Changes in orogenic style and surface environment recorded in Paleoproterozoic foreland successions.

The Earth's interior and surficial systems underwent dramatic changes during the Paleoproterozoic, but the interaction between them remains poorly understood. Rocks deposited in orogenic foreland basins retain a record of the near surface to deep crustal processes that operate during subduction to collision and provide information on the interaction between plate tectonics and surface responses through time. Here, we document the depositional-to-deformational life cycle of a Paleoproterozoic foreland succession from the North China Craton. The succession was deposited in a foreland basin following ca. 2.50-2.47 Ga Altaid-style arc-microcontinent collision, and then converted to a fold-and-thrust belt at ca. 2.0-1.8 Ga due to Himalayan-style continent-continent collision. These two periods correspond to the assembly of supercratons in the late Archean and of the Paleoproterozoic supercontinent Columbia, respectively, which suggests that similar basins may have been common at the periphery of other cratons. The multiple stages of orogenesis and accompanying tectonic denudation and silicate weathering, as recorded by orogenic foreland basins, likely contributed to substantial changes in the hydrosphere, atmosphere, and biosphere known to have occurred during the Paleoproterozoic.

Earth's early continental crust formed from wet and oxidizing arc magmas.

Formation of continental crust has shaped the surface and interior of our planet and generated the land and mineral resources on which we rely. However, how the early continental crust of Earth formed is still debated1-7. Modern continental crust is largely formed from wet and oxidizing arc magmas at subduction zones, in which oceanic lithosphere and water recycle into the mantle8-10. The magmatic H2O content and redox state of ancient rocks that constitute the early continental crust, however, are difficult to quantify owing to ubiquitous metamorphism. Here we combine two zircon oxybarometers11,12 to simultaneously determine magmatic oxygen fugacity (fO2) and H2O content of Archaean (4.0-2.5 billion years ago) granitoids that dominate the early continental crust. We show that most Archaean granitoid magmas were ≥1 log unit more oxidizing than Archaean ambient mantle-derived magmas13,14 and had high magmatic H2O contents (6-10 wt%) and high H2O/Ce ratios (>1,000), similar to modern arc magmas. We find that magmatic fO2, H2O contents and H2O/Ce ratios of Archaean granitoids positively correlate with depth of magma formation, requiring transport of large amounts of H2O to the lower crust and mantle. These observations can be readily explained by subduction but are difficult to reconcile with non-subduction models of crustal formation3-7. We note an increase in magmatic fO2 and H2O content between 4.0 and 3.6 billion years ago, probably indicating the onset of subduction during this period.

High-precision zinc isotopic characterization of twenty soil reference materials from China determined by MC-ICP-MS.

Zinc isotopic ratios serve as powerful tools for tracing biochemical cycling of metals at Earth's surface, including the distribution, transportation, and enrichment of zinc (Zn) in soil. To conduct such studies and enable inter-laboratory comparisons, high-precision Zn isotopic measurements require the use of soil reference materials (RMs). However, there have been limited reports on the high-precision Zn isotope ratios of soil RMs thus far. In this study, we have developed a two-step Zn chemical separation protocol utilizing Bio-Rad AG MP-1M resin columns. This method has demonstrated excellent reproducibility for measuring the external δ66Zn values (relative to JMC-Lyon) of standard soil reference materials over an extended time period, with a better than 0.06‰ (2SD) precision. Remarkably, this study is the first to report the Zn isotopic compositions of 20 soil reference materials from various soil types in China. With the exception of one sample obtained from a mining area, the Zn isotopic compositions of all the analyzed soil reference materials exhibit remarkable similarity, with an average δ66Zn value of 0.31 ± 0.12‰, which aligns closely with the values observed in igneous rocks. The exceptional sample, with a higher δ66Zn value of 0.61 ± 0.02‰, indicates potential contamination during mining activities.

Metallic lead (Pb) nanospheres discovered in Hadean and Eoarchean zircon crystals at Jack Hills.

