Stable Noble Gas Research Articles

Identification of modern meteoric water, glacial meteoric water, and fossil seawater in a deep borehole at the coastal area of Horonobe, north Japan, using groundwater dating and paleoclimatic proxy methods

Groundwater flow in deep areas of coastal regions has attracted significant attention for geological radioactive waste disposal or geological CO2 storage. To investigate groundwater flow in coastal areas, groundwater dating methods with the potential to assess slow groundwater flow were used at depths of up to 1200 m at Hamasato, Horonobe, northern Japan. Multiple groundwater dating methods were applied using pore water in drilling core and pumping groundwater. This study shows that modern meteoric water, glacial meteoric water, and fossil seawater are distributed in sand and silt layers at 300–360 and 90–300 m in depth and in silt and mud layers below 800 m in depth, respectively. Modern meteoric water infiltrated after and glacial meteoric water infiltrated during the latest glacial period were identified using δD and δ18O values, estimated recharge temperature from noble gas concentrations, and 14C concentrations. The estimated recharge temperatures of modern and glacial meteoric waters were 8.1 ± 2.0 and 2.1 ± 2.0 °C, respectively, whereas the δD and δ18O values were −68 ± 3‰ and −10.3 ± 0.2‰, −81 ± 2‰ and −11.4 ± 0.3‰, respectively. The 14C age of modern meteoric water was 10–16 ka. However, the 14C age of glacial meteoric water could not be estimated because it was highly diluted by 14C-free CO2 from methanogenesis and marine carbonate dissolution. Fossil seawater was identified using δD, δ18O, 36Cl, and 4He. δD and δ18O values underwent water-rock interaction and approached inland fossil seawater with increasing depth. 36Cl/Cl values did not reach secular equilibrium in situ in the Yuchi Formation due to its relatively short geological age and consolidation-induced porosity changes. However, the Yuchi Formation seawater is considered extremely old because its 36Cl/Cl ratio is higher than that of modern seawater as a result of 36Cl production, which also explains the observed 36Cl/Cl increases with depth toward the secular equilibrium ratio (36Cl/Clse). 4He concentrations were in the order of 10−6 ccSTP/gw, corresponding to an in situ accumulation age of 1–2 Ma, neglecting the external flux. The contribution of external flux could be negligible for the short geological age and rapid sedimentation rates. 4He ages were equivalent to the geological age of the Yuchi Formation. Core investigations can interpolate groundwater investigations because cores, particularly those from low-hydraulic conductivity layers, can be collected continuously. In addition, stable and radioactive isotopes and noble gases can help identify modern meteoric water, glacial meteoric water, and fossil seawater, assisting in understanding the groundwater flow velocity.

Using 81Kr and isotopic tracers to characterise old groundwater in the Bangkok metropolitan and vicinity areas

ABSTRACT Krypton-81 was applied to investigate the age of groundwater in the aquifer system in the Bangkok metropolitan and vicinity areas. Stable (2H, 18O and 13C) and radioactive (3H, 85Kr and 14C) isotopes and noble gases were applied in parallel. Low levels of 14C and significant radiogenic 4He confirm that groundwater in the deep aquifers is older than 30 ka. 81Kr analysis identified groundwater with ages ranging from 17 to 300 ka. At some sites, large age discrepancies between 81Kr and 14C indicated that inter-aquifer mixing is likely occurring. The interpretation of the noble gases suggests that groundwaters in the deeper aquifers, with apparent ages of 300 to 10 ka, have recharged in slightly colder and wetter climates than those found in the upper aquifers with apparent ages < 10 ka. Degradation of water quality from seawater intrusion was identified in the upper four aquifers. This was also evidenced by higher δ 18O and δ 2H values, typical of seawater. The four deeper aquifers contain high quality water characterised by less enriched 18O and 2H. This work presents new findings of very old groundwater in the Bangkok aquifer system.

