Noble Gas Concentrations Research Articles

Mantle helium in pore fluids of deep-sea sediments around the Azores archipelago

We present noble gas concentrations and helium isotope ratios measured in the pore fluids of two deep-sea sediment cores taken at the Azores Plateau. NeXe concentrations were used to estimate the atmospheric noble gas component within the pore fluids and to then determine the terrigenic helium component. The concentrations of terrigenic 3He indicate the presence of hydrothermal fluids and a mantle He component within the sediment pore space. At both sampling locations, the concentration of terrigenic helium increases with sediment depth. The observed concentration gradients suggest a diffusive transport of He through the sediments. The helium isotope ratio of the source of the terrigenic helium is characterized by a typical mid-ocean ridge basalt (MORB). These results support previous studies suggesting that the pelagic sediments surrounding the Azores host active hydrothermal systems.Our data indicate that the transport of terrigenic helium takes place diffusively over larger areas of the ocean floor, and that the concentration of terrigenic helium in the pelagic sediments increases towards the Mid-Atlantic Ridge and Terceira Rift.The data further suggests that in the Azores region the terrigenic noble gas component is only detectable in the sediment pore fluids and cannot be observed in the overlying bottom water. This highlights the potential of measuring noble gas concentrations and isotope ratios in the sediment column to identify hydrothermal activity in the ocean.

Noble gases in shallow aquifers preserve signatures of boiling events beneath Weishan volcano of Wudalianchi volcanic field, northeast China

The study on whether there is a magma chamber under Wudalianchi is a hot topic recently, as it holds great significances for the theory of plate tectonics, early warning of volcano eruption and geothermal exploration. There is no near surface geothermal abnormality reported in Weishan, the widely used and well-studied tool, geochemistry of geothermal fluids and geothermal gases, cannot be applied to this area. To reveal the thermal conditions under Weishan, we conducted a study about the abundances and isotope ratios of dissolved noble gases in shallow groundwater and springs of Weishan. The concentrations of noble gases display obvious Ne excesses and mass-dependent differentiation, the isotopic ratios indicate that Ne, Ar, Kr, and Xe are atmosphere-derived noble gases (ANGs). We apply the closed-system equilibrium (CE) model to process the data of noble gases, and indicate that the excess ANGs are not caused by the increased hydrostatic pressure or diffusive influx. Neither meltwater mixing nor oxygen consumption alone could generate sufficient noble gas excesses in our samples. Based on the reconstructed abundances of noble gases in vapor phases produced at different boiling temperatures, which are calculated according to the boiling model established on Henry's law, we conclude that the abundances of noble gases in these samples were influenced by vapor–liquid partition caused by underground boiling. The diagrams of 84Kr/36Ar, 20Ne/36Ar and 130Xe/36Ar confine the temperature range where the boiling events occur in ∼100 °C–300 °C. We argued that the excess ANGs in shallow groundwater are geochemical evidence of boiling events, which seems to be continuously happening during the time range confined by the young groundwater in basalt aquifer and old groundwater in sandstone aquifer. Our findings also corroborate the recent results of geophysical survey works that a potential magma chamber exists under Weishan area. We suggest that noble gases dissolved in shallow aquifers represent a reliable geochemical tool to unveil subsurface geothermal state, where no near-surface thermal anomaly occurs.

Geochemical Characteristics and Gas Source Contributions of Noble Gases of the Sulige Large Tight Gas Field of Upper Paleozoic in Ordos Basin, China

