Chichibu AC. The Inuyama basalts are in contact with Jurassic pelagic cherts, but their geochemical features are confusing; they contain phenocrysts of ol, Ti–augite and kaersutite and therefore probably formed in seamounts. The Toba volcanic rocks are a part of the huge ophiolite belt; they have flat to slightly LREE-enriched REE patterns, are characterized by an ol → cpx succession of phenocrysts and they plot in the OIB field in binary plots suggesting they formed in an oceanic plateau.

Compositional variability found in modern mid-ocean ridge basalt (MORB) and ocean island basalt (OIB) reflects differentiation processes associated with material recycling in the mantle-crust system. To investigate the timing at which this recycling system was established and how it transformed into the present-day system, we present geochemical analyses of the Archean basalts from North Pole (NP) in the East Pilbara Craton, Western Australia, and the Isua supracrustal belt (ISB), southern West Greenland. These rocks represent Archean accretionary complexes with ages of ~3.5 Ga and 3.7–3.8 Ga, respectively. We analyzed the trace element contents including rare earth elements (REEs), and Sr and Nd isotopic compositions of the basalts, which may represent MORBs and OIBs, from NP and ISB. Their trace-element compositions are broadly similar, but show distinct geochemical characteristics particularly with respect to REEs that probably reflect differences in both the source mantle and degree of melting. Such differences are also evident in their initial Nd isotopic compositions, which were estimated based on equilibrium partitioning of REEs and well-defined isochron ages. In contrast, the Sr isotopic compositions of the NP and ISB basalts are highly variable and their isochron ages are inconsistent with previous studies. Furthermore, the partitioning of Rb and Sr in the NP basalts indicates disequilibrium, suggesting that the Rb-Sr system has been disturbed by post-igneous alteration and metamorphism. Based on these observations, we propose the following model to explain the temporal variations in the geochemical composition of the Archean mantle: (i) ~3800 Ma: recycling of plate material and melting occurred quite readily and, therefore, MORBs and OIBs were produced from differentiated mantle sources; (ii) 3460 Ma to ~3800 Ma: mantle-crust mixing occurred as the result of an extreme event, such as mantle overturning, reducing the compositional variation of the mantle; and (iii) after ~3460 Ma: mantle heterogeneity gradually developed in the material-recycling system, re-establishing the compositional differences between MORBs and OIBs. This model requires an extreme event to drive the homogenization during stage (ii), which may provide new insights into the evolution of the crust-mantle system.

Fluid inclusions in hydrothermal quartz in the 2.4 Ga Ongeluk Formation, South Africa, are expected to partially retain a component of the ancient seawater. To constrain the origin of the fluid and the quartz precipitation age, we conducted Ar–Ar dating for the quartz via a stepwise crushing method. The obtained argon isotopes show two or three endmembers with one or two binary mixing lines as the crushing proceeds, suggesting that the isotopic compositions of these endmembers correspond to fluid inclusions of each generation, earlier generated smaller 40 Ar- and K-rich inclusions, moderate 40 Ar- and 38 Ar Cl (neutron-induced 38 Ar from Cl)-rich inclusions and later generated larger atmospheric-rich inclusions. The K-rich inclusions show significantly different 40 Ar/ 38 Ar Cl values compared to the 38 Ar Cl -rich inclusions, indicating that it is difficult to constrain the quartz formation age using only fluid inclusions containing excess 40 Ar. The highest obtained 40 Ar/ 36 Ar value from the fluid inclusions is consistent with an expected value of the Ongeluk plume source, suggesting that the quartz precipitation was driven by Ongeluk volcanism. Considering the fluid inclusion generations and their compositions, the hydrothermal system was composed of crustal fluid and magmatic fluid without seawater before the beginning of a small amount of seawater input to the hydrothermal system.

The Earth is a unique planet, which has been highly evolved, diversified and complicated through geologic time, and underwent many key events, including giant impact, magma ocean, core formation, large-scale mantle differentiation and late heavy bombardment, especially in its dawn. But, our knowledge of early Earth is limited due to the lack of the Hadean supracrustal rocks. The supracrustal rocks with the Eoarchean ages provide key evidence for the Earth's early evolution, but few supracrustal rocks have been comprehensively investigated. Therefore, we mapped in seven areas of the Saglek Block, northern Labrador, where ancient supracrustal sequences are interleaved with a diverse assemblage of orthogneisses. Early studies suggested that some of them have the Mesoarchean ages because of the lack of the Mesoarchean Saglek dyke, but we found the Saglek dykes in the areas to recognize the Eoarchean Nulliak supracrustal rocks and Uivak Gneiss in all the areas. Recent reassessment of U–Pb dating and cathodoluminescence observation of zircons from the oldest suites of the Uivak Gneiss showed that the Uivak Gneiss has the Eoarchean age, > 3.95 Ga, and forms the Iqaluk–Uivak Gneiss series. Because our geological survey clearly showed that the Iqaluk–Uivak Gneisses were intruded into the Nulliak supracrustal belts, the Nulliak supracrustal rocks are the oldest supracrustal rock in the world. The supracrustal belts consist of piles of fault-bounded blocks, which are composed of the ultramafic rocks, mafic rocks and sedimentary rocks in ascending order, similar to modern ocean plate stratigraphy (OPS). In addition, small-scale duplex structures are found over the areas. The presence of duplex structure and OPS indicates that the > 3.95 Ga Nulliak supracrustal belts originate from an accretionary complex. The presence of the accretionary complex, ophiolite and granitic continental crust provides the oldest evidence for the plate tectonics on the early Earth.