Here, we report small randomly-distributed crystalline lead (Pb) nanospheres occurring in detrital zircon grains obtained from a weakly metamorphosed Archean conglomerate at Jack Hills, Western Australia, making this the third known global example of this phenomenon. They form in zircon crystals ranging from Hadean (> 4 billion years-Ga) to Eoarchean (> 3.6 Ga) in age, but are absent from Paleoarchean (~ 3.4 Ga) crystals. Unlike previous discoveries of nanospheres in zircon from Precambrian gneisses in Antarctica and India, detrital zircon from Jack Hills shows no evidence of ever undergoing ultra-high temperature (UHT) metamorphism, either before or after deposition, therefore implying that nanospheres can form at temperatures lower than ca. 900 °C. The nanospheres are composed of radiogenic Pb released by the breakdown of uranium (U) and thorium (Th) and are present in zircon irrespective of its U, Th and water contents, its oxygen isotopic composition, and the degree of discordance due to Pb loss or gain. The nanospheres pre-date annealed cracks in the crystals, showing that, once formed, they effectively 'freeze' radiogenic Pb in the zircon structure, precluding any further interaction during subsequent geological processes. Both Pb nanoclusters and nanospheres are now reported from Jack Hills, and it appears likely the former is a precursor stage in the formation of the latter. Although the precise mechanism for this transition remains unresolved, a later thermal event is required, but this likely did not reach UHT conditions at Jack Hills.

Coexisting divergent and convergent plate boundary assemblages indicate plate tectonics in the Neoarchean.

The coexistence of divergent (spreading ridge) and convergent (subduction zone) plate boundaries at which lithosphere is respectively generated and destroyed is the hallmark of plate tectonics. Here, we document temporally- and spatially-associated Neoarchean (2.55-2.51 Ga) rock assemblages with mid-ocean ridge and supra-subduction-zone origins from the Angou Complex, southern North China Craton. These assemblages record seafloor spreading and contemporaneous subduction initiation and mature arc magmatism, respectively, analogous to modern divergent and convergent plate boundary processes. Our results provide direct evidence for lateral plate motions in the late Neoarchean, and arguably the operation of plate tectonics, albeit with warmer than average Phanerozoic subduction geotherms. Further, we surmise that plate tectonic processes played an important role in shaping Earth's surficial environments during the Neoarchean and Paleoproterozoic.

Determination of 87Rb/86Sr and 87Sr/86Sr ratios and Rb-Sr contents on the same filament loading for geological samples by isotope dilution thermal ionization mass spectrometry.

Isotope dilution thermal ionization mass spectrometry (ID-TIMS) is considered the "gold standard" for obtaining precise 87Rb/86Sr and 87Sr/86Sr isotope ratios and accurate elemental concentrations of Rb-Sr. However, the classical ID-TIMS technique is laborious and time-consuming because the purified Rb and Sr fractions must be individually loaded onto different independent filaments due to severe 87Rb isobaric interference on 87Sr. To overcome this issue, we developed a new method whereby Rb and Sr were sequentially measured by TIMS on the same filament, without venting, to obtain both ratios of 87Rb/86Sr and 87Sr/86Sr and concentrations of Rb and Sr. Results obtained from six silicate powders of certified reference materials are in good agreement with recommended values within ±0.002% for the 87Sr/86Sr ratio, ±2% for the 87Rb/86Sr ratio and the Rb and Sr elemental contents. The only exception is JG-1a, with slightly higher 87Rb/86Sr and slightly lower 87Sr/86Sr. This new method improved the analytical efficiency and sample throughput without compromising the analytical accuracy and precision. The filament consumption is reduced by 50% compared with conventional methods and therefore significantly reduces operation costs.

Pb nanospheres in ancient zircon yield model ages for zircon formation and Pb mobilization.