Mineral Crushing Methods for Noble Gas Analyses of Fluid Inclusions

Noble gases are frequently probed for investigating fluid inclusions in minerals to unravel rock-forming processes through time. Over the last decades, heating and crushing have been the two main methods applied for noble gas extraction from fluid inclusions in ultrahigh vacuum (about 10-9 mBar). The heating of minerals or pieces of bulk rock causes the release of noble gases from both fluid inclusions and the mineral or rock matrix, the latter due to temperature-dependent mineral dehydration. Crushing of minerals only affects fluid inclusions and allows a release of noble gases at room temperature with minor contributions from the mineral matrix. This review describes different ultravacuum crushing techniques for noble gas analysis from fluid inclusions. It examines the technical details and operational conditions of each crushing system as well as methods to prepare samples prior to crushing. Crushing systems were found to have unique designs across the different laboratories reviewed; they include single or multiple sample loadings and manual, magnetic, or hydraulic operation of the crushing pistons. Due to the small amounts of noble gases released, the technology requires several mg to a few grams of rock material to achieve a measurement of all stable noble gas isotopes in a single fluid inclusion. While theoretically all stable noble gas isotopes are of interest, the elements and isotopes reported in different studies vary widely and reference materials as well as laboratory intercomparisons are lacking. The review includes applications on the origins of magmatic rocks and geochemical processes in the Earth’s mantle, the origin and chemical composition of deep crustal fluids and how these contribute to the formation of minerals of economic interest, and paleoclimate studies based on speleothems.

A journey in Noble Gas Cosmochemistry and Geochemistry

I started my journey in science by studying noble gases implanted by the solar wind in dust grains on the surface of the Moon, and with many colleagues I have studied solar wind implanted noble gases in natural and artificial samples throughout my career, the latter exposed primarily by the Genesis space mission. Major questions are what noble gases in the solar wind can tell us about the present and the past Sun, and how they can contribute to understanding the formation and history of the planets and their building blocks, represented, for example, by meteorites. Since my early years as a postdoc, I have also been interested in noble gases (and radioactive nuclides) produced in meteorites and other extraterrestrial samples by interactions with energetic elementary particles from galactic cosmic radiation (and the Sun). These so called “cosmogenic” nuclides allow us to study the transport of meteorites to Earth, and the dynamics of the top surface layers (“regoliths”) on the Moon, asteroids, and comets. Cosmogenic noble gases are also crucial for studying even more exotic topics such as the history of tiny presolar grains that formed in the cooling envelopes of earlier generations of stars towards the end of their lives and were eventually incorporated into the meteoritic matter where they are found today. Cosmogenic noble gases in some tiny phases in meteorites are also likely tracers of our highly active Sun at a very early stage in its history. A few years later, I started my third major research topic in cosmochemistry, the study of primordial noble gases in meteorites and other extraterrestrial samples. These noble gases were incorporated into meteorites or their precursors in the early solar system or even in a presolar environment. I also participated in studies by colleagues of isotopic anomalies of other elements important in cosmochemistry, my expertise being mainly in aspects of the influence of cosmic rays on these elements. Although working in an Earth Science institution, it took quite a while before I started to also study noble gases (and radionuclides) in terrestrial samples. This is described in the second part of this contribution. A major focus was on cosmogenic noble gases and radionuclides produced in samples near the Earth’s surface. Although production rates of cosmogenic nuclides on Earth are several orders of magnitude lower than in space, making their analysis more challenging, they have become an important tool in geomorphology. Because stable noble gas nuclides are particularly well suited to the study of ancient landscapes, much of our work focused on areas with arid climates, such as Antarctica and the Andes in Chile, in collaboration with geoscience colleagues. We also participated in the large multinational CRONUS collaboration, funded by the European Union, a community effort to improve our knowledge of nuclide production rates at the Earth’s surface. In another major collaboration with external colleagues we are involved in noble gas analyses of water samples, ranging from lakes to aquifers to tiny inclusions in stalagmites. This research focuses on studying lake and groundwater dynamics, including contributions of mantle-derived noble gases such as in volcanic lakes. Atmospheric noble gases dissolved in suitable samples are also palaeotemperature indicators, supplementing information from other proxies such as oxygen isotopes.