The 3.7–3.8 Ga Isua Supracrustal Belt (ISB), southwest Greenland, might be the oldest accretionary complex on Earth. Regional metamorphism of the ISB has a potential to constrain the tectonothermal history of the Earth during the Eoarchean. Chemical and modal analyses of metabasite in the study area (i.e., the northeast part of the ISB) show that the metamorphic grade increases from greenschist facies in the northern part of the study area to amphibolite facies in the southern part. To determine the precise metamorphic P–T ranges, isochemical phase diagrams of minerals of metabasite were made using Perple_X. A synthesis of the estimated metamorphic P–T ranges of the ISB indicates that both the metamorphic pressure and temperature increase systematically to the south in the study area from 3 kbar and 380 °C to 6 kbar and 560 °C. The monotonous metamorphic P–T change suggests that the northeast part of the ISB preserves regional metamorphism resulting from the subduction of an accretionary complex although the ISB experienced metamorphic overprints during the Neoarchean. Both the presence of the regional metamorphism and an accretionary complex having originating at subduction zone suggest that the ISB may be the oldest Pacific-type orogenic belt. The progressive metamorphism can be considered as a record of intermediate-P/T type geothermal gradient at the subduction zone in the Eoarchean. Intermediate-P/T type geothermal gradient is typical at the current zones of subducting young oceanic crust, such as in the case of the Philippine Sea Plate in the southwest part of Japan. Considering the fact that almost all metamorphisms in the Archean are greenschist–amphibolite facies, the intermediate-P/T type geothermal gradient at the ISB might have been worldwide in the Archean. This would indicate that the subduction of young micro-plates was common because of the vigorous convection of hot mantle in the Archean.

Sponges are widely viewed as the most primitive metazoans. Sponge gemmule-like structures have been recovered from the lower part of the Doushantuo Formation in the Yangtze Gorges area (South China), that were deposited between 635 and 580 Ma. Gemmosclere-like structures are embedded in the outer coat of the sponge structures. Electron probe microanalyses (EPMA) of the gemmoscleresindicate that they have siliceous composition. The naked subspheroidal sponge structures are composed of three layers, consistent with the preservation of a tri-layered theca embedded with the gemmosclere-like structures. The potential fossils of the Ediacaran sponge gemmules in the Doushantuo Formation may provide one of the earliest records of sponges.

To improve estimates of the extent of ocean oxygenation during the late Ediacaran Period, we measured the U and Mo isotope compositions of euxinic (anoxic and sulfidic) organic-rich mudrocks (ORM) of Member IV, upper Doushantuo Formation, South China. The average δ 238 U of most samples is 0.24 ± 0.16‰ (2SD; relative to standard CRM145), which is slightly higher than the average δ 238 U of 0.02 ± 0.12‰ for restricted Black Sea (deep-water Unit I) euxinic sediments and is similar to a modeled δ 238 U value of 0.2‰ for open ocean euxinic sediments in the modern well-oxygenated oceans. Because 238 U is preferentially removed to euxinic sediments compared to 235 U, expanded ocean anoxia will deplete seawater of 238 U relative to 235 U, ultimately leading to deposition of ORM with low δ 238 U. Hence, the high δ 238 U of Member IV ORM points to a common occurrence of extensive ocean oxygenation ca. 560 to 551 Myr ago. The Mo isotope composition of sediments deposited from strongly euxinic bottom waters ([H 2 S] aq >11 μM) either directly records the global seawater Mo isotope composition (if Mo removal from deep waters is quantitative) or represents a minimum value for seawater (if Mo removal is not quantitative). Near the top of Member IV, δ 98 Mo approaches the modern seawater value of 2.34 ± 0.10‰. High δ 98 Mo points to widespread ocean oxygenation because the preferential removal of isotopically light Mo to sediments occurs to a greater extent in O 2 -rich compared to O 2 -deficient marine environments. However, the δ 98 Mo value for most Member IV ORM is near 0‰ (relative to standard NIST SRM 3134 = 0.25‰), suggesting extensive anoxia. The low δ 98 Mo is at odds with the high Mo concentrations of Member IV ORM, which suggest a large seawater Mo inventory in well-oxygenated oceans, and the high δ 238 U. Hence, we propose that the low δ 98 Mo of most Member IV ORM was fractionated from contemporaneous seawater. Possible mechanisms driving this isotope fractionation include: (1) inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater-like δ 98 Mo signature in sediments or (2) delivery of isotopically light Mo to sediments via a particulate Fe–Mn oxyhydroxide shuttle. A compilation of Mo isotope data from euxinic ORM suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late Neoproterozoic and early Paleozoic time. Hence, Member IV does not capture irreversible deep ocean oxygenation. Instead, complex ocean redox variations likely marked the transition from O 2 -deficient Proterozoic oceans to widely oxygenated later Phanerozoic oceans.

