Noble Gas Concentrations Research Articles

Noble gas composition and 40Ar/39Ar age in eclogites from the main hole of the Chinese Continental Scientific Drilling project

We present the first comprehensive noble gas study on eclogites. The four eclogite samples were recovered during the Chinese Continental Scientific Drilling and are from two distinct profile depth sections differing in their degree of interaction with meteoric water, based on their δ 18O-values (surface related and of mantle-type). Hence, noble gas analyses offer the potential to further discriminate between shallow (meteoric) and deep (mantle) fluid sources. Noble gas compositions reveal typical crustal fluid compositions, characterized by a variable mixture of atmospheric gases with significant contributions of nucleogenic neon, radiogenic 4He*, radiogenic 40Ar*, fissiogenic 131–136Xe, and presumably bariogenic 131Xe, but no significant addition of mantle gases. This signature can be also considered to represent one endmember component of eclogitic diamonds. Concentrations of non-radiogenic noble gases are rather low, with depletion of light relative to the heavier noble gases. Eclogites from lower depth which experienced a higher degree of interaction with meteoric water also showed higher contributions of atmospheric gas compared with eclogites recovered from greater depth. This is interpreted to result from interaction with high-salinity fluids during ultrahigh pressure (UHP). It demonstrates that the atmospheric noble gas abundance is a proxy for interaction with surface related fluids. 40Ar/39Ar (inverse) isochron ages of two phengite separates (241.2 ± 0.4 Ma and 275.0 ± 1.8 Ma, 1σ-errors) predate the main phase of UHP metamorphism (ca. 220 Ma). Biotite yields an integrated age of about 1100 Ma. These age values are interpreted to reflect the likely addition of excess 40Ar without any chronological meaning.

Noble gases solubility models of hydrocarbon charge mechanism in the Sleipner Vest gas field

Noble gases are chemically inert and variably soluble in crustal fluids. They are primarily introduced into hydrocarbon reservoirs through exchange with formation waters, and can be used to assess migration pathways and mechanisms, as well as reservoir storage conditions. Of particular interest is the role groundwater plays in hydrocarbon transport, which is reflected in hydrocarbon–water volume ratios. Here, we present compositional, stable isotope and noble gas isotope and abundance data from the Sleipner Vest field, in the Norwegian North Sea. Sleipner Vest gases are generated from primary cracking of kerogen and the thermal cracking of oil. Gas was emplaced into the Sleipner Vest from the south and subsequently migrated to the east, filling and spilling into the Sleipner Ost fields. Gases principally consist of hydrocarbons (83–93%), CO2 (5.4–15.3%) and N2 (0.6–0.9%), as well as trace concentrations of noble gases. Helium isotopes (3He/4He) are predominantly radiogenic and range from 0.065 to 0.116RA; reported relative to air (RA=1.4×10−6; Clarke et al., 1976; Sano et al., 1988), showing predominantly (>98%) crustal contributions, consistent with Ne (20Ne/22Ne from 9.70 to 9.91; 21Ne/22Ne from 0.0290 to 0.0344) and Ar isotopes (40Ar/36Ar from 315 to 489). Air-derived noble gas isotopes (20Ne, 36Ar, 84Kr, 132Xe) are introduced into the hydrocarbon system by direct exchange with air-saturated water (ASW). The distribution of air-derived noble gas species are controlled by phase partitioning processes; in that they preferentially partition into the gas (i.e., methane) phase, due to their low solubilities in fluids. Therefore, the extent of exchange between hydrocarbon phases and formation waters – that have previously equilibrated with the atmosphere – can be determined by investigating air-derived noble gas species. We utilize both elemental ratios to address process (i.e., open vs. closed system) and concentrations to quantify the extent of hydrocarbon–water exchange (i.e., volumetric gas–water ratios). These data are discussed within the framework of several conceptual models: (i) total gas-stripping model, which assumes all noble gases have been stripped from the water phase, thus defining the minimum volume of water to have interacted with the hydrocarbon phase; (ii) equilibrium model, which assumes equilibration between groundwater and hydrocarbon phase at reservoir P, T and salinity; and (iii) open and closed system gas-stripping models, using concentrations and elemental ratios. By applying these models to Ne–Ar data from Sleipner, we estimate volumetric gas–water ratios VgVw between 0.02 and 0.07, which are lower than standard geologic gas–water estimates of ∼0.24, estimated by combining gas-in-place estimates with groundwater porosity estimates. Sleipner Vest data can be best approximated by an open system model, which predicts more than an order of magnitude more groundwater interaction during migration than geologic estimates, indicating a dynamic aquifer system and/or a hydrous migration pathway. In an open system, the extent of gas loss can be estimated to be between 8 and 10 reservoir volumes, which have passed through the system and been lost (i.e., filled and spilled).