Combining 14CDOC and 81Kr with hydrochemical data to identify recharge processes in the South German Molasse Basin

• Combination of 14 C DOC and 81 Kr provides new insight of recharge dynamics in the UJA. • Groundwater dating with 14 C DOC and 81 Kr proves to be useful for deep aquifers. • Groundwater dating revealed high spatial heterogeneity in groundwater ages. • The main recharge area of the UJA may be located at the southern border of the SGMB. • Glaciations may be the driving force for groundwater recharge. To face the challenges of ongoing climate change, renewable energy sources are needed to reduce CO 2 emissions to the atmosphere. The South German Molasse Basin (SGMB) contains an important geothermal aquifer in Germany; however, an enhanced understanding of the flow regime at the basin scale remains a fundamental limiting factor in assessing a long-term and sustainable strategy for using this green energy source. Here we report 14 C DOC and 81 Kr groundwater dating results together with hydrochemical data, stable water isotopes, noble gases and out-diffusion experiments that indicate that the thermal groundwater consists of at least two groundwater sources: a formerly unknown young groundwater component with apparent water ages between 9,800 and 18,700 a and an old groundwater component, which shows an apparent water age of up to approximately 300 ka. The results of the out-diffusion experiments with core material from the Upper Jurassic aquifer (UJA) suggest that diffusion processes between rock-matrix water and more mobile fracture water represent a controlling mechanism for groundwater flow and the observed extended apparent groundwater ages within the UJA. The observed elevated 14 C DOC activities and the high spatial heterogeneity in groundwater ages close to the southern margin of the SGMB were interpreted as a recharge zone of the system. The combination of the 14 C DOC and 81 Kr methods shows the potential as a powerful groundwater dating tool for deep aquifers.

81Kr reveals one-million-year-old groundwater at the Atlantic coast of Argentina as a record of Mid-Pleistocene climate

Sedimentary deposits in both Colorado Basin and Salado Basin, two geological basins originated after the Atlantic rifting in the coastal area of Argentina, contain deep confined aquifers bearing thermal waters. Previous studies on the paleogroundwater of this region have been limited by the radiocarbon dating range. In this study 81Kr dating is applied to reveal groundwater ages up to 1.1 Ma, so far the oldest found in South America. Groundwater in the Colorado Basin, previously assigned to the Last Glacial Maximum (LGM), is reassigned to a period from Marine Isotope Stage 1 to 5 (MIS 1 to MIS 5). The age information combined with water stable isotopes and noble gases suggests the possible existence of the South-American-Low-Level-Jet (SALLJ) in this period, that had carried the recycled water vapor from the tropical Amazonia to locations further south compared to the present time. Also, the inferred recharge conditions in both basins during Mid-Pleistocene agree with the very dry climate in this period suggested by previous studies.

A geochemical study of the Sweet Home mine, Colorado Mineral Belt, USA: formation of deep hydrothermal vein–type molybdenum greisen and base metal mineralization

AbstractDeep hydrothermal Mo, W, and base metal mineralization at the Sweet Home mine (Detroit City portal) formed in response to magmatic activity during the Oligocene. Microthermometric data of fluid inclusions trapped in greisen quartz and fluorite suggest that the early-stage mineralization at the Sweet Home mine precipitated from low- to medium-salinity (1.5–11.5 wt% equiv. NaCl), CO2-bearing fluids at temperatures between 360 and 415 °C and at depths of at least 3.5 km. Stable isotope and noble gas isotope data indicate that greisen formation and base metal mineralization at the Sweet Home mine was related to fluids of different origins. Early magmatic fluids were the principal source for mantle-derived volatiles (CO2, H2S/SO2, noble gases), which subsequently mixed with significant amounts of heated meteoric water. Mixing of magmatic fluids with meteoric water is constrained by δ2Hw–δ18Ow relationships of fluid inclusions. The deep hydrothermal mineralization at the Sweet Home mine shows features similar to deep hydrothermal vein mineralization at Climax-type Mo deposits or on their periphery. This suggests that fluid migration and the deposition of ore and gangue minerals in the Sweet Home mine was triggered by a deep-seated magmatic intrusion. The findings of this study are in good agreement with the results of previous fluid inclusion studies of the mineralization of the Sweet Home mine and from Climax-type Mo porphyry deposits in the Colorado Mineral Belt.