The timing of the emergence of life remains one of the principal unresolved questions in the Earth sciences. Putative relicts of microorganisms in the Eoarchean ( ca. 3.6–3.85 Ga) high-grade metamorphic terranes do not preserve morphological evidence for early life, but some relicts can be identified by their geochemical signatures created by metabolic processes. Among the oldest rocks of sedimentary origin ( ca . 3.8 Ga) occur in the Isua supracrustal belt (ISB), southern West Greenland; these have undergone metamorphism up to the amphibolite facies. Despite intense metamorphism, the carbon isotope compositions of graphite clots from the Isua metasedimentary rocks suggest biological carbon fixation and provide the oldest evidence for this biological process. Microbial dissimilatory iron reduction (DIR) is considered to be an early form of metabolism. The microbial DIR produced Fe 2 + aq with a lower δ 56 Fe value from a precursor Fe 3 + -bearing iron mineral. However, δ 56 Fe values lower than − 1‰ are not found in sedimentary rocks prior to about 2.9 Ga. Here, we report in-situ iron isotope analysis of pyrites in sedimentary rocks from the ISB, using a near infrared-femtosecond-laser ablation-multicollector-ICP-MS (NIR-fs-LA-MC-ICP-MS). A large variation of δ 56 Fe values from − 2.41 to + 2.35‰, was documented from 190 points within pyrite grains from 11 rock specimens, including those interpreted to be banded iron-formations (BIFs), chert, amphibole-rich chert, quartz-rich clastic sedimentary rocks, mafic clastic sedimentary rocks, carbonate rocks and conglomerates. We found that the distribution of δ 56 Fe values depends on the lithology, whereas there is no correlation between their δ 56 Fe values and the metamorphic grade. The δ 56 Fe values of pyrites in BIFs range from + 0.25 to + 2.35‰, indicating partial oxidation in the deep ocean. Especially, the high δ 56 Fe values, up to + 2.35‰, suggest that the BIF was formed through interaction of ferruginous seawater with a highly alkaline hydrothermal fluid under anoxic conditions. Pyrite grains in a conglomerate, carbonate rocks, mafic clastic sedimentary rocks, and amphibole-rich cherts show negative δ 56 Fe values around − 1.5‰, down to − 2.41‰, pointing to microbial DIR in the Eoarchean shallow sea. In addition, the relatively low δ 56 Fe values of pyrites in the shallow water sediments suggest anoxic, anoxygenic photoautotrophic iron oxidation in the photic zone.

金沢大学理工研究域地球社会基盤学系, Granitoids are widespread in Precambrian terranes as well as the Phanerozoic orogenic belts, but they have garnered little attention in paleomagnetic studies, because granitoids often contain abundant coarse-grained, magnetically unstable oxides. In this study, the first example of tiny, needle-shaped, exsolved oxides in plagioclase in a Paleoarchean granitoid is reported. The magnetic properties of single plagioclase crystals with the exsolved oxide inclusions have been studied to determine their paleomagnetic recording fidelity. Demagnetization experiments and hysteresis parameters indicate that the oxide inclusions are near stoichiometric magnetite and magnetically very stable. First-order reversal curve (FORC) diagrams reveal negligible magnetostatic interactions. Minimal interactions are also reflected by very efficient acquisition of anhysteretic remanent magnetization. Single plagioclase crystals exhibit strong magnetic remanence anisotropies, which require corrections to their paleodirectional and paleointensity data. Nonetheless, quantitative consideration of anisotropy tensors of the single plagioclase crystals indicates that the bias can be mitigated by properly averaging data from a few tens of single crystals. From the nonlinear thermoremanence acquisition of the plagioclase crystals, we estimate that the plagioclase crystals can reconstruct paleointensity up to 50 μT. Local metamorphic condition suggests that those magnetite may carry remanence of ∼3.2 to 3.3 Ga. We suggest that exsolved magnetite in granitoids is potentially a suitable target for the study of the early history of the geomagnetic field, and prompt detailed microscopic investigations as well as paleomagnetic tests to constrain the age of remanence. © 2014. American Geophysical Union. All Rights Reserved.