Inherent Tracers for Carbon Capture and Storage in Sedimentary Formations: Composition and Applications

Inherent tracers-the "natural" isotopic and trace gas composition of captured CO2 streams-are potentially powerful tracers for use in CCS technology. This review outlines for the first time the expected carbon isotope and noble gas compositions of captured CO2 streams from a range of feedstocks, CO2-generating processes, and carbon capture techniques. The C-isotope composition of captured CO2 will be most strongly controlled by the feedstock, but significant isotope fractionation is possible during capture; noble gas concentrations will be controlled by the capture technique employed. Comparison with likely baseline data suggests that CO2 generated from fossil fuel feedstocks will often have δ(13)C distinguishable from storage reservoir CO2. Noble gases in amine-captured CO2 streams are likely to be low concentration, with isotopic ratios dependent on the feedstock, but CO2 captured from oxyfuel plants may be strongly enriched in Kr and Xe which are potentially valuable subsurface tracers. CO2 streams derived from fossil fuels will have noble gas isotope ratios reflecting a radiogenic component that will be difficult to distinguish in the storage reservoir, but inheritance of radiogenic components will provide an easily recognizable signature in the case of any unplanned migration into shallow aquifers or to the surface.

How Do the Deep Waters of the Antarctic Form?

Researchers uncover new insights into the life cycle of water in the Antarctic region by measuring noble gas concentrations.

The origin of N2-H2-CH4-rich natural gas seepages in ophiolitic context: A major and noble gases study of fluid seepages in New Caledonia

The study of natural gas seepages in New Caledonia has shown the occurrence of two gas families, one is N2-H2-CH4-rich, the other is N2-rich. The N2-H2-CH4-rich gases are bubbling in hyperalkaline springs (OH–-rich) known in the peridotite massif of the southern part of the island. This family of gas shows contents of N2 between 50 and 62%, H2 between 26 and 36%, and CH4 between 11 and 16%. δ13C values of methane are ranging from −39 to −32‰. We interpret the origin of H2 as a product of fluid-rock interaction between basic-ultrabasic rocks and water with oxidation of Fe2+ and reduction of underground water in the fracture system of the peridotites nappe. Methane is interpreted as the result of a reduction of dissolved inorganic and/or organic carbon in subsurface aquifers. The second family of gas emissions was found in thermal springs in the sedimentary units located structurally below the peridotites nappe. The gas is composed mostly of N2 (between 97 and 98%) associated with relatively high concentration of He. Both gas families show notably high N2 vs fossil noble gas contents (36Ar, 20Ne, 84Kr) suggesting that N2 is not directly issued from gas dissolved in aquifers equilibrated with atmosphere but most likely finds its origin in a deep source, probably within metamorphic sediments which are tectonically buried below the ophiolitic nappe. We interpret the N2-H2-CH4-rich family of gas as a result of a mixing between two end-members, (1) a H2-CH4-rich pole issued from the weathering of peridotite rocks and (2) a N2-rich pole which would be issued from the metamorphosed sediments buried below the ophiolitic units. An unusual inverse correlation between the atmospheric noble gas isotopes 20Ne and 36Ar is interpreted as the result of a degassing of a relatively shallow confined aquifer related to a bubble flow from depth.

