Gas Isotopic Signatures Research Articles

Metal budget and origin of aqueous brines depositing deep-seated Zn-Pb mineralization linked to hydrocarbon reservoirs, North German Basin

The origin, evolution, and interplay of brine and hydrocarbon fluid systems play a crucial role in the formation of deep sediment-hosted base metal ore deposits. Here we investigate ratios of halogens, noble gases, stable C and S isotopes, and metal budgets of aqueous brines, which deposited deep-seated and near-surface hydrothermal Zn-Pb mineralization hosted by Zechstein carbonates in the Lower Saxony Basin (North German Basin), by studies of fluid inclusions in sphalerite and quartz. Major and trace element geochemistry and noble gas isotopic signatures of brine inclusions revealed that the ore-forming fluids were highly reactive and experienced prolonged interactions with host rocks in the constricted, over-pressured metal source regions and consequently evolved from near-neutral, oxidized brines towards more reduced, acidic high-salinity brines. Quartz-hosted halite-saturated fluid inclusions with Th <200°C contain Zn and Pb concentrations up to ca. 9400 μg g-1 and 5200 μg g-1, respectively, and indicate the efficiency of metal scavenging processes. The interactions with Westphalian coals and Corg-rich shales influenced the redox state as well as the trace and critical element budget of the sphalerite-hosted fluid inclusions, with enrichment in Ge, Pd, Sb, Tl, Bi, and Ag. The salinities of metalliferous fluids originated primarily from seawater evaporation, however in addition a significant halite-dissolution component is present in the southern part of the Lower Saxony Basin. High concentrations of radiogenic noble gases and potassium in the sphalerite-hosted fluid inclusions are ascribed to strong interactions with the Paleozoic siliciclastic sedimentary pile and crystalline basement rocks. Reflux of the strongly modified, sulfur-poor, Zn-Pb-bearing acidic brines, proceeded via re-activated structurally controlled pathways into sour gas or gas-saturated brine pools in the Zechstein Ca2 carbonate unit. Here, mixing of the ascending metal-rich brines with H2S derived from thermochemical sulfate reduction (TSR), resulted in the deposition of deep-seated Zn-Pb ores in the Lower Saxony Basin. The overall timing of the Zn-Pb ore formation can be constrained to the Upper Cretaceous basin inversion.

Sources and concentrations of methane, ethane, and CO2 in deep aquifers of the Surat Basin, Great Artesian Basin

Understanding the occurrence and sources of methane in aquifers is an international issue, especially in regions that host oil and gas reservoirs. Multi-isotopic studies are important to understand sources and concentrations of dissolved gases in aquifers of basins that host oil and gas extraction; or future CO2, natural gas, hydrogen storage, or compressed air energy storage. The largest artesian basin in the world, the Great Artesian Basin, extends across more than one fifth of Australia providing a fresh water source from various aquifers. The Precipice and Hutton sandstones, aquifers of the Surat Basin in the eastern Great Artesian Basin, are important water resources for town water supply, agriculture, mines, feedlots, and private landholders in Queensland. Overlying and underlying formations host gas extraction. The southern part of the basin in Queensland additionally hosts an oil field, and potential CO2 storage sites, therefore understanding the aquifer gas concentrations, processes and sources is important for fluid management. The dissolved concentrations of methane and ethane in the Hutton Sandstone were up to 96 mg/L and 1 mg/L respectively, and in the Precipice Sandstone methane ranged up to 2100 mg/L and ethane 6.5 mg/L in the southern Surat Basin. Dissolved gas concentrations were measured by an open and closed sampling method, with the concentrations lower from open sampling, and the gas wetness parameter systematically slightly lower. The Hutton Sandstone aquifer dissolved gas isotopic signatures are mainly consistent with primary microbial CO2 reduction generating methane in situ, with fractionation factors indicating acetate fermentation in a few cases. The Hutton Sandstone δ13C-DIC, δ13C-CO2, and δ13C-CH4 have an enrichment trend with increasing depth that indicate a microbial substrate depletion effect. Moonie Oil Field Precipice Sandstone and Evergreen Formation samples plot in the thermogenic region, with enriched δ13C-CO2 indicating microbial biodegradation is also occurring. The Precipice Sandstone aquifer samples have a mixed microbial CO2 reduction and early mature thermogenic gas signature in both isotope cross plots and gas wetness diagrams, with a subset of sampled δ13C-C2H6 and isotope factors consistent with early mature thermogenic gas. A potential historic source of thermogenic gas is the underlying gas reservoir of the Bowen Basin. Large volumes of water are abstracted from these aquifers, hence dissolved gases may contribute to greenhouse gas emissions.