Tight gas is the fastest developing unconventional natural gas resource, becoming the principal part for gas reserves and production growth in China. The Sulige gas field is the largest gas field and also the typical low porosity and low permeability tight sandstone gas field discovered in China, with an annual natural gas output exceeding 300 billion and cumulative output exceeding 290 billion, playing an important role in ensuring national energy provision, helping China’s energy transformation, and promoting green, low-carbon, environmental protection and high-quality development. Based on sample collection and laboratory analysis, natural gas compositions including hydrocarbons, non-hydrocarbons, light hydrocarbons, and noble gases of the Sulige gas field are systematically analyzed, their genetic identifications are identified, and finally gas source originations and contribution proportions are comprehensively discussed from the perspectives of noble gases and hydrocarbon gases. The main achievements are as follows: 1) natural gases in the Sulige gas field are mainly alkane gases, with high methane content, high drying coefficient, low heavy hydrocarbon contents, low non-hydrocarbon gas contents of CO2 and N2, and relatively low noble gas contents. The helium content is relative 2 order of magnitude higher than the atmospheric value, while neon, argon, krypton, and xenon are relatively about 1–2 orders of magnitudes lower than the atmospheric values. 2) The carbon and hydrogen isotopes of alkanes are generally positive sequence distributions with some part inversion. The 3He/4He values are mainly distributed in magnitude of 10−8, the 40Ar/36Ar is ranged from 506 to 1940, the 129Xe is relative loss, and the 132Xe is relative surplus. 3) Natural gases in the Sulige gas field are typical coal-formed gases generated from a humic organic mother material with maturity from high mature to over mature according to C7 and C8 light hydrocarbons and alkane carbon isotopes. Noble gases are typical crustal genesis, mainly originating from the radioactive decay of crustal source materials. 4) The gas source correlations of noble gases and alkane gases and their quantitative evaluations on source contributions show that natural gases in the Sulige gas field are originated from Carboniferous-Permian coal measure source rocks in Ordos Basin, mainly contributed by coals and supplemented by mudstones, accounting for 55–60% and 40–45%, respectively.

Noble gases, cosmic ray exposure and radiogenic ages in selected ordinary chondrites

Noble gas isotopic ratios and concentrations provide powerful constrains on the nature of trapped component presence in the meteorites. Concentrations and isotopic composition of the noble gases (He, Ne, Ar, Kr and Xe) in eleven bulk ordinary chondrites (OCs), Mahadevpur (H4/5), Didwana-Rajod (H5), Monahans (1998) (H5), Portales Valley (H6), Itawa Bhopji (L3-5), Jodiya (L5), Jalangi (L5/6), Kaprada (L5/6), Devri-Khera (L6), Katol (L6) and Bruderheim (L6) are presented. The aim of the study is to examine the exposure history and radiogenic ages of the recent meteoritic falls. The results of stepwise heating analyses indicate that noble gases are mixture of trapped and cosmic ray produced. Neon isotopes are enriched from galactic cosmic ray (GCR) produce gas, but many samples show a Q-type contribution. Argon isotopes show 40Ar excesses (40Ar/36Ar up to (42.6 ± 0.2) × 104), which is the decay product of 40K. Measured Kr and Xe isotopes in all the studied OCs predominantly shows Q component. Minor contribution from primordial noble gases of HL component is also observed in stepwise heating extractions in few cases. Solar gases are absent in the specimens studied here. The cosmic-ray exposure (CRE) ages of the OCs range from 5.2 ± 0.9 Ma to 36.3 ± 6.7 Ma. These ages are within the range typically observed for the respective meteorite types of OCs. However, the CRE ages of many meteorites are inconsistent with peaks in the exposure age histogram for respective sub classes of OCs, H and L types. The nominal radiogenic age obtained from 40Ar ranges between 0.87 ± 0.09 Ga to 4.57 ± 0.46 Ga in the meteorites with exception of two meteorites. The 4He gas retention ages for the OCs are in the range 0.27 ± 0.03 Ga to 4.40 ± 0.50 Ga, showing different degree of degassing either at a thermal event on the parent body. Radiogenic 129Xe from the decay of 129I was observed in all the studied samples of OCs.

Regional-Scale Distribution of Helium Isotopes in Aquifers: How Informative Are They as Groundwater Tracers and Chronometers?

This study presents an almost entirely unpublished dataset of 121 samples of groundwater analyzed for helium concentration and its isotopic ratio (3He/4He) in two adjacent watersheds of the St. Lawrence Lowlands, in a region with intensive agricultural activities in the southern Québec Province, Eastern Canada. Most of the samples were collected in the regional bedrock fractured aquifer hosted in mid-Ordovician siliciclastic shales, on a total surface of 7500 km2. Even with this low-density sampling, and in a heterogeneous and fractured aquifer, the helium isotopes bring precious information on the recharge conditions and on chemical evolution of water. The helium spatial interpolation does not show a clear isotopic gradient through the basin. However, it shows progressive enrichment of radiogenic 4He in the confined part of the aquifer. The atmospheric and/or tritiogenic-rich helium occurs at the recharge in the Appalachians and in the middle of the plain, where impermeable cover is limited, and local infiltration of meteoric freshwater reaches the bedrock aquifer. The relation between the total dissolved solids (TDS) and 3He/4He ratios remains elusive. However, on discriminating the samples with the dominant chemistry of water, a clear trend is observed with 3He/4He ratio, suggesting that radiogenic 4He accumulates together with dissolved solids and with increasing time (indicated by progressively older 14C ages). Finally, the noble gas temperatures (NGTs) obtained from concentrations of the other noble gases (Ne, Ar, Kr and Xe) brings constraints on the earlier recharge conditions during the Holocene. Particularly, the NGTs showed that the studied aquifers were continuously replenished, even under ice-sheet cover in the last 10,000 years.

