Uranium-Lead Systematics of Lunar Basaltic Meteorite Northwest Africa 2977.

Northwest Africa (NWA) 2977 is a lunar basaltic meteorite that was found in 2005 and has been classified as an olivine cumulate gabbro. This meteorite contains a shock melt vein (SMV) induced by an intense shock event. We report herein on an in-situ analysis of phosphates in the host gabbro and the shock vein for the U-Pb dating of NWA 2977 using an ion microprobe, NanoSIMS. The majority of the analyzed phosphates, in both the SMV and host-rock, lie on a linear regression in 238U/206Pb-207Pb/206Pb-204Pb/206Pb three-dimensional space, indicating a total Pb/U isochron age of 3.15±0.12 Ga (95% confidence level), which is consistent ages determined in previous isotopic studies of NWA 2977 (Sm-Nd age of 3.10±0.05 Ga, Rb-Sr age of 3.29±0.11 Ga, and Pb-Pb baddeleyite age of 3.12±0.01 Ga), and identical to the age of the U-Pb phosphate in a paired meteorite NWA 773, 3.09±0.20 Ga, derived from our dataset. There was no clear difference in the formation age between the phosphates found in the SMV and host-rock, although the shape and size of the grains and the Raman spectra show the evidence of intense shock metamorphism. Based on these findings, the cooling rate of the phosphate was very rapid, constrained to be larger than 140 K/s.

NanoSIMS Analysis of Rare Earth Elements in Silicate Glass and Zircon: Implications for Partition Coefficients.

We have developed a method to analyze all rare earth elements in silicate glasses and zircon minerals using a high lateral resolution secondary ion mass spectrometer (NanoSIMS). A 2nA O- primary beam was used to sputter a 7-8-µm diameter crater on the sample surface, and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV. A high mass resolving power of 9,400 at 10% peak height was attained to separate heavy REE from oxide of light REE. A multi-collector system combined with peak-jumping by magnetic field was adjusted to detect REEs and silicon-30 for calibration. Based on results of NIST SRM610 glass, sensitivities of REEs vary from 3 cps/ppm/nA of Lu to 13 cps/ppm/nA of Eu. Reproducibility of REE/Si ratios is better than 18% at 2σ. Secondary ion yields of REEs show positive relationships with their ionization potential of second valence. REEs of AS3, QGNG, and Torihama zircons were measured and calibrated against those of 91500 standard zircon. SIYs of REEs of zircon are identical to those of the glass standard. AS3 and QGNG data are generally consistent with those of previous work. Torihama REE data combined with the whole rock data provide partition coefficients of REEs between silicate melt and zircon. The relationship between these coefficients and ionic radius is explained by an elastic moduli model.

Influence of normal tide and the Great Tsunami as recorded through hourly-resolution micro-analysis of a mussel shell.

We report here hourly variations of Mg/Ca, Sr/Ca, and Ba/Ca ratios in a Mediterranean mussel shell (Mytilus galloprovincialis) collected at the Otsuchi bay, on the Pacific coast of northeastern Japan. This bivalve was living in the intertidal zone, where such organisms are known to form a daily or bidaily growth line comprised of abundant organic matter. Mg/Ca ratios of the inner surface of the outer shell layer, corresponding to the most recent date, show cyclic changes at 25-90 µm intervals, while no interpretable variations are observed in Sr/Ca and Ba/Ca ratios. High Mg/Ca ratios were probably established by (1) cessation of the external supply of Ca and organic layer forming when the shell is closed at low tide, and (2) the strong binding of Mg to the organic layer, but not of Sr and Ba. Immediately following the great tsunami induced by the 2011 Tohoku earthquake, Mg/Ca enrichment occurred, up to 10 times that of normal low tide, while apparent Ba/Ca enrichment was observed for only a few days following the event, therefore serving a proxy of the past tsunami. Following the tsunami, periodic peaks and troughs in Mg/Ca continued, perhaps due to a biological memory effect as an endogenous clock.

Mantle-derived helium released through the Japan trench bend-faults.