High helium reservoirs in the Four Corners area of the Colorado Plateau, USA

Radiogenic 4He is naturally produced in Earth's crust due to alpha decay of Uranium (U) and Thorium (Th). Helium has unique thermodynamic properties required for the medical imaging industry, aerospace and other fields of high-tech manufacturing, and currently is in increasingly high demand. Despite its economic value, the mechanisms of helium migration and retention in sedimentary basins remain poorly understood.Oil and gas fields with economic helium (>0.3%) concentrations have been discovered in Paleozoic intervals in the Colorado Plateau, southwestern USA. Here we report new noble gas isotope and abundance data for gas samples (n = 31), from actively producing Paleozoic formations within five fields: Ratherford, Tocito Dome, Navajo Springs, Pinta Dome, and Dineh-Bi-Keyah. Helium concentrations range from 0.01% to 7.9% with varying amounts of liquid and gaseous hydrocarbons, N2, and CO2. We present multi-stage gas, water, and oil equilibration models to account for the observed noble gas elemental and isotopic signatures. Oil-dominated systems are explained by a closed system oil/water equilibration and subsequent admixture of air. He-rich dry gas samples exhibit uniform 4He/N2 ratios consistent with the regional mean values, suggesting a common crustal source and no subsequent fractionation. In contrast, air-derived 20Ne/36Ar ratios are highly fractionated. These observations are consistent with a tectonically controlled crustal gas release from the basement, groundwater saturation with 4He and N2, and subsequent degassing. Extensive gas-water interaction (i.e., migration) leads to extreme fractionation of 20Ne/36Ar, but does not affect 4He/N2 due to water saturation with crustal gases released from the basement.We show the volume of rock required to have produced helium in the reservoir to be significantly larger than the current reservoir volume immediately beneath the field. Therefore, the reservoir helium concentration cannot be sourced by in-reservoir decay of U and Th and instead requires a process to incorporate exogenous sources of helium in the reservoir without significant dilution from hydrocarbons. For helium-rich fields, excess helium is sourced from the Precambrian granitic basement likely utilizing a large area beneath the field area (i.e., crustal gas mobilization and transport via fracture zones), consistent with the degree of water contact. Deep crustal faults in the Precambrian basement are in close proximity to the high helium fields, indicating that these structures are potentially serving as primary migration conduits via advective fluid flow.

Binary mixing of lithospheric mantle and asthenosphere beneath Tengchong volcano, SE Tibet: evidence from noble gas isotopic signatures

ABSTRACT The Miocene–Quaternary Tengchong volcanic field in SE Tibet was generated after the main stage of continental collision between India and Eurasia. Consensus on the origin of Tengchong volcanism has not yet been achieved. In this study, we analysed the He-Ar isotopic compositions of olivine and pyroxene phenocrysts, whole-rock major and trace elements and Sr-Nd-Pb isotopic compositions. The 3He/4He ratios range from 4.1 to 8.2 Ra (Ra = 1.4 × 10−6), overlapping the values of mid-ocean ridge basalt (7.0–9.0 Ra) and subcontinental lithospheric mantle (SCLM, 5.2–7.0 Ra). The low 3He/4He (< 7.0 Ra) basalts have high 87Sr/86Sr (average of 0.707928) and La/Yb (average of 22.0) ratios and low Nb/La (average of 0.36) ratios, whereas the high 3He/4He (> 7.0 Ra) basalts exhibit relatively low 87Sr/86Sr (average of 0.706708) and La/Yb (average of 17.0) ratios and relatively high Nb/La (average of 0.52) ratios. These observations indicate that the primitive magmas originated from a mixture of metasomatized SCLM and enriched asthenospheric mantle. The SCLM was likely metasomatized by the subducted Neo-Tethyan oceanic plate, while the asthenospheric mantle was enriched by the subducting Indian oceanic plate. The increasing trend of 3He/4He ratios and decreasing trend of 87Sr/86Sr ratios over time suggest that the contribution of the metasomatized SCLM decreased after the late Pleistocene relative to that of the enriched asthenosphere, reflecting progressive lithospheric extension and thinning. Our results reveal that magmatic He isotopes can be used to constrain deep dynamic processes.