The Neoproterozoic Era records several important events in Earth history. The associations between BIF deposition, Snowball Earth events and the redox state of seawater are the key to explain the re-appearance of banded iron formations (BIF) during the Neoproterozoic. Unraveling ancient iron cycles provides important information about the linkage between the precipitation of BIF and the redox condition in the ocean, but current iron isotopic data are limited to sediments deposited only during the Sturtian glaciations and Ediacaran. We conducted a detailed geological survey of the Tonian to Ediacaran sedimentary succession in Nordaustlandet island, Svalbard. Our chemostratigraphies of δ 13 C carb from pre-Sturtian to post-Marinoan sedimentary successions in the Polarisbreen Group are consistent with those in coeval sediments. We first analyzed iron isotope ratios (δ 56/54 Fe) of individual pyrite grains with diverse shapes in carbonates, black shales, quartz arenites and diamictites in order to constrain the redox condition in seawater. We found large variations in iron isotope ratios; from ca. −2 to ca. +4‰. Positive δ 56/54 Fe values, over +1.0‰, are only preserved in euhedral and aggregated pyrite grains in black shales of the Backlundtoppen Formation and the MacDonaldryggen Member of the Elbobreen Formation. A partial oxidation of ferrous iron in seawater is necessary to explain such high δ 56/54 Fe values, which means that deep seawater was ferruginous (ferrous, iron-rich) before and after the Sturtian glaciation. This stands in opposition to the traditional idea that a glacial cover on an ocean is necessary for the accumulation of ferrous iron in Neoproterozoic seawater. This study presents the first evidence from iron isotopes that supports a deep ferruginous ocean around the Sturtian glaciation. If the deep ocean was intrinsically iron-rich, it is likely that Neoproterozoic BIFs formed by thermohaline circulation during the glaciation and by massive oxidation due to the expansion of oxic oceans after the glaciation.

It was previously revealed that the total CO2 concentration in seawater decreased during the Late Archean. In this paper, to assess the secular change of total CO2 concentration in seawater, we focused on the Paleoproterozoic era when the Earth experienced its first recorded global glaciation. The 2.4 Ga Ongeluk Formation outcrops in the Kaapvaal Craton, South Africa. The formation consists mainly of submarine volcanic rocks that have erupted during the global glaciation. The undeformed lavas are mostly carbonate-free but contain rare disseminated calcites. The carbon isotope ratio of the disseminated calcite (δ13Ccc vs. VPDB) ranges from − 31.9 to − 13.2 ‰. The relatively low δ13Ccc values clearly indicate that the carbonation was partially contributed by 13C-depleted CO2 derived from decomposition of organic matter beneath the seafloor. The absence of δ13Ccc higher than − 13.2‰ is consistent with the exceptionally 13C-depleted CO2 in the Ongeluk seawater during glaciation. The results suggest that carbonation occurred during subseafloor hydrothermal circulation just after the eruption of the lavas. Previously, it was reported that the carbonate content in the uppermost subseafloor crust decreased from 3.2 to 2.6 Ga, indicating a decrease in total CO2 concentration in seawater during that time. However, the average CO2 (as carbonate) content in the Ongeluk lavas (

The authors provide evidence for the existence of life on Earth in the earliest known sedimentary rocks and suggest that the presence of organic carbon, and low stable-isotope values of graphite from sedimentary rocks in Labrador pushes back the existence of organic life to beyond 3.95 billion years. The beginning of organic life on Earth is being pushed back by evidence from the earliest known sedimentary rocks. Tsuyoshi Komiya and colleagues argue that the presence of organic carbon and stable-isotope excursions in graphite from sedimentary rocks in Labrador, Canada, pushes back the existence of organic life to more than 3.95 billion years ago. Together with recent work showing evidence for a diverse range of living organisms around 3.7 billion years ago, including stromatolites living in sunlit surface waters and bacteria living in deep-sea hydrothermal vents, the work shows that life has been around almost as long as there has been a planet that it can call home. The vestiges of life in Eoarchean rocks have the potential to elucidate the origin of life. However, gathering evidence from many terrains is not always possible1,2,3, and biogenic graphite has thus far been found only in the 3.7–3.8 Ga (gigayears ago) Isua supracrustal belt4,5,6,7. Here we present the total organic carbon contents and carbon isotope values of graphite (δ13Corg) and carbonate (δ13Ccarb) in the oldest metasedimentary rocks from northern Labrador8,9. Some pelitic rocks have low δ13Corg values of −28.2, comparable to the lowest value in younger rocks. The consistency between crystallization temperatures of the graphite and metamorphic temperature of the host rocks establishes that the graphite does not originate from later contamination. A clear correlation between the δ13Corg values and metamorphic grade indicates that variations in the δ13Corg values are due to metamorphism, and that the pre-metamorphic value was lower than the minimum value. We concluded that the large fractionation between the δ13Ccarb and δ13Corg values, up to 25‰, indicates the oldest evidence of organisms greater than 3.95 Ga. The discovery of the biogenic graphite enables geochemical study of the biogenic materials themselves, and will provide insight into early life not only on Earth but also on other planets.