Basin architecture controls on the chemical evolution and 4He distribution of groundwater in the Paradox Basin

Fluids such as 4He, H2, CO2 and hydrocarbons accumulate within Earth's crust. Crustal reservoirs also have potential to store anthropogenic waste (e.g., CO2, spent nuclear fuel). Understanding fluid migration and how this is impacted by basin stratigraphy and evolution is key to exploiting fluid accumulations and identifying viable storage sites. Noble gases are powerful tracers of fluid migration and chemical evolution, as they are inert and only fractionate by physical processes. The distribution of 4He, in particular, is an important tool for understanding diffusion within basins and for groundwater dating. Here, we report noble gas isotope and abundance data from 36 wells across the Paradox Basin, Colorado Plateau, USA, which has abundant hydrocarbon, 4He and CO2 accumulations. Both groundwater and hydrocarbon samples were collected from 7 stratigraphic units, including within, above and below the Paradox Formation (P.Fm) evaporites. Air-corrected helium isotope ratios (0.0046 - 0.127 RA) are consistent with radiogenic overprinting of predominantly groundwater-derived noble gases. The highest radiogenic noble gas concentrations are found in formations below the P.Fm. Atmosphere-derived noble gas signatures are consistent with meteoric recharge and multi-phase interactions both above and below the P.Fm, with greater groundwater-gas interactions in the shallower formations. Vertical diffusion models, used to reconstruct observed groundwater helium concentrations, show the P.Fm evaporite layer to be effectively impermeable to helium diffusion and a regional barrier for mobile elements but, similar to other basins, a basement 4He flux is required to accumulate the 4He concentrations observed beneath the P.Fm. The verification that evaporites are regionally impermeable to diffusion, of even the most diffusive elements, is important for sub-salt helium and hydrogen exploration and storage, and a critical parameter in determining 4He-derived mean groundwater ages. This is critical to understanding the role of basin stratigraphy and deformation on fluid flow and gas accumulation.

Extending Noble Gas Solubilities in Water to Higher Temperatures for Environmental Application

Noble gas concentrations in natural waters are widely used to determine ambient temperature conditions during the last intensive contact with the atmosphere (equilibration). Such applications require accurate solubility functions, which so far are available only for the common environmental temperature range between (0 and 35) °C. Nonetheless, environmental scenarios that generate higher surface-water temperatures (such as volcanism) exist. Previous solubility measurements beyond ∼35 °C are sparse or outdated and were determined through equilibration of water with pure noble gases. This can potentially render them not suitable for environmental applications where equilibration with atmospheric air is considered. We therefore conducted new measurements for the solubilities of helium, neon, argon, krypton, and xenon in deionized water equilibrated with atmospheric air at ∼1 bar for temperatures ranging from (25 to 80) °C. These measurements were combined with data from the literature that were obtained in a similar manner and fitted with a commonly used function to determine new noble gas solubility functions valid from (0 to 80) °C. We estimate relative standard uncertainties with a 0.99 level of confidence between 0.015 and 0.030 for the new functions, which are thus suitable for the investigation of environmental high-temperature equilibration scenarios. For temperatures beyond 35 °C, the new functions deviate significantly from previous studies.

3He/4He Signature of Magmatic Fluids from Telica (Nicaragua) and Baru (Panama) Volcanoes, Central American Volcanic Arc