Partitioning of noble gases (He, Ne, Ar, Kr, Xe) during Earth’s core segregation: A possible core reservoir for primordial noble gases

Noble gas isotopes in plume-influenced oceanic-island basalts (OIBs) clearly indicate the existence of distinct reservoirs somewhere in the deep Earth that are characterized by their more primitive noble gas isotopic signatures. As one of the largest differentiated layers on Earth, whether the Earth’s liquid outer core can preserve ‘primordial’ noble gases is fundamental for better understanding the Earth’s formation and the mantle evolution. Since Earth’s core is believed to have formed via liquid iron segregated from magma ocean during the planetary accretion stage, how much noble gases could have been incorporated into Earth’s core depends on the partitioning of noble gases between liquid metal and molten silicates. In this study, we perform thermodynamic integration (TI) calculations based on first-principles molecular dynamics (FPMD) simulation to investigate the partition coefficients of noble gases (NG: He, Ne, Ar, Kr, Xe) between liquid Fe and MgSiO3 melt. The simulations have been performed by adopting conditions that the pressures are from 10 ∼ 135 GPa and the temperatures from 2300 ∼ 5000 K to fully account for possible core-mantle equilibrium conditions. By analyzing the temperature and pressure dependence of the results, we suggest that the metal-silicate partitioning of noble gases (DNG) merely depends on the temperature, with extremely low DNG < 0.001 at temperatures < 2500 K (20 GPa), but increases to different degrees at high temperatures. The DNG tends to be more affected by temperature as the noble gas atomic mass increases, with the least temperature effect on the partition coefficient of He (DHe), which increases from ∼ 10−3 at 2300 K (10 GPa) to ∼ 10−1 (5000 K, 135 GPa) near the core-mantle boundary (CMB), and DNe = 10−6 ∼ 10−3, DAr = 10−6 ∼ 10−2, DKr = 10−7 ∼ 10−1 and DXe = 10−5 ∼ 100 from 2300 to 5000 K, respectively. Analysis of electronic interactions indicates that noble gases have positive chemical bonding with Fe, Mg, and Si atoms, and the bonding strengths increase with pressure as well as increasing noble gas atomic mass. Based on our calculated partition coefficients, we suggest that Earth’s core may have preserved significant amounts of noble gases considering the volatile-rich environment from which the core segregated.

Versatile soil gas concentration and isotope monitoring: optimization and integration of novel soil gas probes with online trace gas detection

Abstract. Gas concentrations and isotopic signatures can unveil microbial metabolisms and their responses to environmental changes in soil. Currently, few methods measure in situ soil trace gases such as the products of nitrogen and carbon cycling or volatile organic compounds (VOCs) that constrain microbial biochemical processes like nitrification, methanogenesis, respiration, and microbial communication. Versatile trace gas sampling systems that integrate soil probes with sensitive trace gas analyzers could fill this gap with in situ soil gas measurements that resolve spatial (centimeters) and temporal (minutes) patterns. We developed a system that integrates new porous and hydrophobic sintered polytetrafluoroethylene (sPTFE) diffusive soil gas probes that non-disruptively collect soil gas samples with a transfer system to direct gas from multiple probes to one or more central gas analyzer(s) such as laser and mass spectrometers. Here, we demonstrate the feasibility and versatility of this automated multiprobe system for soil gas measurements of isotopic ratios of nitrous oxide (δ18O, δ15N, and the 15N site preference of N2O), methane, carbon dioxide (δ13C), and VOCs. First, we used an inert silica matrix to challenge probe measurements under controlled gas conditions. By changing and controlling system flow parameters, including the probe flow rate, we optimized recovery of representative soil gas samples while reducing sampling artifacts on subsurface concentrations. Second, we used this system to provide a real-time window into the impact of environmental manipulation of irrigation and soil redox conditions on in situ N2O and VOC concentrations. Moreover, to reveal the dynamics in the stable isotope ratios of N2O (i.e., 14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O), we developed a new high-precision laser spectrometer with a reduced sample volume demand. Our integrated system – a tunable infrared laser direct absorption spectrometry (TILDAS) in parallel with Vocus proton transfer reaction mass spectrometry (PTR-MS), in line with sPTFE soil gas probes – successfully quantified isotopic signatures for N2O, CO2, and VOCs in real time as responses to changes in the dry–wetting cycle and redox conditions. Broadening the collection of trace gases that can be monitored in the subsurface is critical for monitoring biogeochemical cycles, ecosystem health, and management practices at scales relevant to the soil system.

Quantifying CH4 concentration spikes above baseline and attributing CH4 sources to hydraulic fracturing activities by continuous monitoring at an off-site tower