Nanospheres of lead (Pb) have recently been identified in zircon (ZrSiO4) with the potential to compromise the veracity of U-Pb age determinations. The key assumption that the determined age is robust against the effects of Pb mobility, as long as Pb is not lost from the zircon during subsequent geological events, is now in question. To determine the effect of nanosphere formation on age determination, and whether analysis of nanospheres can yield additional information about the timing of both zircon growth and nanosphere formation, zircons from the Napier Complex in Enderby Land, East Antarctica, were investigated by high-spatial resolution NanoSIMS (Secondary Ion Mass Spectrometry) mapping. Conventional SIMS analyses with >µm resolution potentially mixes Pb from multiple nanospheres with the zircon host, yielding variable average values and therefore unreliable ages. NanoSIMS analyses were obtained of 207Pb/206Pb in nanospheres a few nanometres in diameter that were resolved from 207Pb/206Pb measurements in the zircon host. We demonstrate that analysis for 207Pb/206Pb in multiple individual Pb nanospheres, along with separate analysis of 207Pb/206Pb in the zircon host, can not only accurately yield the age of zircon crystallization, but also the time of nanosphere formation resulting from Pb mobilization during metamorphism. Model ages for both events can be derived that are correlated due to the limited range of possible solutions that can be satisfied by the measured 207Pb/206Pb ratios of nanospheres and zircon host. For the Napier Complex zircons, this yields a model age of ca 3110 Ma for zircon formation and a late Archean model age of 2610 Ma for the metamorphism that produced the nanospheres. The Nanosphere Model Age (NMA) method constrains both the crystallization age and age of the metamorphism to ~±135 Ma, a significant improvement on errors derived from counting statistics.

Direct Rubidium-Strontium Dating of Hydrocarbon Charge Using Small Authigenic Illitic Clay Aliquots from the Silurian Bituminous Sandstone in the Tarim Basin, NW China.

Illitic clay is ubiquitous in clastic hydrocarbon reservoirs, and the host for several radiometric isotopes such as the potassium-argon (K-Ar) and rubidium-strontium (Rb-Sr) systems. This study applied the isotope-dilution thermal ionization mass spectrometry technique for small samples (3-4 mg) to conduct illite Rb-Sr isotope dating of five illitic clay samples from the Silurian bituminous sandstone (SBS) intersected by five drillholes in the Tarim Basin, NW China. The 87Rb/86Sr ratio of clays is fractionated mainly by the addition of Rb during the illitization of mixed-layer illite/smectite (I/S), which is the dominant clay species in the Tarim Basin samples. The subsample-scale Rb/Sr isotope values suggest that each subsample may contain I/S particles of slightly variable degrees of illitization. Three of the analyzed samples (H6, KQ1 and TZ67) generated Rb-Sr isochron ages of 141 ± 61 Ma, 332 ± 32 Ma and 235 ± 8 Ma (errors quoted at 2σ), respectively. These results are similar to the corresponding K-Ar ages (125 Ma, 389 Ma and 234 Ma). The isotopic ages are consistent with the timing of hydrocarbon charge which varies in different drillholes as constrained by basin modelling, indicating that a closed-system behavior is attained by the hydrocarbon charge that inhibits the illitization of I/S. The Rb-Sr isotope analyses of the other two samples (YM35-1 and Q1) that did not yield isochron ages suggest the conditions for producing isochrons were not satisfied, which may be caused by disturbance of the isotope system by a post-charge hydrothermal event. The outcomes of this study show the robust potential of Rb-Sr clay subsample geochronology for cross-checking isotopic ages yielded by other systems (e.g. K-Ar system) and constraining the timing of hydrocarbon charge.

Sr Isotope Analysis of Picogram-Level Samples by Thermal Ionization Mass Spectrometry Using a Highly Sensitive Silicotungstic Acid Emitter.

Thermal ionization mass spectrometry (TIMS) has shown excellent analytical precision for Sr isotopic ratio analysis, even for small masses of material (0.5-10 ng). However, because of the sensitivity limit of TIMS, it is still not possible to obtain high precision 87Sr/86Sr isotope ratios for picogram-level sample sizes (30-100 pg) due to the lack of a highly sensitive emitter. This study is the first to employ a highly sensitive silicotungstic acid emitter to measure Sr isotopes at the picogram-level using TIMS. This emitter produces a 3-fold enhancement in the ionization efficiency of Sr and not only significantly reduces the required sample size but also has good external precision. Analyses of the NIST 987 standard yield an external reproducibility (2 RSD, n = 8) better than ±0.013% even for 30 pg of Sr. It is possible to yield an internal precision (2 RSE) of ±0.003% for 100 pg of sample using the default 1011 Ohm feedback resistors. This method was verified by using a suite of silicate reference materials. Replicate digestions and analyses ( n = 8) of the basalt standard BCR-2 (87Sr/86Sr = 0.704998 ± 0.000028, 2 SD) at the 326 ± 30 pg level demonstrates that good external reproducibility is reached on ultratrace level silicate samples. This method has a wide variety of potential applications for samples containing ultralow amounts of Sr in geoscience and archeological studies, such as single grains of mica, sphalerite, and pyrite, single mantle melt inclusions, precious extra-terrestrial materials, and human hair to name just a few.