Constraining the magmatic 3He/4He signature of fluids degassed from a magmatic system is crucial for making inferences on its mantle source. This is especially important in arc volcanism, where variations in the composition of the wedge potentially induced by slab sediment fluids must be distinguished from the effects of magma differentiation, degassing, and crustal contamination. The study of fluid inclusions (FIs) trapped in minerals of volcanic rocks is becoming an increasingly used methodology in geochemical studies that integrates the classical study of volcanic and geothermal fluids. Here, we report on the first noble gas (He, Ne, Ar) concentrations and isotopic ratios of FI in olivine (Ol) and pyroxene (Px) crystals separated from eruptive products of the Telica and Baru volcanoes, belonging to the Nicaraguan and Panamanian arc-segments of Central America Volcanic arc (CAVA). FIs from Telica yield air corrected 3He/4He (Rc/Ra) of 7.2–7.4 Ra in Ol and 6.1–7.3 in Px, while those from Baru give 7.1–8.0 Ra in Ol and 4.2–5.8 Ra in Px. After a data quality check and a comparison with previous 3He/4He measurements carried out on the same volcanoes and along CAVA, we constrained a magmatic Rc/Ra signature of 7.5 Ra for Telica and of 8.0 Ra for Baru, both within the MORB range (8 ± 1 Ra). These 3He/4He differences also reflect variations in the respective arc-segments, which cannot be explained by radiogenic 4He addition due to variable crust thickness, as the mantle beneath Nicaragua and Panama is at about 35 and 30 km, respectively. We instead highlight that the lowest 3He/4He signature observed in the Nicaraguan arc segment reflects a contamination of the underlying wedge by slab sediment fluids. Rc/Ra values up to 9.0 Ra are found at Pacaya volcano in Guatemala, where the crust is 45 km thick, while a 3He/4He signature of about 8.0 Ra was measured at Turrialba volcano in Costa Rica, which is similar to that of Baru, and reflects possible influence of slab melting, triggered by a change in subduction conditions and the contemporary subduction of the Galapagos hot-spot track below southern Costa Rica and western Panama.

Noble gas adsorption to tuff

A method was developed to measure trace noble gas element adsorption to the surfaces of geologic materials in the presence of a background gas that could potentially compete for surface adsorption sites. Adsorption of four noble gas elements (Ne, Ar, Kr, and Xe) at a concentration of 100 ppm in helium and nitrogen were measured on a sample of crushed tuff at 0, 15, 30, and 45 °C. In addition, Ne, Ar, Kr, and Xe at 250 ppm and 500 ppm in nitrogen at 15 °C were measured. Noble gas adsorption was found to increase with increasing atomic mass and decreasing temperature. It was also observed that the relative increase in noble gas element adsorption with decreasing temperature tends to increase with increasing atomic mass. As the noble gas concentrations in nitrogen increased, adsorption increased in a slightly non-linear fashion which could be modeled using a Freundlich isotherm. For noble gas concentrations that were ≤100 ppm Henry's Law constant were calculated.

Anomalous Noble Gas Solubility in Liquid Cloud Water: Possible Implications for Noble Gas Temperatures and Cloud Physics

AbstractThe noble gas temperature climate proxy is an established tool that has previously been applied to determine the source of groundwater recharge, however, unanswered questions remain. In fractured media (e.g., volcanic islands) recharge can be so rapid that groundwater is significantly depleted in heavy noble gases, indicating that the water has retained noble gas concentrations from higher elevations. Previous studies of rain samples have confirmed a match to patterns seen in fractured‐rock groundwater for heavy noble gases along with a significant helium excess. Snow has been shown to be a credible source for both the helium excess and the observed heavy noble gas pattern. Here, liquid cloud water samples were collected at two mountainous sites and analyzed for noble gas concentrations. A pattern like that of rainwater was found. However, an analysis of diffusive uptake of noble gases into cloud water demonstrates that droplets of 1 mm diameter and smaller should be in constant solubility equilibrium with the atmosphere. To explain this, we present a novel hypothesis that relies on the assumption that liquid water consists of two types of water molecule clusters bounded by hydrogen bonds: a low‐density ice‐like structure and a high‐density condensed structure. In this model, the pressure gradient near the surface of a droplet resulting from surface tension could allow for the formation of a surface layer that is rich in ice‐like low density clusters. This can explain both the helium excess and the heavy noble gas depletion seen in the samples.