Abstract Hydraulic fracturing (hydrofracking) for natural gas has increased rapidly in the area of the Marcellus Shale in the last thirty years and estimates of CH4 emissions from hydrofracking operations are still uncertain. Previous studies on CH4 emissions at hydrofracking operations have used bottom-up approaches collected at discrete timepoints or discrete aerial surveys covering a wide spatial area, constraining the temporal scale of inference regarding these emissions. This project monitored atmospheric CH4 concentrations and stable carbon isotopes at a half-hourly temporal resolution from a 20-m tower downwind of a hydrofracking well pad in West Virginia for eighteen months. We collected four months of baseline observations prior to onsite well development to construct an empirical artificial neural-network model of baseline CH4 concentrations. We compared measured CH4 concentrations against the ANN-modeled CH4 baseline to identify CH4 concentration spikes that coincided with different stages of onsite well development, from the baseline period through fracking. CH4 concentration spikes were significantly more frequent than baseline conditions during the vertical drilling and fracking phases of operations. We found that the median magnitude of CH4 concentration spikes during the vertical drilling phase was 316% larger than that of the baseline phase, and the median magnitude of CH4 concentration spikes was 509% larger in the hydraulic stimulation (fracking) stage compared to the baseline phase. We also partitioned the sources of measured CH4 concentrations to biogenic ruminant and geologic shale gas isotopic signatures by measuring 13CH4 gas at high temporal resolution and using a source-partitioning 13CH4 model. The measured median value of half-hourly CH4 concentration spikes attributed to a geologic shale gas isotopic origin was 27% larger than the median CH4 concentration spikes attributed to ruminants, and the maximum half-hourly CH4 concentration spike attributed to shale gas was up to 179% higher than maximum CH4 concentration spike for ruminant-dominated half-hours. This study developed a framework for off-site, single tower measurements to identify CH4 concentration spikes associated with the phases of unconventional natural gas well development in a complex CH4 emissions airshed.

Evidence of presolar SiC in the Allende Curious Marie calcium aluminum rich inclusion.

Calcium aluminum rich inclusions (CAIs) are one of the first solids to have condensed in the solar nebula, while presolar grains formed in various evolved stellar environments. It is generally accepted that CAIs formed close to the Sun at temperatures above 1500 K, where presolar grains could not survive, and were then transported to other regions of the nebula where the accretion of planetesimals took place. In this context, a commonly held view is that presolar grains are found solely in the fine-grained rims surrounding chondrules and in the low-temperature fine-grained matrix that binds the various meteoritic components together. Here we demonstrate, based on noble gas isotopic signatures, that presolar SiC have been incorporated into fine-grained CAIs in the Allende carbonaceous chondrite at the time of their formation, and have survived parent body processing. This finding provides new clues on the conditions in the nascent solar system at the condensation of first solids.

An overview of types and characterization of hot fluids associated with reservoir formation in petroliferous basins

Increasing petroleum explorations indicate that the formation of many reservoirs is in close association with deep hot fluids, which can be subdivided into three groups including crust-derived hot fluid, hydrocarbon-related hot fluid, and mantle-derived hot fluid. The crust-derived hot fluid mainly originates from deep old rocks or crystalline basement. It usually has higher temperature than the surrounding rocks and is characterized by hydrothermal mineral assemblages (e.g. fluorite, hydrothermal dolomite, and barite), positive Eu anomaly, low δ18O value, and high 87Sr/86Sr ratio. Cambrian and Ordovician carbonate reservoirs in the central Tarim Basin, northwestern China serve as typical examples. The hydrocarbon-related hot fluid is rich in acidic components formed during the generation of hydrocarbons, such as organic acid and CO2, and has strong ability to dissolve alkaline minerals (e.g. calcite, dolomite, and alkaline feldspar). Extremely 13C-depleted carbonate cements are indicative of the activities of such fluids. The activities of hydrocarbon-related hot fluids are distinct in the Eocene Wilcox Group of the Texas Gulf Coast, and the Permian Lucaogou Formation of the Jimusaer Sag and the Triassic Baikouquan Formation of the Mahu Sag in the Junggar Basin. The mantle-derived hot fluid comes from the upper mantle. The activities of mantle-derived hot fluids are common in the rift basins in eastern China, showing a close spatial relationship with deep faults. This type of hot fluid is characterized by high CO2 content, unique gas compositions, and distinct noble gas isotopic signatures. In the Huangqiao gas field of eastern China, mantle-derived CO2-rich hot fluids have created more pore spaces in the Permian sandstone reservoirs adjacent to deep faults.

Evidence of hotspot paths below Arabia and the Horn of Africa and consequences on the Red Sea opening