Stable Noble Gas Compounds Based on Superelectrophilic Anions [B12 (BO)11 ]- and [B12 (OBO)11

Superelectrophilic monoanions [B12 (BO)11 ]- and [B12 (OBO)11 ]- , generated from stable dianions [B12 (BO)12 ]2- and [B12 (OBO)12 ]2- , show great potential for binding with noble gases (Ngs). The binding energies, quantum theory of atoms in molecules (QTAIM), natural population analysis (NPA), energy decomposition analysis (EDA), and electron localization function (ELF) were carried out to understand the B-Ng bond in [B12 (BO)11 Ng]- and [B12 (OBO)11 Ng]- . The calculated results reveal that heavier noble gases (Ar, Kr, and Xe) bind covalently with both [B12 (BO)11 ]- and [B12 (OBO)11 ]- with large binding energies, making them potentially feasible to be synthesized. Only [B12 (OBO)11 ]- could form a covalent bond with helium or neon but the small binding energy of [B12 (OBO)11 He]- may pose a challenge for its experimental detection.

U-PB DATING AND GEOCHEMICAL CONSTRAINTS TO EARLY CRETACEOUS HYDROTHERMAL DOLOMITIZATION IN THE PROVENÇAL DOMAIN (MARITIME ALPS, NW ITALY - SE FRANCE)

In the Maritime Alps (NW Italy - SE France), the Middle Triassic-Berriasian platform carbonates of the Provencal Domain are locally affected by an intense hydrothermal dolomitization. This dolomitization resulted from a large-scale hydrothermal circulation related to deep-rooted faults, and is indirect evidence of a significant earliest Cretaceous fault activity in this part of the Alpine Tethys European palaeomargin. New carbonate U-Pb dating and geochemical (stable isotope and noble gases on inclusion-hosted water, 87Sr/86Sr, clumped isotopes) data allowed a better understanding of the timing and mechanisms of the hydrothermal circulation. Hydrothermal fluids probably originated from seawater, which was involved in a deep circulation within the underlying crystalline basement, undergoing heating to more than 200°C and substantial compositional modification by prolonged interaction with basement rocks. Thin cement rims rich in carbonaceous material, locally alternated with hydrothermal dolomite cements, are interpreted as remnants of ephemeral microbial communities that could colonize the upper part of hydrothermal conduits during periods of reduced hot fluid flow and contemporaneous downward seawater infiltration.

Recycling of nitrogen and light noble gases in the Central American subduction zone: Constraints from 15N15N

How much nitrogen and light noble gases are recycled in modern subduction zones is unclear. Fumaroles act as a means for passive degassing in arcs. They receive variable contributions of volatiles from arc magmas, themselves sourced from the mantle wedge. The gas compositions reflect the extent of volatile enrichment in sub-arc mantle sources and constrain slab dehydration. However, contributions from atmospheric components in fumaroles are unavoidable. For N2, neon and argon, the atmospheric components are challenging to discern from slab-derived components. Here, we report 15N15N measurements from eight fumaroles and seven bubbling springs, along the Central American arc. Our new 15N15N data are coupled with noble gases measurements and show that air-derived components in volcanic gas discharges can easily be underestimated, in both fumaroles and springs, using conventional stable isotope or noble gases methods. We show that, in the absence of 15N15N data, previously used tracers for air (e.g., δ15N, N2/Ar, N2/He, among others) may lead to erroneous conclusions regarding the origin of volatiles in mixed gases. In contrast, 15N15N data provide quantitative constraints on the nature and contributions of both atmospheric and magmatic components. Most springs are heavily dominated by air-derived N2, while fumaroles show substantial contributions of volcanic endmembers. Based on the fumarole data, we show that magma sources beneath the central American arc are enriched in all volatiles relative to 3He, by two to three orders of magnitude compared to the MORB source. We use new 15N15N data to obtain source N2/3He, 3He/36Ar and 3He/22Ne ratios which we then use to compute volcanic N2, Ar and Ne degassing fluxes. Using this approach, we show that outgassing fluxes appear to match subduction fluxes in the Central America subduction zone. We determine an N2 outgassing flux of between 4.0×108 and 1.0×109 mol N2/y, comparable to the subduction flux of 5.7×108 mol N2/yr determined previously. We obtain a similar conclusion for 22Ne and 36Ar. Overall, the volatile fluxes in the central American subduction zone no longer seem to require net transfer of N2, Ar, and Ne, to the deep mantle.