Noble gas exposure ages of samples from Cone and North Ray craters: Implications for the recent lunar cratering chronology

AbstractCosmic ray exposure (CRE) ages of rocks that were ejected by the impacts that created Cone and North Ray craters provide two crucial calibration points at <100 Ma for the lunar cratering chronology function, which relates the crater density of geological units on the Moon to their absolute age. To reassess the formation ages of these two craters, we determine here the accumulated abundances of “cosmogenic” noble gas nuclides (3Hecosm, 21Necosm, 38Arcosm), as well as the corresponding CRE ages, in six Apollo 14 rocks (i.e., one breccia and five basalts) and two Apollo 16 anorthosites that were collected near the rims of Cone and North Ray craters, respectively. Although noble gas concentrations allow CRE ages to be derived, the calculated 21Ne and 38Ar exposure ages of a given sample cover a significant range of values because published empirical or theoretical production rates of cosmogenic nuclides are highly variable. Nonetheless, it is evident that mare basalts 14053 and 14072 as well as breccia 14068, which were collected near the rim of Cone crater, were exposed at the lunar surface more recently than the three KREEP basalts (14073, 14077, 14078) collected farther away. The 38Ar exposure ages of anorthosites 67075 and 67955 from North Ray crater slightly exceed those of samples 14053, 14068, and 14072. These results confirm that Cone crater is younger than North Ray crater. However, the formation ages of Cone and North Ray craters have larger uncertainties than previously acknowledged. This implies that the uncertainties of noble gas exposure ages should be taken into account when remotely dating young surfaces on the Moon and on other planetary bodies in the solar system.

Light noble gas records and cosmic ray exposure histories of recent ordinary chondrite falls

AbstractWe measured noble gas concentrations and isotopic ratios (He, Ne, and Ar isotopes) in six recent ordinary chondrite falls: Mangui (L6), Viñales (L6), Ozerki (L6), Tamdakht (H5), Kheneg Ljouâd (LL5/6), and Katol (L6). Among them, the three L6 chondrites Mangui, Viñales, and Ozerki fell in only a few months' interval; their apparent similar petrographic and mineralogic characteristics might indicate source crater pairing. To test this hypothesis, we have investigated those meteorites for their cosmic ray exposure (CRE) histories, using the cosmogenic noble gases 3He, 21Ne, and 38Ar. We systematically (re)calculated the CRE ages as well as the gas retention ages of these meteorites. The CRE age of the Mangui is, based on noble gases, <1 Ma, which is unusually short for an L chondrite. Indeed, the range of exposure ages for L chondrites is generally distributed between ˜1 and ˜60 Ma, with major peaks occurring around ˜5, ˜30, and ˜40 Ma. In addition, the cosmogenic 3Hecos data of two Mangui duplicates are consistent with a remarkably high loss of helium by diffusion due to heating by solar radiation. Such a short parent body‐Earth transfer time (<1 Ma) can be explained by a delivery from an Earth‐crossing object. Regarding the other L6 chondrites, Viñales has a nominal CRE age of ˜9.4 Ma, whereas the Ozerki meteorite has a nominal CRE age of ˜1.2 Ma, which is consistent with Korochantseva et al. (2019). Based on their CRE ages as well as on their gas retention ages, it appears that none of these three recent L6 chondrite falls are source crater paired, and therefore, all three originate from different meteoroids. The nominal exposure ages of Tamdakht, Kheneg Ljouâd, and Katol are ˜3.2, ˜11, and ˜30 Ma, respectively, and are consistent with identified age peaks on the exposure age histogram of H, LL, and L chondrites, respectively. The nominal CRE age of Tamdakht is consistent with previous observations for H chondrites and implies that they are dominated by small impact events occurring in several parent bodies.

Diffuse gases in soil of Araró-Simirao geothermal system, Michoacán, Mexico

The Araró-Simirao geothermal system is located in the southeastern part of the Cuitzeo Lake depression, in the central part of the TransMexican Volcanic Belt (TMVB) province. It is a convective hydrothermal system dominated by sodium chloride water and high boron content. The thermal springs mainly release CO2 and lower concentrations of H2S, H2, and noble gases (He, Ne, and Ar). The aim of this study was to delimit the upflow areas in this geothermal system by determining the relationships between diffuse gas emission concentrations in soils and the zones of the greatest plausible permeability. Three sampling campaigns were carried out in 2018 (August and November) and 2019 (May). In these campaigns, diffuse gas emission in soils (CO2, Rn, and Hg vapors) and soil temperature were measured. The diffuse gas emission measurements ranged from 0.8 to 1,421 g m-2d-1 for CO2 flux, from 0.49 to 2,914 ng/m3 for gaseous elemental mercury (GEM), from 1,060 to 124,100 Bq/m3 for 222Rn, and from 0 to 7,511 Bq/m3 for 220Rn. The highest values were obtained in the dry season (May). Several anomalous zones of CO2 fluxes, GEM, and 222Rn were found to match faults and lineaments, interpreted as the greatest permeability zones. The zone with the highest values of these three parameters was located in the so-called mud pool at the crossing of the Araró-Simirao fault with a NW-SE (south zone) lineament, which is associated with the upflow zone of the system. Other anomalous zones were located in fracture and/or lineament zones in the central and northern parts of the system, which are associated with the outflow zone. According to the data obtained herein, CO2 could work as a carrier of Hg and 222Rn in the upflow zone; and this gas may be dissolved in the groundwater in the outflow zone.