Plate bending-related normal faults (i.e. bend-faults) develop at the outer trench-slope of the oceanic plate incoming into the subduction zone. Numerous geophysical studies and numerical simulations suggest that bend-faults play a key role by providing pathways for seawater to flow into the oceanic crust and the upper mantle, thereby promoting hydration of the oceanic plate. However, deep penetration of seawater along bend-faults remains controversial because fluids that have percolated down into the mantle are difficult to detect. This report presents anomalously high helium isotope (3He/4He) ratios in sediment pore water and seismic reflection data which suggest fluid infiltration into the upper mantle and subsequent outflow through bend-faults across the outer slope of the Japan trench. The 3He/4He and 4He/20Ne ratios at sites near-trench bend-faults, which are close to the isotopic ratios of bottom seawater, are almost constant with depth, supporting local seawater inflow. Our findings provide the first reported evidence for a potentially large-scale active hydrothermal circulation system through bend-faults across the Moho (crust-mantle boundary) in and out of the oceanic lithospheric mantle.

Sulfur assimilation in corals with aposymbiotic and symbiotic zooxanthellae.

Although sulfate ions are the main form of sulfur in the ocean, there is limited knowledge on their use by living organisms. Stable isotope labelling and NanoSIMS analysis were used in this study to clarify how sulfate, in seawater, is assimilated by corals and zooxanthellae at the cellular level. Aposymbiotic and symbiotic coral juveniles from the genus Acropora were incubated for 2 days in filtered seawater with 34 S-labelled sulfate. Further, the labelled corals were incubated for additional 2 days in natural seawater. Mapping of sulfur isotopes (34 S/32 S) showed that the 'hotspots' were enriched in 34 S on a sub-micro level and were heterogeneously distributed in the coral soft tissues. Specifically, 34 S hotspots were found in both the symbiotic zooxanthellae and coral host tissues. In aposymbiotic corals, 34 S was detected in the tissues, indicating that the host corals directly assimilated the sulfate ions without any aid from the zooxanthellae. Even after 2 days in normal seawater, the 34 S label was clearly seen in both symbiotic and aposymbiotic corals, indicating that the assimilated sulfur was retained for at least 2 days.

Landside tritium leakage over through years from Fukushima Dai-ichi nuclear plant and relationship between countermeasures and contaminated water.

There has been tritium groundwater leakage to the land side of Fukushima Dai-ichi nuclear power plants since 2013. Groundwater was continuously collected from the end of 2013 to 2019, with an average tritium concentration of approximately 20 Bq/L. Based on tritium data published by Tokyo Electric Power Company Holdings (TEPCO) (17,000 points), the postulated source of the leakage was (1) leaks from a contaminated water tank that occurred from 2013 to 2014, or (2) a leak of tritium that had spread widely over an impermeable layer under the site. Based on our results, sea side and land side tritium leakage monitoring systems should be strengthened.

Groundwater oxygen anomaly related to the 2016 Kumamoto earthquake in Southwest Japan.

Here, we report the groundwater oxygen isotope anomalies caused by the 2016 Kumamoto earthquake (MJMA7.3) that occurred in Southwest Japan on April 16, 2016. One hundred and seventeen groundwater samples were collected from a deep well located 3 km to the southeast of the epicenter in Mifune Town, Kumamoto Prefecture; they were drinking water packed in PET bottles and distributed in the area between April 2015 and March 2018. Further, the oxygen and hydrogen isotopes were evaluated via cavity ring-down spectroscopy without performing any pretreatment. An anomalous increase was observed with respect to the δ18O value (up to 0.51‰) soon after the earthquake along with a precursory increase of 0.38‰ in January 2016 before the earthquake. During these periods, there was no noticeable change in the hydrogen isotopic ratios. Rapid crustal deformation related to the earthquake may have enhanced the microfracturing of the aquifer rocks and the production of new surfaces, inducing δ18O enrichment via oxygen isotopic exchange between rock and porewater without changing δ2H.

High nitrogen solubility in stishovite (SiO2) under lower mantle conditions.

Nitrogen is a crucial volatile element in the early Earth's evolution and the origin of life. Despite its importance, nitrogen's behavior in the Earth's interior remains poorly understood. Compared to other volatile elements, nitrogen is depleted in the Earth's atmosphere (the so-called "missing nitrogen"), calling for a hidden deep reservoir. To investigate nitrogen's behavior in the deep Earth including how the reservoir formed, high-pressure and high-temperature experiments were conducted at 28 GPa and 1,400-1,700 °C. To reproduce the conditions in the lower mantle, the redox was controlled using a Fe-FeO buffer. We observed that depending on the temperature conditions, stishovite can incorporate up to 90-404 ppm nitrogen, experimentally demonstrating that stishovite has the highest nitrogen solubility among the deep mantle minerals. Stishovite is the main mineral component of subducted nitrogen-rich sedimentary rocks and eroded continental crust that are eventually transported down to the lower mantle. Our results suggest that nitrogen could have been continuously transported into the lower mantle via subduction, ever since plate tectonics began.