Accelerated ageing and durability of double-glazed sealed insulating window panes and impact on heating demand in buildings

A crucial property for double-glazed sealed insulating window panes is to maintain their thermal insulating properties and thus low U-values. However, degradation and thus subsequent reduction or loss of low-conductance gas concentration may occur in the sealed glazing units by their exposure to outdoor climate.The choice of spacers is important to keep as low thermal transport through the window panes as possible, i.e. low U-value. In addition, the type of spacers may also influence their durability and resistance towards ageing, which hence may be characterized by the low-conductance noble gas concentration, e.g. argon, krypton or xenon. Ageing and degradation of window panes may lead to a decreased or total loss of noble gas concentration and hence subsequent increased heating energy demand in buildings.Thus, several double-glazed sealed insulating window panes, with aluminium spacers and Super Spacers, have been subjected to accelerated ageing by climate ageing and elevated temperature ageing. The durability and ageing of the sealed window panes have been studied and characterized by their spacer type and gas concentration. Furthermore, the decrease of gas concentration in sealed insulating window panes and the impact on the energy performance and in particular heating demand of buildings have been investigated.

Flood-Controlled Excess-Air Formation Favors Aerobic Respiration and Limits Denitrification Activity in Riparian Groundwater

The saturated riparian zones of rivers act as spatially and temporally variable biogeochemical reactors. This complicates the assessment of biogeochemical transport and transformation processes. During a flood event, excess-air formation, i.e. the inclusion and dissolution of air bubbles into groundwater, can introduce high amounts of dissolved O2 and thereby affect biogeochemical processes in groundwater. With the help of a field-installed membrane-inlet mass-spectrometer we resolved the effects of flood induced excess-air formationon organic carbon and nitrogen transformations in groundwater of different riparian zones of a restored section of the River Thur, Switzerland. The results show that the flood event triggered high aerobic respiration activity in the groundwater below a zone densely populated with willow plants. The flood introduced high concentrations of O2 (230 µmol L–1) to the groundwater through the formation of excess air and transported up to ~400 µmol L 1 organic carbon from the soil/root layer into groundwater during the movement of the water table. A rapid respiration process, quantified via the measurements of O2, CO2 and noble-gas concentrations, led to fast depletion of the introduced O2 and organic carbon and to high CO2 concentration (590 µmol L–1) in the groundwater shortly after the flood. The synchronous analysis of different nitrogen species allowed studying the importance of denitrification activity. The results indicate that in the willow zone excess-air formation inhibited denitrification through high O2 concentration input. Instead, the observed decrease in nitrate concentration (~50 µmol N L 1) may be related to fostered nitrate uptake by plants. In the other riparian zones closer to the river, no significant excess-air formation and corresponding respiration activity was observed. Overall, analyzing the dissolved gases in the groundwater significantly contributed to deciphering biogeochemical processes in the riparian aquifer characterized by pronounced changes in the flow regime and by spatial heterogeneity of the vegetation. Measuring excess-air formation helped identifying and explaining the low denitrification activity in a zone with high organic carbon turnover and to quantify organic carbon sources.

Halogens and noble gases in Mathematician Ridge meta-gabbros, NE Pacific: implications for oceanic hydrothermal root zones and global volatile cycles