Long-term time series of environmental tracers reveal recharge and discharge conditions in shallow karst aquifers in Hungary and Slovakia

Study regionThree karst regions in Hungary and Slovakia. Study focusTime series of environmental tracers both in the groundwater recharge and discharge provide important insights into how a karst water system works. The aim of the present work was to study the response of discharging karst waters to recharge using time series of environmental tracers, such as tritium, stable water isotopes, noble gases and SF6. New hydrological insights for the regionOur results show that sampling frequency plays a significant role in detecting short residence times (months): the seasonality of 18O isotope composition of a selected karst spring indicates a 10 % contribution of recent water with a residence time of half a year. The contribution of an older component can be proven by the decrease of the tritium content of the waters, which compares to the decreasing trend of the tritium time series of the precipitation. However, the tritium concentrations are just slightly lower than those of the precipitation and the recharge water, hence the residence times of these shallow springs are supposed to be short. 3H/3He and SF6 apparent ages confirm this to be between 0 and 10 years, with a median of 1.4 years. Our study demonstrates that long-term time series are preferable to provide better estimation to the age distribution than individual, short-term investigations.

Generation and structural modification of the giant Kengdenongshe VMS-type Au-Ag-Pb-Zn polymetallic deposit in the East Kunlun Orogen, East Tethys: Constraints from geology, fluid inclusions, noble gas and stable isotopes

The Kengdenongshe giant Au-Ag-Pb-Zn polymetallic deposit is located in the East Kunlun Orogen (EKO). It contains about 42.2 t of Au, 608.6 t of Ag and 1.05 Mt of Pb and Zn with an average grade of Au 2.31 g/t, Ag 19.29 g/t and Pb + Zn 3.49 wt% (Pb: 1.23 wt%, Zn: 2.26 wt%). The NWW-trending ore bodies are predominantly hosted in Late Permian to Triassic rhyolitic tuff, which formed during Late Permian back-arc extension to Triassic arc-continental collision. The ore bodies are subdivided into Pb-Zn rich ore bodies on the top with high grades of Pb and Zn and low grades of Au and Ag, and Au-Ag rich ore bodies below with high grades of Au and Ag and low grades of Pb and Zn. The Pb-Zn rich ore bodies occur as vein, stockwork, and in breccia, and comprise quartz, pyrite, galena, sphalerite, and small amounts of chalcopyrite. The Au-Ag rich ore bodies consist of auriferous barite-sulfide-oxide veins and contain barite, pyrite (early strawberry and oolitic pyrite and later eu- to subhedral pyrite), galena, sphalerite, chalcopyrite, tetrahedrite and covellite. Gold is present as electrum, kustelite and native gold and silver is present as polybasite, pearceite, kongsbergite, and as minor native silver in microfractures in sulfides. The hydrothermal alteration minerals include, from bottom to top, quartz + barite + calcite around the Au-Ag rich orebodies, quartz + chlorite + epidote around the Pb-Zn rich orebodies, and quartz + K-feldspar within the tuff. Fluid inclusions from both the Pb-Zn rich and the Au-Ag rich orebodies consist of two phases (V–L-type) fluid inclusions of which the vapor phase has a size of 10–40 vol%. Fluid inclusions microthermometry reveal homogenization temperatures of fluid inclusions in Pb-Zn rich and Au-Ag rich ore bodies of 128–230 °C and 110–320 °C, with corresponding salinities of 0.7–9.9 and 0.2–18.3 wt% NaCl equivalent, respectively. H-O-S-Pb stable isotope and He-Ar noble gas isotope data indicate a mixed magmatic water-seawater source for both the Pb-Zn and Au-Ag rich ore bodies, and an additional meteoric water component for the Au-Ag rich ore bodies. The Pb-Zn and Au-Ag rich ore bodies share the same sulfur and lead sources, i.e. sulfur is derived from crustal magma and seawater/marine sulfate, and the lead originated from a mixed magmatic-ancient crustal sedimentary source. Collectively, the regional geology, mineralogy, alteration, and geochemistry indicate that the Kengdenongshe Au-Ag-Pb-Zn polymetallic deposit can be characterized as a VMS-type (volcanic-associated massive sulfide) deposit. Formation of the ore-hosting rhyolite tuff and mineralization are associated with Late Permian to Triassic marine volcanic exhalation. Middle to Late Triassic basin closure and arc-continent collision modified the deposit and resulted in the location inversion of the Pb-Zn and Au-Ag rich orebodies.