This report describes in situ ion microprobe U–Pb dating of a protoconodont, an early Cambrian phosphate microfossil, using laterally high-resolution secondary ion mass spectrometry (NanoSIMS). On a single fragment of a fossil (approximately 850 μm × 250 μm) derived from a sedimentary layer in the Meishucunian Yuhucun Formation, Yunnan Province, southern China, 23 spots provide a 238U/206Pb isochron age of 547 ± 43 Ma (2σ, MSWD = 1.9), which is consistent with the depositional age, 536.5 ± 2.5 Ma estimated using zircon U–Pb dating of interbedded tuffs. However, five spots on a small region (approximately 250 μm × 100 μm) in the same protoconodont yield an isochron age of 417 ± 74 Ma (2σ, MSWD = 0.31), apparently younger than the formation age. The younger age might be attributable to a later hydrothermal event, perhaps associated with Caledonian orogenic activity recorded in younger zircon with an age of 420–440 Ma. We also measured 87Sr/86Sr ratios of the protoconodont by NanoSIMS. In the older domain, 19 spots give the 87Sr/86Sr ratio of 0.71032 ± 0.00023 (2σ), although seven spots on the younger region provide the ratio of 0.70862 ± 0.00045; this is significantly less radiogenic than the older domain. This is the first report of U–Pb age and Sr isotope heterogeneity within a single fragment of micro-fossil (215).

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ15NTN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ15NTN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ15N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the 15N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ13Ccarb and δ15NTN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO2 with recycled organic nitrogen. After the Shuram event, the δ15N value continued to decrease despite that δ13Ccarb rose back to + 4‰. The continued δ15N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ13Ccarb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ13Ccarb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.

The Ediacaran and Cambrian periods were one of the most important periods for the evolution of life. The biodiversity drastically expanded in the period. However, the origins are still ambiguous because surface environmental changes through the time have not been well understood yet. We conducted in-situ analyses of the phosphorus contents of carbonate minerals with a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) to estimate the phosphorus contents of seawater from the Ediacaran to the early Cambrian. Carbonate rocks contain not only the carbonate minerals but also detrital and authigenic materials such as silicate and phosphate minerals. Therefore, the whole rock compositions of carbonate rocks are not directly related with seawater composition. To avoid the influence of the involvement of the phosphate minerals, we performed the microscopic observation, elemental mapping of Si, Ca, Mg, Fe, and P contents with an electron probe microanalyzer (EPMA), and investigation of time profiles of signal intensities of Ca, Sr, Mn, P, La and Ba with the LA-ICP-MS. Especially, samples with low Mn/Sr ratios and primary textures such as oolites are suitable to estimate the primary phosphorus contents of the carbonates. The chemostratigraphy of the phosphorus contents of carbonates from the drill core and outcrop samples displays that the phosphorus contents decrease from ca. 400 ppm in the Ediacaran through ca. 200 ppm around the terminal Ediacaran and the beginning of the Cambrian to ca. 50 ppm in the early Cambrian. Previous works on 87Sr/86Sr chemostratigraphy from the Ediacaran to the Cambrian sections suggested relatively high continental influx in the middle Ediacaran, and around the Precambrian–Cambrian (PC/C) boundary. The high phosphorus content in the Ediacaran was possibly due to the high continental flux. On the other hand, previous works on chemostratigraphy of carbon isotope values of carbonate carbon from the Ediacaran to the Cambrian sections showed some large negative anomalies in the Ediacaran and around the Precambrian–Cambrian (PC/C) boundary, and suggested that the negative anomalies were caused by remineralization and respiration of dissolved organic matter. The degradation of the organic matter also accounts for the high phosphorus contents in the Ediacaran. The high phosphorus content of seawater favors enhancement of primary productivity and formation of phosphorites. The high phosphorus contents in the seawater possibly led to the emergence of the large, and motile organism through the enhancement of primary productivity and the consequent increase of oxygen content of the seawater.

Phosphatized microfossils from ca. 580 Ma from the Doushantuo Formation in the Weng'an region of South China were analyzed by Fourier transform infrared (FTIR) microspectroscopy for their chemical characterization. Two morpho-types of phosphatized embryo-like fossils ( Megasphaera and Megaclonophycus ) were analyzed, together with algal fossils. Transmission IR spectra of the microfossils have absorption bands of around 2960 cm − 1 and 2925 cm − 1 , indicating the presence of aliphatic hydrocarbon (anti-symmetric aliphatic CH 3 and aliphatic CH 2 ), and have an additional band of around 1595 cm − 1 , probably derived from aromatic moieties (aromatic C C). In addition, IR microscopic mapping shows that aliphatic hydrocarbon and aromatics are distributed inside the embryo-like fossils. The embryo-like fossils appear to show three types of CH 3 /CH 2 peak height ratios (R 3/2 ) and aromatic C C/CH 2 peak height ratios (R C C/2 values): (1) high-R 3/2 /low-R C C/2 type (R 3/2 = ~ 0.2–1.0 and R C C/2 ~ 0–2), (2) low-R 3/2 /medium-R C C/2 type (R 3/2 = ~ 0.2–0.6 and R C C/2 = ~ 1–4); and (3) low-R 3/2 /high-R C C/2 type (R 3/2 = ~ 0.2–0.6 and R C C/2 ~ 1–8). All three types are contained in both Megasphaera and Megaclonophycus . Raman spectra for the carbonaceous matter within the rock sample show a similar degree of thermal alteration, indicating that the organics were embedded in situ prior to thermal maturation. The IR spectroscopic differences might reflect differences in original organic compositions of microorganisms, and/or immediate post-mortem alteration. This suggests that the origins of phosphatized embryo-like fossils are more diverse than was previously recognized on the basis of their morphology. A comparison of R 3/2 and R C C/2 values in the embryo-like fossils with those of the algal fossils and the extant microorganisms indicates the possible interpretation that some of the embryo-like fossils belong to animal embryo, others are algae, but none of them originate from bacteria.