Six variably amphibolitised meta-gabbros cut by quartz–epidote veins containing high-salinity brine, and vapour fluid inclusions were investigated for halogen (Cl, Br, I) and noble gas (He, Ne, Ar, Kr, Xe) concentrations. The primary aims were to investigate fluid sources and interactions in hydrothermal root zones and determine the concentrations and behaviours of these elements in altered oceanic crust, which is poorly known, but has important implications for global volatile (re)cycling. Amphiboles in each sample have average concentrations of 0.1–0.5 wt% Cl, 0.5–3 ppm Br and 5–68 ppb I. Amphibole has Br/Cl of ~0.0004 that is about ten times lower than coexisting fluid inclusions and seawater, and I/Cl of 2–44 × 10−6 that is 3–5 times lower than coexisting fluid inclusions but higher than seawater. The amphibole and fluid compositions are attributed to mixing halogens introduced by seawater with a large halogen component remobilised from mafic lithologies in the crust and fractionation of halogens between fluids and metamorphic amphibole formed at low water–rock ratios. The metamorphic amphibole and hydrothermal quartz are dominated by seawater-derived atmospheric Ne, Ar, Kr and Xe and mantle-derived He, with 3He/4He of ~9 R/Ra (Ra = atmospheric ratio). The amphibole and quartz preserve high 4He concentrations that are similar to MORB glasses and have noble gas abundance ratios with high 4He/36Ar and 22Ne/36Ar that are greater than seawater and air. These characteristics result from the high solubility of light noble gases in amphibole and suggest that all the noble gases can behave similarly to ‘excess 40Ar’ in metamorphic hydrothermal root zones. All noble gases are therefore trapped in hydrous minerals to some extent and can be inefficiently lost during metamorphism implying that even the lightest noble gases (He and Ne) can potentially be subducted into the Earth’s mantle.

Spreading of Greenland meltwaters in the ocean revealed by noble gases

AbstractWe present the first noble gas observations in a proglacial fjord in Greenland, providing an unprecedented view of surface and submarine melt pathways into the ocean. Using Optimum Multiparameter Analysis, noble gas concentrations remove large uncertainties inherent in previous studies of meltwater in Greenland fjords. We find glacially modified waters with submarine melt concentrations up to 0.66 ± 0.09% and runoff 3.9 ± 0.29%. Radiogenic enrichment of Helium enables identification of ice sheet near‐bed melt (0.48 ± 0.08%). We identify distinct regions of meltwater export reflecting heterogeneous melt processes: a surface layer of both runoff and submarine melt and an intermediate layer composed primarily of submarine melt. Intermediate ocean waters carry the majority of heat to the fjords' glaciers, and warmer deep waters are isolated from the ice edge. The average entrainment ratio implies that ocean water masses are upwelled at a rate 30 times the combined glacial meltwater volume flux.

Glacial–interglacial temperature change in the tropical West Pacific: A comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquid–vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O (‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glacial–interglacial cycles (Marine Isotope Stages (MIS) 12–9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquid–vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion δ18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion δ18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glacial–interglacial temperature change, indicating temperature shifts of 4–5 °C. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

Noble gases in sulfide deposits of modern deep-sea hydrothermal systems: Implications for heat fluxes and hydrothermal fluid processes

Studies of noble gases in seafloor sulfide deposits are an important tool for understanding the origin of ore-forming fluids, both enabling the determination of noble gas sources and revealing the degree of fluid–rock interaction and mantle degassing. The noble gas concentrations and isotopic compositions of 27 sulfide, 3 sulfate, and 2 opal mineral aggregate samples have been studied in different hydrothermal fields from the East Pacific Rise, Mid-Atlantic Ridge, Central Indian Ridge, Southwest Indian Ridge, and North Fiji Back-Arc Basin. The helium concentrations and isotopic ratios in the sulfide aggregate samples are variable (4He 0.12 to 22×10−8cm3 STP/g; 3He/4He ~0.6 to 10.4 Ra), and most of the sulfide helium concentrations are higher than those in the opal mineral samples (4He 0.017 and 0.028×10−8cm3 STP/g), suggesting that the low-temperature fluids have lost their mantle helium during cooling. The helium of high (>7 Ra), medium (1–7 Ra), and low (≈1 Ra) 3He/4He ratio samples is derived mainly from the MORB or OIB mantle by magma degassing, from mixing between hydrothermal fluid and seawater during ore-forming processes, and from ambient seawater, respectively. The high 3He/4He ratios (>7 Ra) of sulfides imply that high-temperature sulfides retain the helium isotopic compositions of the primary hydrothermal fluid, whereas low-temperature sulfides, sulfates, and opal minerals do not.The neon, argon, krypton, and xenon concentrations in the sulfide aggregate samples are also variable; in most of the sulfide aggregates, they are significantly lower than in the sulfate and opal mineral samples. It is known that barite and opal minerals are characteristic of low-temperature (<200°C) paragenetic associations, indicating that heavier noble gases (Ne, Ar, Kr and Xe) are enriched under low-temperature conditions. Most of the sulfide, sulfate and opal mineral aggregate samples possess heavy noble gas elemental abundances similar to those of air-saturated seawater and Ne, Ar, and Xe isotopic compositions that span narrow ranges around atmospheric values, an observation which is most easily explained by the dominance of a seawater-derived component.In addition, based on the calculated helium/heat ratios, global helium and heat fluxes to high-temperature hydrothermal vents are approximately 0.05–6×104kg per year and 0.1–12×1012W, meaning that roughly 0.3% of ocean heat is supplied by seafloor high-temperature hydrothermal activity.