Origin of water masses in Floridan Aquifer System revealed by 81Kr

Groundwater in coastal aquifers serves as an essential resource in densely populated areas throughout the world. However, hydrological connection to the ocean leaves it at risk of salinization via changes in climate and hydrological cycles. Therefore, an accurate hydrological characterization of coastal aquifers is of the utmost importance. Although localized salinization of shallow aquifers has commonly been studied, geochemical constraints on the time scale of regional freshwater and seawater in coastal aquifers are limited especially in carbonate aquifers. Such information is not only crucial for water resource management, but also for understanding solute flux over the land-ocean boundary and for interpreting the geochemical signatures that each water mass carries. Toward this goal, we report tracer-based, subsurface residence times of groundwater in the Floridan Aquifer System in southern Florida, which is one of the most productive aquifers on Earth. The first application of 81Kr—an emerging tracer of old groundwater—to this aquifer has identified freshwater recharge during the last glacial period as anticipated from previous studies using other geochemical tools including radiocarbon, stable isotopes and noble gas concentrations. Moreover, freshwater of Holocene age was also detected at 100 km-distance from the recharge area, suggesting the possibility of an active flow system in the upgradient region. A contribution of fossil seawater that predates the last glacial maximum was locally identified, suggesting slow seawater circulation and limited but significant solute flux from the ocean into the aquifer for dolomitization. This also implies that the deep saline coastal groundwater can potentially serve as a paleo-seawater archive.

Exposure history, petrology, and shock‐induced sulfidization reaction of Alatage Mountain 001 strewn field samples

AbstractSeveral hundred meteorites with a total mass of over 100 kg were collected as the Alatage Mountain (AM) strewn field located in the Kumtag desert, Xinjiang Province, China. Twelve AM meteorites were studied in this work. Petrography, mineralogy, bulk chemistry, bulk oxygen isotopic compositions, and light noble gas concentrations and isotopic compositions were determined for all or for a selection of the meteorites. The studied meteorites are L‐chondrites that suffered a very strong impact; impact melt veins and melt pockets are widely distributed. More than 50% of the troilite exists in the form of blebs and veins in olivine and pyroxene. Some of these meteorites are impact melt recrystallized rocks (e.g., AM 037). The strong impact caused the decomposition of troilite, which led in AM 034 to the sulfidization reaction of olivine. The metal in most meteorites is almost completely altered, and the troilite has been significantly oxidized. Weathering resulted in the depletion of Mg, Fe, Co, and Ni, and the enrichment of Sr, Ba, Pb, and U in these meteorites. The cosmic ray exposure (CRE) ages measured for these specimens range between 6.2 ± 1.9 Ma and 9.0 ± 2.7 Ma, depending on the cosmogenic nuclide used. The average CRE age is 7.6 ± 1.3 Ma. Both 4He and 40Ar gas retention ages indicate that the strong impact which caused the shock effects occurred about 320 Ma ago.

Noble gases in CM carbonaceous chondrites: Effect of parent body aqueous and thermal alteration and cosmic ray exposure ages