The bivalved bradoriid arthropod Kunmingella douvillei ( Mansuy, 1912 ) is the most common species in the Lower Cambrian Chengjiang Lagerstatte. Its soft anatomy has been reported based on well-preserved specimens. However, as with other Cambrian arthropods, its reproductive behavior is poorly documented. Rare specimens of K. douvillei preserved with eggs have been reported. Our new collections confirm that the eggs were directly attached to the last three pairs of biramous appendages and verify the head–trunk boundary suggested by previous work. The brooding behavior of K. douvillei was most probably related to its small body size, as in living crustaceans. The K. douvillei female could carry 50–80 eggs ranging from 150–180 μm in diameter, possibly indicating a K-reproductive strategy; its ontogenetic and reproductive mode might have been an adaptation in response to increasing predatory pressure across the Ediacaran–Cambrian boundary. All of the three main directions of development in the life history of living marine invertebrates, namely planktotrophic larvae, lecithotrophic larvae, and brood care, most likely evolved by Stage 3 of the Cambrian.

The Ediacaran–Cambrian was one of the most important periods for the evolution of life. Recent studies have provided detailed chemostratigraphies that decipher the linkages between ambient surface environmental changes and biological evolution. The occurrence of skeletal fossils in Ediacaran rocks suggests that the possible onset of Ca-biomineralization started in the latest Neoproterozoic. Molecular clocks also predict the emergence of animals containing Ca-carbonate spicules in the Neoproterozoic. Therefore, it is important to estimate the transition of the Ca cycle in seawater. Ancient Ca cycles in the oceans are estimated from the calcium isotopic compositions of carbonate rocks. However, the lack of continuous Ca isotopic data in the Ediacaran leaves the Ca cycle unresolved. The almost continuously exposed, Ediacaran and Cambrian strata in South China mainly comprise carbonate rocks with subordinate black shales and sandstones, which contain many fossils, suitable for the study of environmental and biological changes. We conducted drilling from the Liantuo, via the Nantuo, Doushantuo, Dengying and Yanjiahe to the Shuijingtuo formation at four sites in the Three Gorges area in order to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed 44 Ca/ 42 Ca ratios in carbonate rocks with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) screened for diagenetic alteration. The resultant δ 44/42 Ca ratios exhibit a smooth curve. The values of δ 44/42 Ca are anomalously high relative to those in the Phanerozoic, and they gradually decrease towards the end of the Ediacaran. Our new Ca isotope chemostratigraphy suggests that a different Ca cycle had existed during the Ediacaran. The long-term, high δ 44/42 Ca is not simply explicable by changes in temperature, differences in carbonate mineralogy, or changes in the input/output fluxes of Ca to the ocean. We propose three possible explanations for the observed high δ 44/42 Ca ratios in the Ediacaran: high δ 44/42 Ca ratios of Ca inputs, potential undiscovered sinks of Ca with low δ 44/42 Ca values, and negligible isotope fractionation between carbonate and seawater; we consider that one or all of these contributed to the high δ 44/42 Ca ratios. Of these, we prefer the small isotope fractionation, which implies that the Ca concentration in seawater was initially low in the early Ediacaran and increased throughout that period.

Environmental investigation of the Early Cambrian is assessed through molecular fossils based from three core samples drilled in the Three Gorges area, South China. The core samples record environmental information dating from the earliest part of the Early Cambrian to nearly the end of the Early Cambrian, making this investigation unique from previous investigations because a more far-reaching temporal record is assessed. This record includes unusually high abundance of longer chain n-alkanes (LCA) around n C 27 , having been recognized in the earliest Cambrian strata. Based on no odd–even preference of the LCA and comparisons to hydrocarbons in cultured cells of microorganisms, the LCA may be derived from hydrocarbons of sulfate reducing bacteria. On the other hand, a phototrophic origin of the SCA is supported by a clear positive correlation with pristane. The relative abundance of LCA to SCA increased in the earliest Cambrian, suggesting predominance of sulfate reducers against phototrophs. This LCA abundance with simultaneous decrease of pristane/phytane may indicate a euxinic condition, where sulfate reducers remineralize organic carbon in the water column. This is consistent with the concomitant decrease of the δ 13 C carb value probably due to a massive reoxidation of organic carbon. The inferred reducing condition is further supported by the enhanced appearance of squalane that could be derived from an Archeal lipid. Our results suggest the euxinia of the Yangtze platform in the earliest Cambrian that may relate to the emergence of the large nektonic animals which require sufficient level of free oxygen.