Insights into controls on hexavalent chromium in groundwater provided by environmental tracers, Sacramento Valley, California, USA

Environmental tracers are useful for determining groundwater age and recharge source, yet their application in studies of geogenic Cr(VI) in groundwater has been limited. Environmental tracer data from 166 wells located in the Sacramento Valley, northern California, were interpreted and compared to Cr concentrations to determine the origin and age of groundwater with elevated Cr(VI), and better understand where Cr(VI) becomes mobilized and how it evolves along flowpaths. In addition to major ion and trace element concentrations, the dataset includes δ18O, δ2H, 3H concentration, 14C activity (of dissolved inorganic C), δ13C, 3He/4He ratio, and noble gas concentrations (He, Ne, Ar, Kr, Xe). Noble gas recharge temperatures (NGTs) were computed, and age-related tracers were interpreted in combination to constrain the age distribution in samples and sort them into six different age categories spanning from <60yr old to >10,000yr old. Nearly all measured Cr is in the form of Cr(IV). Concentrations range from <1 to 46μgL−1, with 10% exceeding the state of California’s Cr(VI) maximum contaminant level of 10μgL−1. Two groups with elevated Cr(VI) (⩾5μgL−1) were identified. Group 1 samples are from the southern part of the valley and contain modern (<60yr old) water, have elevated NO3− concentrations (>3mgL−1), and commonly have δ18O values enriched relative to local precipitation. These samples likely contain irrigation water and are elevated due to accelerated mobilization of Cr(VI) in the unsaturated zone (UZ) in irrigated areas. Group 2 samples are from throughout the valley and typically contain water 1000–10,000yr old, have δ18O values consistent with local precipitation, and have unexpectedly warm NGTs. Chromium(VI) concentrations in Group 2 samples may be elevated for multiple reasons, but the hypothesis most consistent with all available data (notably, the warm NGTs) is a relatively long UZ residence time due to recharge through a deep UZ near the margin of the basin. A possible explanation for why Cr(VI) may be primarily mobilized in the UZ rather than farther along flowpaths in the oxic portion of the saturated zone is more dynamic cycling of Mn in the UZ due to transient moisture and redox conditions.

Evidence of groundwater degassing in a deep confined aquifer: noble gas concentrations with hydrogen, oxygen and carbon isotope data

“Excess air” caused by the excessive dissolution of air bubbles is often observed and discussed in groundwater studies [e.g., noble gas temperature (NGT) calculations and 4He dating]. However, “gas loss” is inevitable for groundwater degassing whenever temperatures change or the groundwater head fluctuates, which can lead to a misunderstanding of the initial gas content, resulting in the false assessment of groundwater recharge temperature and age. Twenty-two groundwater samples were observed with a He and Ne excess, Kr loss, and Ar and Xe excess and loss in different samples from the third aquifer of the North China Plain. The loss of Kr and Xe in groundwater samples indicated that groundwater degassing had occurred, because the loss of Ne, Ar, Kr, and Xe in sequences in groundwater is caused by a continuous degassing. A temperature increase can also cause groundwater degassing, for the recharge groundwater temperatures (δD-calculated 0.6–5.0 °C) are much lower than the NGTs (3.4–32.1 °C) in the same groundwater samples. All the groundwater were speculated to have uniformly experienced temperatures as high as 32.1 °C in the recharge zone before entering the third aquifer and resulted in groundwater degassing.