Remnants of Eoarchean continental crust derived from a subducted proto-arc.

Eoarchean [3.6 to 4.0 billion years ago (Ga)] tonalite-trondhjemite-granodiorite (TTG) is the major component of Earth's oldest remnant continental crust, thereby holding the key to understanding how continental crust originated and when plate tectonics started in the early Earth. TTGs are mostly generated by partial melting of hydrated mafic rocks at different depths, but whether this requires subduction remains enigmatic. Recent studies show that most Archean TTGs formed at relatively low pressures (≤1.5 GPa) and do not require subduction. We report a suite of newly discovered Eoarchean tonalitic gneisses dated at ~3.7 Ga from the Tarim Craton, northwestern China. These rocks are probably the oldest high-pressure TTGs so far documented worldwide. Thermodynamic and trace element modeling demonstrates that the parent magma may have been generated by water-fluxed partial melting of moderately enriched arc-like basalts at 1.8 to 1.9 GPa and 800° to 830°C, indicating an apparent geothermal gradient (400° to 450°C GPa-1) typical for hot subduction zones. They also locally record geochemical evidence for magma interaction with a mantle wedge. Accordingly, we propose that these high-pressure TTGs were generated by partial melting of a subducted proto-arc during arc accretion. Our model implies that modern-style plate tectonics was operative, at least locally, at ~3.7 Ga and was responsible for generating some of the oldest continental nuclei.

Linking magmatism with collision in an accretionary orogen.

A compilation of U-Pb age, geochemical and isotopic data for granitoid plutons in the southern Central Asian Orogenic Belt (CAOB), enables evaluation of the interaction between magmatism and orogenesis in the context of Paleo-Asian oceanic closure and continental amalgamation. These constraints, in conjunction with other geological evidence, indicate that following consumption of the ocean, collision-related calc-alkaline granitoid and mafic magmatism occurred from 255 ± 2 Ma to 251 ± 2 Ma along the Solonker-Xar Moron suture zone. The linear or belt distribution of end-Permian magmatism is interpreted to have taken place in a setting of final orogenic contraction and weak crustal thickening, probably as a result of slab break-off. Crustal anatexis slightly post-dated the early phase of collision, producing adakite-like granitoids with some S-type granites during the Early-Middle Triassic (ca. 251-245 Ma). Between 235 and 220 Ma, the local tectonic regime switched from compression to extension, most likely caused by regional lithospheric extension and orogenic collapse. Collision-related magmatism from the southern CAOB is thus a prime example of the minor, yet tell-tale linking of magmatism with orogenic contraction and collision in an archipelago-type accretionary orogen.

Continental flood basalts derived from the hydrous mantle transition zone.

It has previously been postulated that the Earth's hydrous mantle transition zone may play a key role in intraplate magmatism, but no confirmatory evidence has been reported. Here we demonstrate that hydrothermally altered subducted oceanic crust was involved in generating the late Cenozoic Chifeng continental flood basalts of East Asia. This study combines oxygen isotopes with conventional geochemistry to provide evidence for an origin in the hydrous mantle transition zone. These observations lead us to propose an alternative thermochemical model, whereby slab-triggered wet upwelling produces large volumes of melt that may rise from the hydrous mantle transition zone. This model explains the lack of pre-magmatic lithospheric extension or a hotspot track and also the arc-like signatures observed in some large-scale intracontinental magmas. Deep-Earth water cycling, linked to cold subduction, slab stagnation, wet mantle upwelling and assembly/breakup of supercontinents, can potentially account for the chemical diversity of many continental flood basalts.

Metallic lead nanospheres discovered in ancient zircons.