A remarkable increase of the animal genera and a subsequent mass extinction in the late Early Cambrian are well known as the “Cambrian explosion” and the “Botomian–Toyonian crisis.” A composite global curve of the carbon isotope ratios for inorganic carbon (δ13Ccarb) shows multiple fluctuations during the evolution events, and it indicates significant changes of the oceanic carbon cycle at that time. This study reveals a new continuous isotopic chemostratigraphy for inorganic carbon (δ13Ccarb) from the bottom of the Shipai to the base of the Shilongdong formations in Three Gorges area, South China. This section covers the Canglangpuian to the Longwangmiaoian stages in the Lower Cambrian. The δ13Ccarb variation exhibits three negative excursions: a remarkably negative excursion down to ca. − 12‰ in the middle Canglangpuian stage, a negative excursion to ca. − 1.0‰ in the upper Canglangpuian stage, and a negative excursion to ca. − 1.0‰ in the Longwangmiaoian stage, respectively. The largest negative δ13Ccarb excursion and a positive excursion before the excursion are definitely consistent with the δ13Ccarb negative shift (AECE) during the mass extinction and the δ13Ccarb positive values (MICE) during the increase of animal genera, respectively. However, the minimum values of the negative shifts among South China, Siberia, and Canada sections are different from each other. The positive δ13Ccarb excursion at the bottom of the Canglangpuian stage indicates that primary productivities and organic carbon burial were enhanced. A sea level rise in the Qiongzhusian to bottom of the Canglangpuian stages in South China corresponds to the Sinsk transgression event in Siberia and Canada. A eutrophication due to higher continental weathering during the transgression after the long-term retrogression enhanced the high primary production and consequently promoted the significant increase of animal diversity. On the other hand, deposition of laminated black shales without bioturbation signatures and a decline of trilobite diversity are observed during the negative δ13Ccarb excursion in the Canglangpuian stage, indicating that the shallow water environment became anoxic at that time. The negative δ13Ccarb shift indicates an influx of abundant 12CO2 due to oxidation of organic carbons in seawater. The difference of the minimum values among sections implies the local difference in size of the organic carbon reservoirs and extent of the degradation of the carbons. The largest δ13C anomaly in South China suggests the presence of the largest OCPs due to higher activity of primary production and high degree of oxidation of the OCPs because of higher activity of animals. The coincidence of the timing of the negative δ13C excursions in the Canglangpuian stage among the sections indicates a global event, and suggests that the onset was caused by increase of oxygen contents of seawater and atmosphere. Abundant oxygen yielded by the increased primary productivity in the Atdabanian and the Qiongzhusian stages caused onset of the oxidation of OCP, and possibly led to the shallow water anoxia and the mass extinction of benthic animals in the Botomian and the Canglangpuian stage.

Before continents attained a critical aerial dimension on the early Earth, hydrothermal carbonation of subseafloor crust is considered to have played the dominant role in fixing CO 2 from the CO 2 -rich ocean. However, it is uncertain how and when the seawater CO 2 level decreased and the strong carbonation of oceanic crust ceased. Here we report the depth profiles of the volume concentration and the carbon isotopes of calcites in the Late Archean/Paleoproterozoic volcanic rocks (Fortescue and Hamersley groups), exposed in the southwestern Pilbara Craton, Western Australia. The depth profiles indicate that 2.6 Ga seafloor hydrothermal carbonation is well preserved in the study area and that the CO 2 content of subseafloor crust per seafloor unit area is estimated to be clearly lower than those in the Early and Middle Archean and similar to the Phanerozoic equivalents. This suggests that the CO 2 concentration in seawater decreased from the Middle Archean to the Late Archean. This period broadly corresponds to the time of the first appearance of supercontinent on Earth. The amalgamation of continents has the potential to decrease seawater CO 2 concentration due to the removal of platform carbonate to continental interior. Subsequent fragmentation of supercontinent likely cause the carbonate deposition around newly created continental shelves. It is therefore implied that seawater CO 2 concentration in the early Earth was lowered by not only the hydrothermal carbonation of subseafloor crust but also through the formation and breakup of supercontinent in the Late Archean.

[1] Analysis of Hadean and Archean rocks for 16O-17O-18O isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2 Ga. The homogenization of oxygen isotopes required to produce such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact. But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle.