Attenuation of diffusive noble-gas transport in laminated sediments of the Stockholm Archipelago

A sediment core has been sampled at a spatial resolution of about two centimeters for noble-gas analysis of the sediment pore water. This high-resolution sampling allowed an excess of dissolved atmospheric gases to be identified in the pore water at a sediment depth of 40 cm. Sedimentological evidence indicates that the observed gas excess is related to a past mass movement that trapped and conserved the gas surplus for more than a century. The measured noble-gas concentrations support the hypothesis that, depending on the sediment texture or particular structures in the sediment, the transport of noble gases in the pore space can be significantly attenuated compared to molecular diffusion in bulk water. The atmospheric noble-gas abundance in the pore water allows the deposition of sediments originally located near the air/water interface to be identified. Although the nature of the physical processes that limit the fluid transport in the pore space could not be fully assessed, our observations indicate that noble-gas concentration profiles can be archived for unexpectedly long times in specific sedimentary sequences. This finding represents a significant step forward in the interpretation of noble-gas concentrations in sediment pore waters in terms of past environmental conditions.

The search for an underground nuclear test

In a month-long exercise, the on-site inspection capabilities of the Comprehensive Nuclear-Test-Ban Treaty Organization were put to the test.

Noble gases, nitrogen, and methane from the deep interior to the atmosphere of Titan

Titan’s thick N2–CH4 atmosphere is unlike any in the Solar System, and its origin has been shrouded in mystery for over half a century. Here, I perform a detailed analysis of chemical and isotopic data from the Cassini–Huygens mission to develop the hypothesis that Titan’s (non-photochemical) atmospheric gases came from deep within. It is suggested that Titan’s CH4, N2, and noble gases originated in a rocky core buried inside the giant satellite, and hydrothermal and cryovolcanic processes were critical to the creation of Titan’s atmosphere. Mass balance and chemical equilibrium calculations demonstrate that all aspects of this hypothesis can be considered geochemically plausible with respect to contemporary observational, experimental, and theoretical knowledge. Specifically, I show that a rocky core with a bulk noble gas content similar to that in CI carbonaceous meteorites would contain sufficient 36Ar and 22Ne to explain their reported abundances. I also show that Henry’s law constants for noble gases in relevant condensed phases can be correlated with the size of their atoms, which leads to expected mixing ratios for 84Kr (∼0.2ppbv) and 132Xe (∼0.01ppbv) that can explain why these species have yet to be detected (Huygens upper limit <10ppbv). The outgassing of volatiles into Titan’s atmosphere may be restricted by the stability of clathrate hydrates in Titan’s interior. The noble gas geochemistry also provides significant new insights into the origin of N2 and CH4 on Titan, as I find that Ar and N2, and Kr and CH4 should exhibit similar phase partitioning behavior on Titan. One implication is that over 95% of Titan’s N2 may still reside in the interior. Another key result is that the upper limit from the Huygens GC–MS on the Kr/CH4 ratio in Titan’s atmosphere is far too low to be consistent with accretion of primordial CH4 clathrate, which motivates me to consider endogenic production of CH4 from CO2 as a result of geochemical reactions between liquid water and anhydrous rock (i.e., serpentinization). I show that sufficient CH4 can be produced to replenish Titan’s atmosphere many times over in the face of irreversible photolysis and escape of CH4, which is consistent with the favored model of episodic cryovolcanic outgassing. There should also have been enough NH3 inside Titan so that its thermal decomposition in a hot rocky core can generate the observed atmospheric N2, and if correct this model would imply that Titan’s interior has experienced vigorous hydrothermal processing. The similarity in 14N/15N between cometary NH3 and Titan’s N2 is consistent with this picture. As for the isotopes in CH4, I show that their observed relative abundances can be explained by low-temperature (∼20°C) equilibria with liquid water (D/H) and the expected aqueous alteration mineral calcite (12C/13C), provided that nickel was present to catalyze isotopic exchange over geologic timescales. The present hypothesis is chemically and isotopically consistent with the Cassini–Huygens data, and it implies that the formation of Titan’s atmosphere would have been an unavoidable consequence of volatile processing that was driven by the geophysical evolution of the interior. If all of the atmospheric N2 and CH4 have an endogenic origin, then no more than ∼1.6 times the present amount of N2 can be lost by photochemistry and escape over the history of the atmosphere; and the D/H ratio in Titan’s water should be much lower than that in Enceladus’ plume. Given its important implications to the origin and evolution of volatiles in the outer Solar System, we must go back to Titan to acquire additional isotopic data that will allow more rigorous tests of models of the origin of its atmosphere. I predict the following isotopic ratios: 20Ne/22Ne≈8.9, 36Ar/38Ar≈5.3, (14N/15N)NH3≈130–170, (12C/13C)CO2≈84, (D/H)H2O≈1.7×10-4; and recommend that future in situ instrumentation have the capability to measure the rare isotopologues of N2 and CH4, which represent previously unconsidered but potentially valuable sources of geochemical information on the origin and evolution of Titan’s atmosphere.