Rifts are often associated with ancient traces of hotspots, which are supposed to participate to the weakening of the lithosphere. We investigated the expected past trajectories followed by three hotspots (Afar, East-Africa and Lake-Victoria) located around the Red Sea. We used a hotspot reference frame to compute their location with respect to time, which is then compared to mantle tomography interpretations and geological features. Their tracks are frequently situated under continental crust, which is known to strongly filter plume activity. We looked for surface markers of their putative ancient existence, such as volcanism typology, doming, and heat-flow data from petroleum wells. Surface activity of the East-Africa hotspot is supported at 110 Ma, 90 Ma and 30 Ma by uplift, volcanic activity and rare gas isotopic signatures, reminiscent of a deep plume origin. The analysis of heat-flow data from petroleum wells under the Arabian plate shows a thermal anomaly that may correspond to the past impact of the Afar hotspot. According to derived hotspot trajectories, the Afar hotspot, situated (at 32 Ma) 1000 km north-east of the Ethiopian–Yemen traps, was probably too far away to be accountable for them. The trigger of the flood basalts would likely be linked to the East-Africa hotspot. The Lake-Victoria hotspot activity appears to have been more recent, attested only by Cenozoic volcanism in an uplifted area. Structural and thermal weakening of the lithosphere may have played a major role in the location of the rift systems. The Gulf of Aden is located on inherited Mesozoic extensional basins between two weak zones, the extremity of the Carlsberg Ridge and the present Afar triangle, previously impacted by the East-Africa hotspot. The Red Sea may have opened in the context of extension linked to Neo-Tethys slab-pull, along the track followed by the East Africa hotspot, suggesting an inherited thermal weakening.

Learning from soil gas change and isotopic signatures during 2012 Emilia seismic sequence

Soil surveys were performed in Medolla (Italy), a peculiar area characterized by spotty high soil temperature, gas vent, and lack of vegetation, to determine the migration mechanisms and spatial behavior of gas species. Hereby we present soil gas measurements and their isotopic ratios measured between 2008 and 2015, including the 2012 Emilia-Romagna seismic sequence. We found that soil gas concentrations markedly changed during the main shocks of May 20 and 29, 2012 (Mw 6.1 and 6.0, respectively), highlighting the presence of a buried fault intersecting the gas vents. We suggest that crustal dilation associated with seismic activity favored the uprising of geogas towards the surface. Changes in the isotopic signature highlight the contribution of two distinct sources, one deeper, thermogenic and another superficial related to organic-rich layer, whose relative contribution varied before, during and after the earthquake. We suppose an increase of microbial component likely due to the ground shaking of shallower layers linked to seismic sequence, which masks the thermogenic contribution. Although the changes we detect are specific for an alluvial plain, we deduce that analogous processes may be active elsewhere, and that soil gas geochemistry represents an useful tool to discriminate the gas migration related to seismic activity.

Postcollisional mafic igneous rocks record recycling of noble gases by deep subduction of the continental crust

Recycling of noble gases from crustal rocks into the mantle is indicated not only by oceanic basalts and mantle xenoliths, but also by ultrahigh-pressure metamorphic rocks in collisional orogens. It is intriguing whether noble gases in continental crust were recycled into the mantle by deep subduction of the continental crust to mantle depths. Here we firstly report the He, Ne and Ar isotopic compositions of pyroxene from postcollisional mafic igneous rocks in the Dabie orogen, China. The results show that the pyroxene separates from the mafic rocks have low 3He/4He ratios of 0.002 to 1.8Ra and air-like Ne isotope compositions. Furthermore, the pyroxene exhibits low 40Ar/36Ar ratios of 393.6 to 1599.8, close to those of the air. In combination with whole-rock geochemistry it is found that pyroxene 3He/4He ratios are correlated with whole-rock (La/Yb)N and Sr/Y ratios, εNd(t) values and MgO contents. These observations demonstrate the mass transfer from the deeply subducted continental crust to the overlying mantle wedge, recording the source mixing between the crust-derived melt and the mantle peridotite in the continental subduction zone. A direct addition of the crustal He via crust-derived melt to the mantle leads to the extremely low 3He/4He ratios in the orogenic lithospheric mantle, and the dissolved atmospheric Ar and Ne in the subducted supracrustal rocks results in the air-like Ar and Ne isotope ratios. Therefore, the noble gas isotopic signatures of supracrustal rocks were carried into the mantle by the continental deep subduction to subarc depths and then transferred to the postcollisional mafic igneous rocks via the melt–peridotite reaction at the slab–mantle interface in a continental subduction channel. Our finding firstly establishes the slab–mantle interaction model for recycling of supracrustal noble gases in the continental subduction zone.

Increased stray gas abundance in a subset of drinking water wells near Marcellus shale gas extraction

Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (δ(13)C-CH4, δ(13)C-C2H6, and δ(2)H-CH4), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas (4)He to CH4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living <1 km from gas wells have drinking water contaminated with stray gases.