Displaced cratonic mantle concentrates deep carbon during continental rifting.

Continental rifts are important sources of mantle carbon dioxide (CO2) emission into Earth's atmosphere1-3. Because deep carbon is stored for long periods in the lithospheric mantle4-6, rift CO2 flux depends on lithospheric processes that control melt and volatile transport1,3,7. The influence of compositional and thickness differences between Archaean and Proterozoic lithosphere on deep-carbon fluxes remains untested. Here we propose that displacement of carbon-enriched Tanzanian cratonic mantle concentrates deep carbon below parts of the East African Rift System. Sources and fluxes of CO2 and helium are examined over a 350-kilometre-long transect crossing the boundary between orogenic (Natron and Magadi basins) and cratonic (Balangida and Manyara basins) lithosphere from north to south. Areas of diffuse CO2 degassing exhibit increasing mantle CO2 flux and 3He/4He ratios as the rift transitions from Archaean (cratonic) to Proterozoic (orogenic) lithosphere. Active carbonatite magmatism also occurs near the craton edge. These data indicate that advection of the root of thick Archaean lithosphere laterally to the base of the much thinner adjacent Proterozoic lithosphere creates a zone of highly concentrated deep carbon. This mode of deep-carbon extraction may increase CO2 fluxes in some continental rifts, helping to control the production and location of carbonate-rich magmas.

Heterogeneous nitrogen fixation rates confer energetic advantage and expanded ecological niche of unicellular diazotroph populations.

Nitrogen fixing plankton provide nitrogen to fuel marine ecosystems and biogeochemical cycles but the factors that constrain their growth and habitat remain poorly understood. Here we investigate the importance of metabolic specialization in unicellular diazotroph populations, using laboratory experiments and model simulations. In clonal cultures of Crocosphaera watsonii and Cyanothece sp. spiked with 15N2, cellular 15N enrichment developed a bimodal distribution within colonies, indicating that N2 fixation was confined to a subpopulation. In a model of population metabolism, heterogeneous nitrogen (N2) fixation rates substantially reduce the respiration rate required to protect nitrogenase from O2. The energy savings from metabolic specialization is highest at slow growth rates, allowing populations to survive in deeper waters where light is low but nutrients are high. Our results suggest that heterogeneous N2 fixation in colonies of unicellular diazotrophs confers an energetic advantage that expands the ecological niche and may have facilitated the evolution of multicellular diazotrophs.

Isotopic ratios of uranium and caesium in spherical radioactive caesium-bearing microparticles derived from the Fukushima Dai-ichi Nuclear Power Plant.

Spherical radioactive caesium (Cs)-bearing microparticles (CsMPs) were emitted during the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident in March, 2011. The emission source (timing) and formation process of these particles remain unclear. In this study, the isotopic ratios of uranium (235U and 238U) and caesium (133Cs, 134Cs, 135Cs, and 137Cs) isotopes in the five spherical CsMPs (ca. 2 µm in size) sampled at 50 km west of the FDNPP were determined using secondary ion mass spectrometry and laser ablation-ICPMS, respectively. Results showed that the 235U/238U ratios of CsMPs were homogeneous (1.93 ± 0.03, N = 4) and close to those estimated for the fuel cores in units 2 and 3, and that the Cs isotopic ratios of CsMP were identical to those of units 2 and 3. These results indicated that U and Cs in the spherical CsMPs originated exclusively from the fuel melt in the reactors. Based on a thorough review of literatures related to the detailed atmospheric releases of radionuclides, the flow of plumes from the FDNPP reactor units during the accident and the U and Cs isotopic ratio results in this study, we hereby suggest that the spherical CsMPs originate only from the fuel in unit 2 on the night of 14 March to the morning of 15 March. The variation range of the analysed 235U/238U isotopic ratios for the four spherical particles was extremely narrow. Thus, U may have been homogenised in the source through the formation of fuel melt, which ultimately evaporating and taken into CsMPs in the reactor and was released from the unit 2.

Evidence in the Japan Sea of microdolomite mineralization within gas hydrate microbiomes.