Disequilibrium degassing model determination of the 3He concentration and 3He/22Ne of the MORB and OIB mantle sources

Models of the dynamics of eruptive degassing provide a unique insight into the pre-eruptive concentrations of the major volatiles (CO2, H2O), noble gases, and the mantle reservoirs supplying them: a fundamental component in describing the accretion and evolution of the Earth. We investigate and develop a disequilibrium degassing model, exploring the parameters required to reproduce noble gas compositions observed in two ocean island basalt (OIB) and one mid-ocean ridge basalt (MORB) sample suites from the East Pacific Rise (EPR), Loihi Seamount, and Iceland. The original model assumed an identical loss of major volatile components for each degassing step (Gonnermann and Mukhopadhyay, 2007). We recalculate the major volatile vapor phase composition for each degassing step, taking account of the degassing history over previous steps. Final noble gas elemental ratios, using the same eruption parameters, can differ by orders of magnitude from the original model's calculations. We further adapt our model variant to take into account both decompression-driven degassing during magma ascent and degassing at constant pressure during sample quenching. Our results show that elemental ratios and noble gas concentrations can be effectively decoupled by the different degassing stages of an eruption. Ascent rate determines whether degassing during magma ascent is modeled as predominantly closed or open system degassing. The closed system conditions that dominate the slowly ascending MORB result in a less dramatic decrease in degassed elemental ratios than for the OIB models, consistent with the observed data. The MORB model also constrains the initial MORB source melt 3He/22Ne ratio, allowing that the MORB mantle could have a ratio as low as the OIB ratio, a feature required by steady state mantle models. The two OIB sample suites show very similar noble gas ratios and concentrations despite a large difference in final eruption pressures. We propose that this can fit our model if the effect of gas loss by quenching is negligible. Our model then shows that only a small amount of degassing takes place during magma ascent, meaning that initial OIB He melt concentrations must be similar to or lower than MORB source melt concentrations, although greater initial CO2 concentrations are required. This result is entirely consistent with mantle models which see a significant recycled component in the OIB-source mantle: such material would be expected to have higher CO2 but lower 3He concentrations than the depleted mantle.

Characteristics of noble gases in the large Gaoshiti-Moxi gas field in Sichuan Basin, SW China