Primary and secondary processes constraining the noble gas isotopic signatures of carbonatites and silicate rocks from Brava Island: evidence for a lower mantle origin of the Cape Verde plume

We present and discuss noble gas compositions of minerals from silicate rocks (olivines) and carbonatites (apatites and calcites) from Brava Island. The presence of an almost ubiquitous atmosphere-derived fingerprint is explained as reflecting contamination by seawater. Because of the high U and Th content in apatites, which are responsible for 4He production by α-decay, the high measured 4He/3He ratios do not represent magmatic signatures. In contrast, low values of 4He/3He in calcites (≥61,223; R/Ra ≤ 11.80) and olivines (≥56,240; R/Ra ≤ 12.85) are considered to be representative of signatures trapped at the time of crystallization, given that there are no evidences for significant cosmogenic additions. These relatively low 4He/3He ratios depicted by silicate and carbonatite rocks imply the contribution of a reservoir that evolved under low (U + Th)/3He; this is considered a strong evidence for the genesis of Brava by a mantle plume deeply anchored in the lower mantle. The inferred low 4He/40Ar* ratio (≈0.3), before degassing, is thought to reflect the contribution to the carbonatites source of a mantle domain evolving under high K/U, which cannot be explained by recycling of crustal components. The possible link between the low 4He/40Ar* source and the “missing Ar reservoir” is discussed. The usually referred geochemical dichotomy between Northern and Southern Cape Verde islands, which is markedly evident from Sr, Nd, and Pb isotope signatures, is not apparent from Brava Island (Southern Cape Verde), where some samples present relatively unradiogenic 4He/3He signatures, similar to those reported for the Northern islands of the archipelago.

Geochemical and isotopic evidences of magmatic inputs in the hydrothermal reservoir feeding the fumarolic discharges of Tacora volcano (northern Chile)

Tacora volcano is a nearly unknown and understudied 5980 m high volcano located on the northernmost border between Chile and Peru. Tacora is characterized by intense fumarolic activity with extensive, white-colored, hydrothermal areas along the NW and W flanks of the volcanic structure. The chemical and isotopic features of gas emissions indicate that the hydrothermal reservoir is significantly affected by contributions from magmatic degassing, despite relatively low outlet temperatures (82–93 °C). Water and gas isotopic signatures stem from degassing of andesitic magmas produced from the sediment-poor subducting slab. Isotopic data suggests CH 4–CO 2 isotopic equilibration occurs at ~ 400 °C, likely in the deepest portion of the hydrothermal-magmatic fluid reservoir. The H 2–H 2O, CO–CO 2, H 2–Ar, CH 4–CO 2 and C 2–C 3 alkenes/alkanes pairs tend to approach a chemical equilibrium at temperatures between 200 and 320 °C when redox conditions are more oxidizing than those determined by the typical FeO/FeO 1.5 rock buffer system. Boiling occurs at shallow depth at 85 °C within a discontinuous, thin aquifer, enough as thermal buffer but not able to scrub the uprising magmatic-related acidic gases.

Fluid sources and the role of abiogenic-CH 4 in Archean gold mineralization: Constraints from noble gases and halogens

The St Ives Goldfield of Western Australia hosts high grade gold mineralization in a variety of lithologies within ∼2.7 Ga greenstone belts. The low salinity CO 2-bearing fluids responsible for gold mineralization could have been generated either by metamorphic processes within the greenstones, or from external magmatic sources, and independently sourced abiogenic-CH 4 has been suggested as an important control on gold mineralization. In order to better constrain possible fluid sources, we applied a combination of He–Ne–Ar–Kr–Xe isotope and Cl–Br–I analyses to quartz and carbonate veins containing H 2O–CO 2 fluid inclusions, pyrite ± magnetite/hematite; and quartz veins containing CH 4-rich fluid inclusions, pyrrhotite ± pyrite. Samples containing H 2O–CO 2 fluid inclusions have higher Br/Cl and I/Cl values and less radiogenic noble gas isotope signatures than suggested for CH 4-rich fluid inclusions. The samples containing CH 4 fluid inclusions have maximum 40Ar/ 36Ar of ∼50,000; 20Ne/ 22Ne of ≤9.8 and maximum 21Ne/ 22Ne of ∼0.56. In contrast, H 2O–CO 2 fluid inclusions have maximum 40Ar/ 36Ar of only ∼20,000 and maximum 21Ne/ 22Ne of ∼0.14. The use of 40Ar– 39Ar methodology to measure K simultaneously with 40Ar/ 36Ar, enables us to show the highest 40Ar/ 36Ar ratios are representative of the fluids trapped at ∼2.65 Ga, and have not been significantly modified by post-entrapment 40Ar R production ( 40Ar R = radiogenic 40Ar). Furthermore, the 40Ar/ 36Ar ratio is correlated with the 21Ne/ 22Ne and 136Xe/ 130Xe ratios, demonstrating that other heavy noble gas isotope ratios are also close to their original composition. The highly radiogenic noble gas isotope signatures are unlikely to have been generated within the greenstone host-rocks, because seawater altered-volcanic rocks have high abundances of non-radiogenic atmospheric noble gas isotopes. In contrast, the strongly radiogenic noble gas isotope signatures are likely to have been generated in ancient basement rocks underlying the greenstones at ∼2.65 Ga. The combined noble gas and halogen data are consistent with models in which redox reactions triggered by interaction of independently and distally sourced H 2O–CO 2 and CH 4 localized high-grade gold mineralization. We suggest that the fluids were intimately associated with crustal magmatism in the St Ives Goldfield and that abiogenic CH 4 could be an important moderator of redox processes in other crustal environments.