Over the past 15 years, massive gas hydrate deposits have been studied extensively in Joetsu Basin, Japan Sea, where they are associated primarily with active gas chimney structures. Our research documents the discovery of spheroidal microdolomite aggregates found in association with other impurities inside of these massive gas hydrates. The microdolomites are often conjoined and show dark internal cores occasionally hosting saline fluid inclusions. Bacteroidetes sp. are concentrated on the inner rims of microdolomite grains, where they degrade complex petroleum-macromolecules present as an impurity within yellow methane hydrate. These oils show increasing biodegradation with depth which is consistent with the microbial activity of Bacteroidetes. Further investigation of these microdolomites and their contents can potentially yield insight into the dynamics and microbial ecology of other hydrate localities. If microdolomites are indeed found to be ubiquitous in both present and fossil hydrate settings, the materials preserved within may provide valuable insights into an unusual microhabitat which could have once fostered ancient life.

Mantle degassing along strike-slip faults in the Southeastern Korean Peninsula.

On September 12, 2016, a ML 5.8 earthquake hit Gyeongju in the southeastern part of the Korean Peninsula (SeKP), although the area is known to be far from the boundary of the active plate. A number of strike-slip faults are observed in heavily populated city areas (e.g., Busan, Ulsan, Pohang, and Gyeongju). However, dissolved gases related to the active faults have rarely been studied despite many groundwater wells and hot springs in the area. Here we report new results of gas compositions and isotope values of helium and carbon dioxide (CO2) in fault-related fluids in the region. Based on gas geochemistry, the majority of gas samples are abundant in CO2 (up to 99.91 vol.%). Measured 3He/4He ratios range from 0.07 to 5.66 Ra, showing that the mantle contribution is up to 71%. The range of carbon isotope compositions (δ13C) of CO2 is from -8.25 to -24.92‰, showing mantle-derived CO2 is observed coherently where high 3He/4He ratios appear. The weakening of faults seems to be related to enhanced pressures of fluids containing mantle-derived helium and CO2 despite the ductile lower crust underneath the region. Thus, we suggest that the SeKP strike-slip faults penetrate into the mantle through ductile shearing.

Mantle fluids associated with crustal-scale faulting in a continental subduction setting, Taiwan.

We report noble gas signatures of groundwater, hot springs, and bedrock samples from a major fault system that separates regional-scale blocks of accreted, continental materials in southern Taiwan. Despite the continental setting, the isotopic signatures argue for the presence of mantle derived fluids, suggesting that the active fault system is deep-seated. This is consistent with deep, non-volcanic tremors identified in the same area. We speculate that the mantle fluids are escaping along a crustal-scale fault marked by clusters of non-volcanic tremors directly beneath the southern Central Range. The evidence of these tremors and electrical conductivity anomalies along the strike of the fault recognized previously correlated up dip with the surface trace of a major active fault support the hypothesis.

Assimilation of nitrogen and carbon isotopes from fish diets to otoliths as measured by nanoscale secondary ion mass spectrometry.

RATIONALE: Nitrogen and carbon stable isotope ratios (δ15 N and δ13 C values) of carbonate-bound organic materials in otoliths can provide information to address the biological and ecological functions of fish. Correct interpretation of otolith δ15 N and δ13 C profiles requires knowledge of the metabolic routes of nitrogen and carbon isotopes. However, the isotopic assimilation of δ15 N and δ13 C compositions from diets to otoliths has rarely been investigated. METHODS: This study traced the daily nitrogen and carbon isotopic assimilation between diets and otoliths using nanoscale secondary ion mass spectrometry (NanoSIMS). Isotopically labeled algae (Tetraselmis chui) were fed to tilapia (Oreochromis niloticus) for 14-17 days. NanoSIMS and conventional isotope ratio mass spectrometry were used to measure δ15 N and δ13 C variations in the otoliths and fish muscle, respectively. RESULTS: Otolith δ15 N values abruptly surged from natural abundance levels by 1000-2300‰ after the fish ate 15 N-spiked algae with δ15 N values of approximately 2200‰. However, the δ15 N values of fish muscle increased to only approximately 500‰ at the end of the feeding experiment. Much higher δ15 N values (3700-14 000‰) and moderate δ13 C values (60-200‰) were detected in the otoliths after the tilapia ate 15 N- and 13 C-spiked algae with a δ15 N value of 36667‰ and a δ13 C value of 272‰. Mapping analysis showed sub-micrometer-scale distribution of 15 N embedded in the otolith growth increments with a low-to-high δ15 N signal after the tilapia shifted diets from non-spiked to 15 N-labeled algae. CONCLUSIONS: These results suggest that otolith nitrogen and carbon isotopes from food were directly assimilated on the same day. Food is the major and in some cases only source of otolith nitrogen isotopes but makes only a partial contribution to otolith carbon isotopes. Therefore, the δ15 N values recorded in the sclerochronological layers of the otoliths can be used to determine the trophic levels, food sources and diet changes of fish.