Like most primitive carbonaceous chondrites, the CM chondrites experienced varying degrees of asteroidal aqueous alteration, which may have overprinted pre-accretionary processing. Several aqueous alteration scales for CM chondrites (and other carbonaceous chondrites) have been proposed based on alteration-dependent changes in various petrological and geochemical characteristics. Given the possibility that the intensity of aqueous alteration could be recorded in the primordial noble gas compositions, we test potential correlations between petrologic, geochemical and noble gas characteristics in a detailed study on 39 CM chondrites, including some of the most pristine CM chondrites identified to date, and 4 CM-related carbonaceous chondrites. We mainly compare our noble gas data with the alteration schemes proposed by Alexander et al. (2013) and Howard et al. (2015). In addition to the noble gas analyses, we determined the phyllosilicate fractions of 17 of the CM chondrites using X-ray diffraction (XRD) to complement missing data points in the Howard alteration scheme. The influence of post-hydration thermal modification on noble gases in CM chondrites is investigated by comparison of heated and unheated samples. Cosmic-ray exposure (CRE) ages are determined for all samples in this study as well as for 26 more samples based on CM chondrite literature noble gas data.The noble gas inventory in CM chondrites represents a mixture of cosmogenic, radiogenic, and abundant primordially trapped noble gases. Additionally, about 50 % of our CM bulk samples contain detectable solar wind (SW), which implies that many but not all CM chondrites are regolith breccias or carry SW from a pre-accretion irradiation phase. Aqueous alteration affects primordial noble gas abundances and elemental and isotopic compositions in CM chondrites. In particular, the process causes loss of an Ar-rich component, different in elemental and isotopic composition to known noble gas components. This component is lost during the early stages of aqueous alteration until complete degassing of its carrier material (possibly upon at least partial destruction) below petrologic type of ~1.5 on the Howard et al. (2015) scale. Likely, small amounts of Q gases were additionally released by aqueous alteration. Strong thermal modification at >750 °C results in a significant additional loss of noble gases, whereas peak temperatures <500 °C likely have minor effects on the noble gas inventories of CM chondrites. Some of the described trends of noble gas contents and elemental and isotopic ratios in this study are observable across multiple carbonaceous chondrite groups, in particular also the CR chondrites. Hence, these carbonaceous chondrites may have started with similar initial noble gas inventories due to accretion of material from a common reservoir. The CRE ages of most of our CM samples fall within the typical range of <10 Myr previously observed for CM chondrites. A few CM chondrites, however, show longer CRE ages, with the longest CRE age of ~20Myr determined for the SW-rich CM Allan Hills (ALH) 85013. The degree of aqueous and thermal alteration is variable among CM chondrites with similar CRE ages.

Noble gases in cluster chondrite clasts and their host breccias.

We measured noble gases in “cluster chondrite clasts” from nine unequilibrated ordinary chondrites (UOCs). For five meteorites, we also present data for so‐called “clastic matrix,” the impact‐brecciated material in which the angular to subrounded cluster chondrite clasts are often embedded. Cluster chondrite clasts are characterized by close‐fit texture of deformed and indented chondrules with lower amounts of fine‐grained interchondrule matrix than in other UOCs (Metzler 2012). They are ubiquitous in UOCs and may indicate accretion and compaction of hot and deformable chondrules within hours or days after formation. Clastic matrix of four of the five meteorites contains He and Ne implanted by the solar wind (SW), indicating that they are regolith breccias. In contrast, cluster chondrite clasts are essentially devoid of SW, confirming that they are fragments of “primary accretionary rocks” (Metzler 2012). Trapped Kr and Xe in all samples are essentially primordial (type “Q”). Trapped Xe concentrations in cluster chondrite clasts are similar to values in other UOCs of similar metamorphic grade despite their low fractions of primordial gas‐bearing fine‐grained materials. This possibly indicates that the interchondrule matrix in cluster chondrite clasts is more pristine than matrix of regular UOCs. Later loss of primordial gases during parent body metamorphism is mirrored in the decreasing concentrations of primordial noble gases with increasing petrologic type. Relative to cluster chondrite lithologies, clastic matrix often contains excesses of cosmogenic noble gases, most likely due to precompaction exposure in the parent body regolith.

Noble gas tracers in gas streams at Norwegian CO2 capture plants

Carbon capture and storage (CCS) may play a significant role in reducing greenhouse gas emissions. Noble gases are potential tracers to monitor subsurface CO2 storage sites and verify their containment. Naturally occurring noble gases have been used successfully to refute alleged CO2 leakage in the past.We present results from several sampling campaigns at two Norwegian CO2 capture facilities, the demonstration plant Technology Centre Mongstad (TCM) and the natural gas processing plant with CO2 capture and storage on Melkøya. The gas streams in the capture plants were monitored with a combination of on-site mass spectrometry and subsequently analysed discrete samples. This allows us to define the factors controlling noble gas concentrations in captured CO2, to monitor temporal variation of noble gas concentrations and finally evaluate the potential to use noble gases as inherent environmental tracers for labelling CO2 in storage reservoirs.At both sites, CO2 is captured using amine gas treatment. Noble gas concentrations in the gas streams were observed to decrease by several orders of magnitude during the processing. Isotopic ratios are air-like for CO2 captured after natural gas combustion at TCM and natural gas-like for CO2 captured from natural gas processing on Melkøya. Further, we detected a solubility trend caused by the amine solvent at TCM with higher solubility for heavier noble gases.We find that the relative concentrations of noble gases in the captured CO2 are defined by the gas from which the CO2 is captured and the design of the amine gas treatment process. Both factors were observed to cause temporal variation in the captured CO2.Using mixing and noble gas partitioning calculations we show that the significant depletion in noble gas concentrations, together with degassing of noble gas enriched formation water, means that the injected CO2 will inherit the noble gas signature of the storage formation, even following the injection of significant CO2 volumes. Any CO2 leaked from the storage formation is thus likely to have a crustal noble gas signature, characteristic of the storage site, which can be targeted for monitoring.