Theoretical Prediction on the New Types of Noble Gas Containing Anions OBONgO- and OCNNgO- (Ng = He, Ar, Kr and Xe).

The fluorine-less noble gas containing anions OBONgO− and OCNNgO− have been studied by correlated electronic structure calculation and density functional theory. The obtained energetics indicates that for Ng=Kr and Xe, these anions should be kinetically stable at low temperature. The molecular structures and electron density distribution suggests that these anions are stabilized by ion-induced dipole interactions with charges concentrated on the electronegative OBO and OCN groups. The current study shows that in addition to the fluoride ion, polyatomic groups with strong electronic affinities can also form stable noble gas containing anions of the type Y−…NgO.

Factors Affecting Shale Gas Chemistry and Stable Isotope and Noble Gas Isotope Composition and Distribution: A Case Study of Lower Silurian Longmaxi Shale Gas, Sichuan Basin

The Weiyuan (WY) and Changning (CN) fields are the largest shale gas fields in the Sichuan Basin. Though the shale gases in both fields are sourced from the Longmaxi Formation, this study found notable differences between them in molecular composition, carbon isotopic composition, and noble gas abundance and isotopic composition. CO2 (av. 0.52%) and N2 (av. 0.94%) were higher in Weiyuan than in Changning by an average of 0.45% and 0.70%, respectively. The δ13C1 (−26.9% to −29.7%) and δ13C2 (−32.0% to −34.9%) ratios in the Changning shale gases were about 8% and 6% heavier than those in Weiyuan, respectively. Both shale gases had similar 3He/4He ratios but different 40Ar/36Ar ratios. These geochemical differences indicated complex geological conditions and shed light on the evolution of the Lonmaxi shale gas in the Sichuan Basin. In this study, we highlight the possible impacts on the geochemical characteristics of gas due to tectonic activity, thermal evolution, and migration. By combining previous gas geochemical data and the geological background of these natural gas fields, we concluded that four factors account for the differences in the Longmaxi Formation shale gas in the Sichuan Basin: a) A different ratio of oil cracking gas and kerogen cracking gas mixed in the closed system at the high over-mature stage. b) The Longmaxi shales in WY and CN have had differential geothermal histories, especially in terms of the effects from the Emeishan Large Igneous Province (LIP), which have led to the discrepancy in evolution of the shales in the two areas. c) The heterogeneity of the Lower Silurian Longmaxi shales is another important factor, according to the noble gas data. d) Although shale gas is generated in closed systems, natural gas loss throughout geological history cannot be avoided, which also accounts for gas geochemical differences. This research offers some useful information regarding the theory of shale gas generation and evolution.

The origin of continental carbonates in Andean salars: A multi-tracer geochemical approach in Laguna Pastos Grandes (Bolivia)

In continental volcanic settings, abundant carbonate precipitation can occur with atypical facies compared to marine settings. The (bio-)chemical processes responsible for their development and early diagenesis are typically complex and not fully understood. In the Bolivian Altiplano, Laguna Pastos Grandes hosts a 40-km2 carbonate platform with a great diversity of facies and provides an ideal natural laboratory to understand the processes responsible for the precipitation of carbonates in a continental province dominated by volcanism. In order to trace the origin of both water and solutes in the lagoon, the major element and stable isotope compositions (δ2H-δ18O, δ37Cl, δ7Li, δ11B and 87Sr/86Sr) of the spring and stream waters were characterized, as well as the stable isotope compositions (δ13C, δ15N) and noble gas isotope ratios of hydrothermal gases associated with spring waters. The results show that thermal springs discharging on the carbonate platform are close to saturation with calcite. PHREEQC modeling, together with fluid geochemistry and temperature estimated from a combination of geothermometers, indicate that Ca in these springs is inherited from the alteration of the volcanic bedrock by aqueous fluids heated at ∼225 °C and enriched in magmatic mantle-derived CO2. Our results clearly show that the main driver for the precipitation of modern carbonates in Laguna Pastos Grandes is the deeply sourced CO2, which boosts the alteration of volcanic rocks at depth.