Eclogites and associated high-pressure (HP) rocks in collisional and accretionary orogenic belts preserve a record of subduction and exhumation, and provide a key constraint on the tectonic evolution of the continents. Most eclogites that formed at high pressures but low temperatures at > 10-11 kbar and 450-650 degrees C can be interpreted as a result of subduction of cold oceanic lithosphere. A new class of high-temperature (HT) eclogites that formed above 900 degrees C and at 14 to 30 kbar occurs in the deep continental crust, but their geodynamic significance and processes of formation are poorly understood. Here we show that Neoarchaean mafic-ultramafic complexes in the central granulite facies region of the Lewisian in NW Scotland contain HP/HT garnet-bearing granulites (retrogressed eclogites), gabbros, Iherzolites, and websterites, and that the HP granulites have garnets that contain inclusions of omphacite. From thermodynamic modeling and compositional isopleths we calculate that peak eclogite-facies metamorphism took place at 24-22 kbar and 1060-1040 degrees C. The geochemical signature of one (G-21) of the samples shows a strong depletion of Eu indicating magma fractionation at a crustal level. The Sm-Nd isochron ages of HP phases record different cooling ages of ca. 2480 and 2330 Ma. We suggest that the layered mafic-ultramafic complexes, which may have formed in an oceanic environment, were subducted to eclogite depths, and exhumed as HP garnet-bearing orogenic peridotites. The layered complexes were engulfed by widespread orthogneisses of tonalite-trondhjemite-granodiorite (TTG) composition with granulite facies assemblages. We propose two possible tectonic models: (1) the fact that the relicts of eclogitic complexes are so widespread in the Scourian can be taken as evidence that a >90 km x 40 km-size slab of continental crust containing mafic-ultramafic complexes was subducted to at least 70 km depth in the late Archaean. During exhumation the gneiss protoliths were retrogressed to granulite facies assemblages, but the mafic-ultramafic rocks resisted retrogression. (2) The layered complexes of mafic and ultramafic rocks were subducted to eclogite-facies depths and during exhumation under crustal conditions they were intruded by the orthogneiss protoliths (TTG) that were metamorphosed in the granulite facies. Apart from poorly defined UHP metamorphic rocks in Norway, the retrogressed eclogites in the central granulite/retrogressed eclogite facies Lewisian region, NW Scotland have the highest crustal pressures so far reported for Archaean rocks, and demonstrate that lithospheric subduction was transporting crustal rocks to HP depths in the Neoarchaean. (C) 2012 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

We have measured the U–Pb age of zircon grains separated from podiform chromitites from the Luobusa ophiolite, Southern Tibet, using laser ablation microprobe – inductively coupled plasma mass spectrometer (LA-IC-PMS), to determine the age relationship between the podiform chromitites and the host mantle peridotite. Spot analyses with LA-IC-PMS, assisted by cathodoluminescence images gave a wide age range, from the Cretaceous to the Late Archean (ca 100–2700 Ma). The minimum ages of ca 100 Ma, plotted on the concordia curve, were slightly lower than the metasomatic (magmatic) event in the supra-subduction zone (120 ± 10 Ma), suggesting that the zircons suffered some Pb loss. However, most of the ages found are much older than those of the chromitite and ophiolite formation. Laser Raman spectroscopy analyses revealed that the zircons recovered from the chromitites contain crustal mineral inclusions, such as quartz and K-feldspar, but lack mantle minerals (e.g., olivine, pyroxene, and chromite), suggesting that they had a crustal origin. The results indicate that crustal zircons in chromitites had a xenocrystic origin and resided in the mantle peridotite for a long period before being entrained into the chromitite during its formation. This indicates that the mantle peridotite under the Neo-Tethys Ocean was affected by the crustal material contamination. Our results are consistent with previous reports that mid-oceanic ridge basalts in the Indian Ocean have the isotopic signature of crustal material contamination. From these results, and previous isotopic studies on Gondwana geology, we conclude that ancient zircons from podiform chromitites could provide evidence of crustal material being recycled through the upper mantle.

Multicellular animals first appeared on the earth during the Ediacaran period. However, the relationship between the abrupt biological evolution and environmental changes is still ambiguous. In order to examine seawater temperature and the carbon cycle through the Ediacaran, we analyzed the carbon and oxygen isotope compositions of carbonate rocks from drill cores from the Three Gorges area, South China. Importantly, the core samples include the Nantuo tillite, corresponding to the Marinoan glaciation, through the Doushantuo to the lower Dengying Fms. in ascending order. The δ13C profile displays five positive and five negative anomalies (PI-1 to 5 and NI-1 to 5), and the oxygen isotopes display very high absolute values around 0‰ with the highest at + 1.83‰. The combined δ18O and δ13C chemostratigraphies display both positive and negative correlations between the δ18O and δ13C values. The occurrence of the negative correlations supports the preservation of primary δ18O and δ13C values. The sample NI-4 has a negative correlation of the δ18O and δ13C excursions. The correlation supports a primary signature for both δ18O and δ13C variations. The positive δ18O excursion, accompanied by evidence of a eustatic sea-level fall, provides direct evidence for global cooling in the mid-Ediacaran; the 580 Ma Gaskiers Glaciation is a potential candidate for this global cooling event. The negative δ13C excursion was possibly caused by an increase in remineralization of dissolved organic carbon (DOC) due to enhanced continental weathering during the glaciation. Sample NI-5 is characterized by very low δ13C values, down to − 10‰, corresponding to the Shuram-Wonoka-Pertatataka Excursion. The cause of the δ13C negative excursion is still not clear. However, a ubiquitous occurrence in excursions worldwide, and the lower δ13C values in deeper sections favor the enhancement of remineralization and respiration rather than secondary alteration, a restricted sea environment and lithification in coastal areas.