Recycled gabbro signature in hotspot magmas unveiled by plume–ridge interactions

The geochemistry of lavas erupted at locations where mantle plumes interact with mid-ocean ridges reflects the mixing between the two sources. Analysis of lavas erupted above the Foundation hotspot, near the Pacific–Antarctic Ridge, reveal a geochemical signature indicative of both a primitive mantle plume source and a recycled oceanic lithosphere source. Lavas erupted within plate interiors above upwelling mantle plumes have chemical signatures that are distinct from mid-ocean ridge lavas. When a plume interacts with a mid-ocean ridge, the compositions of both their lavas changes, but there is no consensus as to how this interaction occurs1,2,3. For the past 15 Myr, the Pacific–Antarctic mid-ocean ridge has been approaching the Foundation hotspot4 and erupted lavas have formed seamounts. Here we analyse the noble gas isotope and trace element signature of lava samples collected from the seamounts. We find that both intraplate and on-axis lavas have noble gas isotope signatures consistent with the contribution from a primitive plume source. In contrast, near-axis lavas show no primitive noble gas isotope signatures, but are enriched in strontium and lead, indicative of subducted former oceanic lower crust melting within the plume source5,6,7. We propose that, in a near-ridge setting, primitive, plume-sourced magmas formed deep in the plume are preferentially channelled to and erupted at the ridge-axis. The remaining residue continues to rise and melt, forming the near-axis seamounts. With the deep melts removed, the geochemical signature of subduction contained within the residue becomes apparent. Lavas with strontium and lead enrichments are found worldwide where plumes meet mid-ocean ridges6,7,8, suggesting that subducted lower crust is an important but previously unrecognised plume component.

Extreme methane deuterium, nitrogen and helium enrichment in natural gas from the Homorod seep (Romania)

Methane (CH 4) in terrestrial environments, whether microbial, thermogenic, or abiogenic, exhibits a large variance in C and H stable isotope ratios due to primary processes of formation. Isotopic variability can be broadened through secondary, post-genetic processes, such as mixing and isotopic fractionation by oxidation. The highest and lowest 13C and 2H (or D, deuterium) concentrations in CH 4 found in various geologic environments to date, are defined as “natural” terrestrial extremes. We have discovered a new extreme in a natural gas seep with values of deuterium concentrations, δD CH4, up to + 124‰ that far exceed those reported for any terrestrial gas. The gas, seeping from the small Homorod mud volcano in Transylvania (Romania), also has extremely high concentrations of nitrogen (> 92 vol.%) and helium (up to 1.4 vol.%). Carbon isotopes in CH 4, C 2H 6 and CO 2, and nitrogen isotopes in N 2 indicate a primary organic sedimentary origin for the gas (a minor mantle component is suggested by the 3He/ 4He ratio, R/Ra ~ 0.39). Both thermogenic gas formation modeling and Rayleigh fractionation modeling suggest that the extreme deuterium enrichment could be explained by an oxidation process characterised by a δD CH4 and δ 13C CH4 enrichment ratio (ΔH/ΔC) of about 20, and may be accounted for by abiogenic oxidation mediated by metal oxides. All favourable conditions for such a process exist in the Homorod area, where increased heat flow during Pliocene–Quaternary volcanism may have played a key role. Finally we observed rapid variations (within 1 h) in C and H isotope ratios of CH 4, and in the H 2S concentrations which are likely caused by mixing of the deep oxidized CH 4–N 2–H 2S–He rich gas with a microbial methane generated in the mud pool of one of the seeps. We hypothesize that the unusual features of Homorod gas can be the result of a rare combination of factors induced by the proximity of sedimentary organic matter, mafic, metal-rich volcanic rocks and salt diapirs, leading to the following processes: a) primary thermogenic generation of gas at temperatures between 130 and 175 °C; b) secondary alteration through abiogenic oxidation, likely triggered by the Neogene–Quaternary volcanism of the eastern Transylvanian margin; and c) mixing at the surface with microbial methane that formed through fermentation in the mud volcano water pool. The Homorod gas seep is a rare example that demonstrates how post-genetic processes can produce extreme gas isotope signatures (thus far only theorized), and that extremely positive δD CH4 values cannot be used to unambiguously distinguish between biotic and abiotic origin.