Noble gases in sediment pore water yield insights into hydrothermal fluid transport in the northern Guaymas Basin

We present noble gas concentrations determined in pore water of deep-sea sediments close to a recently discovered hydrothermal vent site, consisting of a mound structure and several black smokers, located in the northern Guaymas Basin, Gulf of California. Noble gases were used as tracers to identify the origin of fluids within the sediment pore space and to gain insight into transport dynamics of hydrothermal fluids in this region. Our data suggest that Guaymas Basin bottom water is the only source of pore water in the pelagic sediment body close to the hydrothermal vent field. In particular, there is no evidence of any direct (diffusive or advective) transport of hydrothermal fluids through the deep-sea sediments surrounding the black smoker system. This finding implies that at this black smoker site hydrothermal fluids are transported upwards from the fluid source in very narrow pathways below the smokers. Thus, the fluids are only injected into the ocean directly through the chimneys of the black smokers and no additional emission from the surrounding sediment takes place. Helium isotope data show that during a more active phase of the vent field in the past (supposedly representing the early onset of the black smokers 5–6 kyrs ago), bottom water with a different isotopic signature was incorporated into the sediment column.

Noble Gases as Monitoring Tracers in CCS: A Case Study with CO2 from the Waste-to-Energy Plant Klemetsrud, Norway

To design monitoring schemes for CO2 storage sites, the composition of the injected CO2 needs to be characterized. Noble gases are one of the environmental tracers, which could be cost-effective since they are naturally inherent in the CO2 and the storage reservoir fluids. The elemental, e.g. He/Ne, He/CO2, or isotopic, e.g. 3He/4He ratios of a gas are potentially diagnostic fingerprints which can be used to discriminate gas sources in the environment, e.g. deep crustal versus shallow, biogenic gas. The waste-to-energy (WtE) plant Klemetsrud, which generates 460000 tCO2/a, was investigated as a future source of captured CO2 for storage in the up-coming large-scale CCS project ‘Longship’, in Norway, aimed to be operational by 2024. In 2019, a demonstration capture facility at the WtE plant was set up to establish the feasibility of future large-scale CO2 capture. We sampled the main gas streams on-site and present the analysis of noble gases in (I) the exhaust of the waste incineration, i.e. the flue gas stream with high concentrations of CO2, (II) the capture outlet, i.e. the CO2-depleted gas stream and (III) the captured, concentrated CO2 gas stream. Noble gas concentrations are depleted in the captured CO2 after the amine treatment by several orders of magnitude compared to the flue gas. Isotopic ratios are air-like. This behavior has been observed at other CO2 capture plants. However, absolute concentrations of noble gases measured at Klemetsrud are significantly lower for all species, except He, which is within the range of previously measured concentrations. Further, we apply phase partitioning calculations to investigate the application of inherent noble gas in CCS monitoring schemes. The low noble gas concentrations, and their associated elemental and isotopic ratios, would only be preserved when the injected CO2 remains almost pure and does not mix or interact with fluids already present in the reservoir (e.g. native gas, formation water). Interaction of the CO2 with the formation water will lead to noble gas stripping that overprints the highly depleted composition of the captured CO2 with a noble gas elemental and isotopic ratios characteristic of deep crustal fluids. This characteristic signature, especially when coupled with the distinct major gas composition of leaked CO2 (e.g. extreme CO2/CH4 ratios) may form an effective tracer to discriminate a CO2 leakage from other gas sources at the seabed (e.g. shallow biogenic, dissolved air or hydrate decomposition). To take advantage of this low cost tracer, baseline geochemical surveys should include inventories of the background dissolved noble gas load in the formation water of storage reservoirs, in other (hydrocarbon bearing) formations along the migration route and in existing seabed gas seeps overlying the storage site.