Magmatic fluids play a role in the development of active gas chimneys and massive gas hydrates in the Japan Sea

The Earth's marine continental margins hold significant amount of carbon in the form of gas hydrate which can interact dynamically with seawater and the atmosphere and potentially influence global climate. It is generally assumed that degradation of organic matter, through either biogenic or thermogenic processes, is responsible for the majority of the gas hydrate presently found in these deposits. We present stable isotope and noble gas results from gas hydrates in the eastern margin of the Japan Sea and compare them with previously published data regarding gases which are found nearby in deep hydrocarbon wells associated with Early Miocene igneous and sedimentary rocks. Our results show that most of the gases which accumulate in the hydrate can be described as a mixture between a deeply-sourced methane-rich thermogenic/crustal source (TC), a methane-rich admixture of biogenic gases with relatively shallow air-saturated seawater (BASW) and a methane-poor magmatic-mantle source (MM). The presence of hydrate with a mantle 3He/4He signatures indicates that fluids enriched in mantle gases are responsible for the mobilization of thermogenic gas within active Japan Sea chimney structures. The growth of primary hydrate at shallow marine sediment depths is ongoing, as is the cycling of gas to hydrate which is eventually buried and dissociated at the base of the gas hydrate stability zone, leading to large pockmark structures.

Mapping Fluid‐Filled Inclusions in Stalagmites Using Coupled X‐Ray and Neutron Computed Tomography: Potential as a Water Excess Proxy

AbstractApplication of novel proxies, such as the stable isotope compositions and noble gas concentrations of fossil drip water trapped as inclusions in stalagmites, have the potential to provide unique constraints on past hydroclimate states and surface temperatures. Geochemical analysis of inclusion waters, however, requires an understanding of the three‐dimensional spatial distribution of dominantly liquid‐ versus air‐filled inclusions in a given stalagmite. Here we couple neutron computed tomography and medium‐ to high‐resolution X‐ray computed tomography to map out the three‐dimensional calcite density and distribution of liquid‐ versus air‐filled inclusions within a Sierra Nevada stalagmite (ML‐1), which formed during the last deglaciation (18.5 to 11.7 ka). Comparison of coupled neutron computed tomography‐X‐ray computed tomography results with a time series of stalagmite calcite fabrics indicates that although highest density calcite contains abundant liquid (fluid)‐filled inclusions, calcite density and fabric overall were secondary controls on the liquid inclusion distribution (LID). Furthermore, a multistatistical evaluation of the stalagmite time series indicates a significant relationship at the multicentury‐ to millennial‐scale between LID and calcite δ18O and δ13C that suggests a potential link between LID and water availability to the cave.

Diamond-forming media through time – Trace element and noble gas systematics of diamonds formed over 3 billion years of Earth’s history

Ten individual gem-quality monocrystalline diamonds of known peridotite/eclogite paragenesis from Southern Africa (Koffiefontein, Letlhakane, Orapa) were studied for trace element concentrations and He and Ar abundances and isotopic compositions. In addition, two samples, consisting of pooled fragments of gem-quality peridotitic diamonds from Finsch and DeBeers Pool respectively, were analysed for noble gases. Previous studies (Richardson et al., 1984; Pearson et al., 1998; Gress et al., 2017; Timmerman et al., 2017) provided age constraints of 0.09, 1.0–1.1, 1.7, 2.3, and 3.2–3.4 Ga on mineral inclusions in the studied diamonds, allowing us to study trace elements and noble gases over 3 Gyr of geological time. Concentrations of trace elements in the diamonds are very low – a few hundred ppt to several tens of ppbs – and are likely dependent on the amount of sub-micron inclusions present. Trace element patterns and trace element/3He ratios of the studied monocrystalline diamonds are similar to those in fibrous diamonds, suggesting that trace elements and stable noble gas isotopes reside within the same locations in diamond and track the same processes that are reflected in the trace element patterns. We cannot discern any temporal differences in these geochemical tracers, suggesting that the processes generating them have been occurring over at least the past 2.3 Ga. 3He/4He ratios decrease and 4He and 40Ar* contents increase with increasing age of peridotitic and some eclogitic diamonds, showing the importance of in-situ radiogenic 4He and 40Ar ingrowth by the decay of U-Th-Sm and K respectively. For most gem-quality monocrystalline diamonds, uncertainties in the 3He/4He evolution of the continental lithospheric mantle combined with large analytical uncertainties and possible spatial variability in U-Th-Sm concentrations limit our ability to provide estimates of diamond formation ages using 4He ingrowth. However, the limited observed 4He ingrowth (low U + Th/3He) together with a R/Ra value of 5.3 for peridotitic diamond K306 is comparable to the present-day sub-continental lithospheric mantle value and supports the young diamond formation age found by Re-Os dating of sulphides in the same diamond by Pearson et al. (1998). After correction for in-situ radiogenic 4He produced since diamond formation a large variation in 3He/4He remains in ∼1 Ga old eclogitic diamonds that is suggested to result from the variable influence of subducted altered oceanic crust that has low 3He/4He. Hence, the 3He/4He isotope tracer supports an origin of the diamond-forming fluids from recycled oceanic crust for eclogitic diamonds, as indicated by other geochemical proxies.