Groundwater oxygen isotope anomaly before the M6.6 Tottori earthquake in Southwest Japan.

Geochemical monitoring of groundwater in seismically-active regions has been carried out since 1970s. Precursors were well documented, but often criticized for anecdotal or fragmentary signals, and for lacking a clear physico-chemical explanation for these anomalies. Here we report - as potential seismic precursor - oxygen isotopic ratio anomalies of +0.24‰ relative to the local background measured in groundwater, a few months before the Tottori earthquake (M 6.6) in Southwest Japan. Samples were deep groundwater located 5 km west of the epicenter, packed in bottles and distributed as drinking water between September 2015 and July 2017, a time frame which covers the pre- and post-event. Small but substantial increase of 0.07‰ was observed soon after the earthquake. Laboratory crushing experiments of aquifer rock aimed to simulating rock deformation under strain and tensile stresses were carried out. Measured helium degassing from the rock and 18O-shift suggest that the co-seismic oxygen anomalies are directly related to volumetric strain changes. The findings provide a plausible physico-chemical basis to explain geochemical anomalies in water and may be useful in future earthquake prediction research.

Origin of methane-rich natural gas at the West Pacific convergent plate boundary.

Methane emission from the geosphere is generally characterized by a radiocarbon-free signature and might preserve information on the deep carbon cycle on Earth. Here we report a clear relationship between the origin of methane-rich natural gases and the geodynamic setting of the West Pacific convergent plate boundary. Natural gases in the frontal arc basin (South Kanto gas fields, Northeast Japan) show a typical microbial signature with light carbon isotopes, high CH4/C2H6 and CH4/3He ratios. In the Akita-Niigata region - which corresponds to the slope stretching from the volcanic-arc to the back-arc -a thermogenic signature characterize the gases, with prevalence of heavy carbon isotopes, low CH4/C2H6 and CH4/3He ratios. Natural gases from mud volcanoes in South Taiwan at the collision zone show heavy carbon isotopes, middle CH4/C2H6 ratios and low CH4/3He ratios. On the other hand, those from the Tokara Islands situated on the volcanic front of Southwest Japan show the heaviest carbon isotopes, middle CH4/C2H6 ratios and the lowest CH4/3He ratios. The observed geochemical signatures of natural gases are clearly explained by a mixing of microbial, thermogenic and abiotic methane. An increasing contribution of abiotic methane towards more tectonically active regions of the plate boundary is suggested.

Nitrogen recycling at the Costa Rican subduction zone: The role of incoming plate structure.

Efficient recycling of subducted sedimentary nitrogen (N) back to the atmosphere through arc volcanism has been advocated for the Central America margin while at other locations mass balance considerations and N contents of high pressure metamorphic rocks imply massive addition of subducted N to the mantle and past the zones of arc magma generation. Here, we report new results of N isotope compositions with gas chemistry and noble gas compositions of forearc and arc front springs in Costa Rica to show that the structure of the incoming plate has a profound effect on the extent of N subduction into the mantle. N isotope compositions of emitted arc gases (9-11 N°) imply less subducted pelagic sediment contribution compared to farther north. The N isotope compositions (δ15N = -4.4 to 1.6‰) of forearc springs at 9-11 N° are consistent with previously reported values in volcanic centers (δ15N = -3.0 to 1.9‰). We advocate that subduction erosion enhanced by abundant seamount subduction at 9-11 N° introduces overlying forearc crustal materials into the Costa Rican subduction zone, releasing fluids with lighter N isotope signatures. This process supports the recycling of heavier N into the deep mantle in this section of the Central America margin.

Early trace of life from 3.95 Ga sedimentary rocks in Labrador, Canada.

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 possible, and biogenic graphite has thus far been found only in the 3.7-3.8 Ga (gigayears ago) Isua supracrustal belt. 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 Labrador. 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.