Zircon (ZrSiO4) is the most commonly used geochronometer, preserving age and geochemical information through a wide range of geological processes. However, zircon U-Pb geochronology can be affected by redistribution of radiogenic Pb, which is incompatible in the crystal structure. This phenomenon is particularly common in zircon that has experienced ultra-high temperature metamorphism, where ion imaging has revealed submicrometer domains that are sufficiently heterogeneously distributed to severely perturb ages, in some cases yielding apparent Hadean (>4 Ga) ages from younger zircons. Documenting the composition and mineralogy of these Pb-enriched domains is essential for understanding the processes of Pb redistribution in zircon and its effects on geochronology. Using high-resolution scanning transmission electron microscopy, we show that Pb-rich domains previously identified in zircons from East Antarctic granulites are 5-30 nm nanospheres of metallic Pb. They are randomly distributed with respect to zircon crystallinity, and their association with a Ti- and Al-rich silica melt suggests that they represent melt inclusions generated during ultra-high temperature metamorphism. Metallic Pb is exceedingly rare in nature and previously has not been reported in association with high-grade metamorphism. Formation of these metallic nanospheres within annealed zircon effectively halts the loss of radiogenic Pb from zircon. Both the redistribution and phase separation of radiogenic Pb in this manner can compromise the precision and accuracy of U-Pb ages obtained by high spatial resolution methods.

A light carbon reservoir recorded in zircon-hosted diamond from the Jack Hills.

The recent discovery of diamond-graphite inclusions in the Earth's oldest zircon grains (formed up to 4,252 Myr ago) from the Jack Hills metasediments in Western Australia provides a unique opportunity to investigate Earth's earliest known carbon reservoir. Here we report ion microprobe analyses of the carbon isotope composition of these diamond-graphite inclusions. The observed delta(13)C(PDB) values (expressed using the PeeDee Belemnite standard) range between -5 per mil and -58 per mil with a median of -31 per mil. This extends beyond typical mantle values of around -6 per mil to values observed in metamorphic and some eclogitic diamonds that are interpreted to reflect deep subduction of low-delta(13)C(PDB) biogenic surface carbon. Low delta(13)C(PDB) values may also be produced by inorganic chemical reactions, and therefore are not unambiguous evidence for life on Earth as early as 4,250 Myr ago. Regardless, our results suggest that a low-delta(13)C(PDB) reservoir may have existed on the early Earth.

Hadean diamonds in zircon from Jack Hills, Western Australia.

Detrital zircons more than 4 billion years old from the Jack Hills metasedimentary belt, Yilgarn craton, Western Australia, are the oldest identified fragments of the Earth's crust and are unique in preserving information on the earliest evolution of the Earth. Inclusions of quartz, K-feldspar and monazite in the zircons, in combination with an enrichment of light rare-earth elements and an estimated low zircon crystallization temperature, have previously been used as evidence for early recycling of continental crust, leading to the production of granitic melts in the Hadean era. Here we present the discovery of microdiamond inclusions in Jack Hills zircons with an age range from 3,058 +/- 7 to 4,252 +/- 7 million years. These include the oldest known diamonds found in terrestrial rocks, and introduce a new dimension to the debate on the origin of these zircons and the evolution of the early Earth. The spread of ages indicates that either conditions required for diamond formation were repeated several times during early Earth history or that there was significant recycling of ancient diamond. Mineralogical features of the Jack Hills diamonds-such as their occurrence in zircon, their association with graphite and their Raman spectroscopic characteristics-resemble those of diamonds formed during ultrahigh-pressure metamorphism and, unless conditions on the early Earth were unique, imply a relatively thick continental lithosphere and crust-mantle interaction at least 4,250 million years ago.

Comment on "Heterogeneous Hadean hafnium: evidence of continental crust at 4.4 to 4.5 Ga".

Harrison et al. (Reports, 23 December 2005, p. 1947) proposed that plate tectonics and granites existed 4.5 billion years ago (Ga), within 70 million years of Earth's formation, based on geochemistry of >4.0 Ga detrital zircons from Australia. We highlight the large uncertainties of this claim and make the more moderate proposal that some crust formed by 4.4 Ga and oceans formed by 4.2 Ga.