Abstract Taking the large Gaoshiti-Moxi gas field of Sichuan Basin as an example, the total composition contents and isotopes of noble gases in the natural gases from the Sinian Dengying Formation and Cambrian Longwangmiao Formation are analyzed, and then their geneses are identified. The content value of helium in the natural gases of the large Gaoshiti-Moxi gas field is generally 1-2 orders of magnitude higher than that of air, and the average content in the second member of the Dengying Formation is 512×10−6, reaching the industrial utilization standard. The content values of Neon, Argon, Krypton and Xenon are relative low, lower than the corresponding content value in air. The total composition contents of noble gases in the natural gas of the large Gaoshiti-Moxi gas field gradually reduce in the sequence of the second member of Dengying Formation, the fourth memeber of Dengying Formation, and Cambrian Longwangmiao Formation. The noble gases 3He/4He value in the natural gases of the large Gaoshiti-Moxi gas field is in 10−8 order of magnitude, the 40Ar/36Ar value is usual from 1 024 to 9 559, 132Xe is relatively surplus and 129Xe is relatively loss. The comprehensive genetic identification of Helium, Argon, Xenon indicates that the noble gases in the large Gaoshiti-Moxi gas field are typical crustal source genesis, and the study area has stable tectonic background and does not have active deep fractures or mantle connecting fractures.

Noble gases in the sediments of Lake Van – solute transport and palaeoenvironmental reconstruction

Sediment samples acquired in 2010 from the long cores of the International Continental Scientific Drilling Program (ICDP) PaleoVan drilling project on Lake Van for noble-gas analysis in the pore water allow determination of the local terrestrial He-gradient as a function of depth within a sediment column of more than 200 m. These measurements yield first insights into the physical transport mechanisms of terrigenic He through the uppermost part of unconsolidated lacustrine sediments overlying the continental crust.In line with our previous work on the spatial distribution of the terrigenic He release into Lake Van, we identify a high He concentration gradient in the uppermost 10 m of the sediment column. The He concentration gradient decreases below this depth down to approx. 160m following in general the expectations of the modelling of radiogenic He production and transport in a sediment column with homogeneous fluid transport properties. Overall the in-situ radiogenic He production due to the decay of U and Th in the mineral phases of the sediments accounts for about 80% of the He accumulation. At approx. 190m we observe a very high He concentration immediately below a large lithological unit characterised by strong deformations. We speculate that this local enrichment is the result of the lower effective diffusivities in the pore space that relate to the abrupt depositional history of this deformed unit. This particular lithological unit seems to act as a barrier that limits the transport of solutes in the pore space and hence might “trap” information on the past geochemical conditions in the pore water of Lake Van.The dissolved concentrations of atmospheric noble gases in the pore waters of the ICDP PaleoVan cores are used to geochemically reconstruct salinity on the time scale of 0–55 ka BP. Higher salinities in the pore water at a depth of about 20 m suggest a significantly lower lake level of Lake Van in the past.

Composition and sources of volatiles and noble gases in fluid inclusions in pyroxenites and carbonatites of the Seblyavr Massif, Kola Peninsula

Carbonatites and related pyroxenites from the Seblyavr alkaline-ultramafic massif were analyzed for isotopic composition and concentrations of carbon (in carbon dioxide), nitrogen, and noble gases using the stepwise crushing technique. The C isotopic composition in crushing steps of calcite from the carbonatite varies from −6.6 to −15.0‰ (PDB) with average values from −8.5 to −10.5‰, which is lower than the mantle range for $\delta ^{13} C_{(CO_2 )} $ (from −3 to −5‰) and can likely be explained by long-term isotopic exchange between the carbon of CO2 in inclusions and their host Ca carbonate. The 40Ar/36Ar ratios in the crushing extractions of the calcites vary from the atmospheric value of 296 to 3200. Diopside from the pyroxenite has these ratios as high as 26000–33000 (such high values for pyroxenite in the Kola alkaline-ultramafic province have been obtained for the first time), which corresponds to the values obtained for MORB chilled glasses. Nitrogen in the samples is isotopically heavy, δ15N from +1 to +2 on average, which is consistent with earlier data on carbonatite massifs in the Kola alkaline province (Dauphas and Marty, 1999) and carbonatites of the Guli Massif (Buikin et al., 2011). The N2 content in the crushing extractions is correlated with the 36Ar concentration, which is an indicator of atmospheric contamination and suggests the dominance of the crustal N component in the samples, likely as a result of subduction or penetration of the ancient meteoric water into the magma chamber or a metasomatic source. The variations in the isotopic and elemental composition of the gas components between crushing steps suggest that the investigated samples contain inclusions of at least two populations.