Double Beta Decay Experiments With Loaded Liquid Scintillator

Liquid scintillator detectors have many properties which are highly advantageous for neutrino research at the MeV energy scale. There are various choices of additives to an organic liquid scintillator which typically function as the nuclear targets in a neutrino interaction. More recently, new techniques for loading a large amount of nuclei into liquid scintillator enable sensitive searches for double beta decay with various nuclei. KamLAND was an existing detector constructed for neutrino physics at the MeV scale, later upgraded to a sensitive detector for double beta decay (KamLAND-Zen). In this experiment, isotopically enriched xenon gas was loaded into the highly radiopure liquid scintillator. As xenon is a stable noble gas, the scintillation performance changes little, and it is safe for long-term use. To mitigate backgrounds, xenon was loaded only into the liquid scintillator in the central part of the detector, contained in a small nylon balloon. Owing to the large amount of xenon and low background level, the KamLAND-Zen experiment achieved the most sensitive search to date for neutrinoless double beta decay. The next phase of the experiment plans to increase the amount of xenon by almost double. In the future, sensitivity can be further enhanced by detector upgrades. SNO+ (successor to the Sudbury Neutrino Observatory) is a liquid scintillator detector that is currently being commissioned and will soon be taking data. Originally, SNO+ developed a technique to load neodymium into the liquid scintillator in order to conduct a double beta decay search with the isotope $^{150}$Nd. Later, SNO+ developed two new techniques that enable loading tellurium into liquid scintillator. The large natural abundance of $^{130}$Te and the ability to load tellurium at a significant concentration in the SNO+ liquid scintillator, while maintaining excellent scintillation optical properties, offer the prospect of a very sensitive search for neutrinoless double beta decay. This article will discuss both experiments, KamLAND-Zen and SNO+, highlighting the results achieved, the techniques involved in loading the liquid scintillator, and describing the purification of components of the loaded liquid scintillator to very low background levels.

The Xe‐SiO2 System at Moderate Pressure and High Temperature

AbstractXenon (Xe), the heaviest of the stable noble gases, is missing by a factor of 20 relatively to other noble gases, when comparing the Earth's and Mars's atmospheres with chondrites. In this work, the possibility of Xe retention in quartz, a major mineral of the continental crust, is tested. The Xe‐SiO2 system is investigated from 0.7 to 2.7 GPa and up to 1900 K, by in situ X‐ray powder diffraction and infrared spectroscopy. Experimental data are complemented by ab initio calculations to retrieve Xe incorporation mechanisms. An excess of quartz unit cell volume up to 4.2% is observed, consistent with a Xe for Si substitution in the quartz structure. Xe has a linear oxygen environment composed of two O atoms located at 1.98–2.00 Å from the Xe atom. Moreover, a new phase is evidenced above Xe melting curve at 0.8–1.0 GPa. The new (Xe,Si)O2 phase is orthorhombic and corresponds to an elongation of the quartz unit cell. In this phase, Xe substitutes for Si with a nearly planar oxygen environment composed of four O atoms located at 2.06–2.09 Å from the Xe atom. Xe incorporation in SiO2 proves to be significant, as previously shown for olivine. Xe incorporation is therefore expected to occur in the whole range of lithospheric silicate minerals. These findings emphasize the need to consider Xe incorporation in crust and upper mantle minerals as a process to store and fractionate xenon, in the framework of the “missing xenon” issue.