Dual isotope and isotopomer measurements for the understanding of N2O production and consumption during denitrification in an arable soil

The aim of our research was to obtain information on the isotopic fingerprint of nitrous oxide (N2O) associated with its production and consumption during denitrification. An arable soil was preincubated at high moisture content and subsequently amended with glucose (400 kg C ha−1) and KNO3 (80 kg N ha−1) and kept at 85% water‐filled pore space. Twelve replicate samples of the soil were incubated for 13 days under a helium‐oxygen atmosphere, simultaneously measuring gas fluxes (N2O, N2 and CO2) and isotope signatures (δ18O‐N2O, δ15Nbulk‐N2O, δ15Nα, δ15Nβ and 15N site preference) of emitted N2O. The maximum N2O flux (6.9 ± 1.8 kg N ha−1 day−1) occurred 3 days after amendment application, followed by the maximum N2 flux on day 4 (6.6 ± 3.0 kg N ha−1 day−1). The δ15Nbulk was initially −34.4‰ and increased to +4.5‰ during the periods of maximum N2 flux, demonstrating fractionation during N2O reduction, and then decreased. The δ18O‐N2O also increased, peaking with the maximum N2 flux and remaining stable afterwards. The site preference (SP) decreased from the initial +7.5 to −2.1‰ when the N2O flux peaked, and then simultaneously increased with the appearance of the N2 peak to +8.6‰ and remained stable thereafter, even when the O2 supply was removed. We suggest that this results from a non‐homogenous distribution of NO in the soil, possibly linked to the KNO3 amendments to the soil, causing the creation of several NO pools, which affected differently the isotopic signature of N2O and the N2O and N2 fluxes during the various stages of the process. The N2O isotopologue values reflected the temporal patterns observed in N2O and N2 fluxes. A concurrent increase in 15N site preference and δ18O of N2O was found to be indicative of N2O reduction to N2.

Gas isotopic signatures (He, C, and Ar) in the Lake Kivu region (western branch of the East African rift system): Geodynamic and volcanological implications

On 17 January 2002, the city of Goma was partly destroyed by two of the several lava flows erupted from a roughly N‐S oriented fracture system opened along the southern flank of Mount Nyiragongo (Democratic Republic of Congo), in the western branch of the East African rift system. A humanitarian and scientific response was promptly organized by international, governmental, and nongovernmental agencies coordinated by the United Nations and the European Union. Among the different scientific projects undertaken to study the mechanisms triggering this and possible future eruptions, we focused on the isotopic (He, C, and Ar) analysis of the magmatic‐hydrothermal and cold gas discharges related to the Nyiragongo volcanic system, the Kivu and Virunga region. The studied area includes the Nyiragongo volcano, its surroundings, and peripheral areas inside and outside the rift. They have been subdivided into seven regions characterized by distinct 3He/4He (expressed as R/Rair) ratios and/or δ13C‐CO2 values. The Nyiragongo summit crater fumaroles, whose R/Rair and δ13C‐CO2 values are up to 8.73 and from −3.5‰ to −4.0‰ VPDB, respectively, show a clear mantle, mid‐ocean ridge basalt (MORB)‐like contribution. Similar mantle‐like He isotopic values (6.5–8.3 R/Rair) are also found in CO2‐rich gas emanations (mazukus) along the northern shoreline of Lake Kivu main basin, whereas the 13δC‐CO2 values range from −5.3‰ to −6.8‰ VPDB. The mantle influence progressively decreases in (1) dissolved gases of Lake Kivu (2.6–5.5 R/Rair) and (2) the distal gas discharges within and outside the two sides of the rift (from 0.1 to 1.7 R/Rair). Similarly, δ13C‐CO2 ratios of the peripheral gas emissions are lighter (from −5.9‰ to −11.6‰ VPDB) than those of the crater fumaroles. Therefore, the spatial distribution of He and C signatures in the Lake Kivu region is mainly produced by mixing of mantle‐related (e.g., Nyiragongo crater fumaroles and/or mazukus gases) and crustal‐related (e.g., gas discharges in the Archean craton) fluids. The CO2/3He ratio (up to 10 × 1010) is 1 order of magnitude higher than those found in MORB, and it is due to the increasing solubility of CO2 in the foiditic magma feeding the Nyiragongo volcano. However, the exceptionally high 40Ar*/4He ratio (up to 8.7) of the Nyiragongo crater fumaroles may be related to the difference between He and Ar solubility in the magmatic source. The results of the present investigation suggest that in this area the uprising of mantle‐originated f luids seems strongly controlled by regional tectonics in relation to the geodynamic assessment of the rift. These fluids are mainly localized in a relatively small zone between Lake Kivu and Nyiragongo volcano, with important implications in terms of volcanic activity.