Gas Isotopic Compositions Research Articles

Basin inversion, drifting and hyper-extension in the Central Atlantic Ocean and Maghrebian Tethys as fluid driving mechanisms for the superimposed base metal mineralization events in the Jbel Bou Dahar carbonate-hosted Pb-Zn-Ba deposits (High Atlas, Morocco)

The Early Jurassic Jbel Bou Dahar reef-bearing carbonate platform in the eastern High Atlas, Morocco, contains numerous carbonate-hosted and fault-controlled Pb-Zn-Ba deposits, prospects, and showings. Combined field, petrographic and geochemical data, including REE + Y analyses, stable (C-O-S), radiogenic (SrPb) and noble gas (He, Ne, Ar) isotopic compositions, record two temporally distinct metallogenic events. Both events are related to post-rifting and inversion of the inherited Mesozoic Atlas paleorift. The ore deposits are thought to have been formed during large-scale episodes of transtensional basin evolution, which developed as a far-field effect of the drifting of the Central Atlantic Ocean and Maghrebian Tethys while the basin continued to invert in response to the ongoing convergence between the African and the Eurasian plates. The paragenetically earliest Zn-rich ore was generated in a transtensional setting coincident with the hyper-extension of Maghrebian Tethys and the initial stages of drifting and formation of the Central Atlantic passive margin. Crustal extension and high heat fluxes provided by the hot upwelling mantle would have triggered buoyancy-driven convection of deeply sourced fluids and maturation of organic matter dispersed within the host carbonates to produce hydrocarbons within an extensional basin setting. These relatively reduced Zn-rich ore-forming fluids acquired metals mainly through protracted interaction with the country rocks including the underlying Triassic siliciclastic series and the granitic basement rocks. Regional ENE- to E-W-trending major faults would have acted as conduits for upward fluid flow and traps for Zn-Pb-Ba mineralization. Conversely, the late Pb-rich mineralization stage II is broadly constrained to have occurred between ca. 70 Ma and 10 Ma and is thought to be related to the transition from orogenic shortening (late Eocene) to post-orogenic crustal extension and exhumation (early Miocene) following Alpine orogenic collapse. Mixing of down-ward percolating meteoric fluids and ascending rock-buffered hydrothermal brines that had previously equilibrated with the radiogenic basement rocks along with thermochemical sulfate reduction of transported sulfate and/or thermal cracking, would have been the main ore-forming processes that controlled ore deposition. Given these fluid characteristics and geodynamic settings, the Jbel Bou Dahar ore field is classified as a hybrid carbonate-hosted Pb-Zn-Ba district formed by the juxtaposition of two deposit types rather than one progressively evolving mineralizing system. From an exploration standpoint, new delineation here of the two metallogenic events provides valuable exploration tools for further targeting PbZn and barite resources in the Atlas system of North Africa and other areas where similar orogenic belts experienced post-rift subsidence and basin inversion.

Substantiating of oil and gas prospects of Mesozoic sediments based on the geochemical model of mud volcanoes in the Shamakhi-Gobustan structural element of the South Caspian megadepression

There are up to 120 mud volcanoes in the Shamakhi-Gobustan region. During the process of mud volcano eruptions, a large amount of solid, liquid, and gaseous products are thrown to the Earth’s surface, which are widely used for the identification of oil and gas deposits and are considered the main indicator of the productivity of the basin. According to laboratory results from the analysis of solid, liquid, and gas products of mud volcanoes, it is possible to obtain detailed information about the oil-gas content of deep-lying sediments. Therefore, the study of the geochemical composition of the mud volcanoes in the Shamakhi-Gobustan trough plays a major role in the discovery of new oil-gas and gas-condensate deposits. To clarify the changes in the chemical and isotopic composition of gases from mud volcanoes in the Shamakhi-Gobustan trough and to evaluate the oil-bearing and gas-bearing potential of Mesozoic sediments, the characteristics of changes in the isotopic composition of methane gas, heavy hydrocarbons, carbon dioxide, ni- trogen, as well as CH4 and CO2, were studied. The amount of methane in the gas emissions released from mud volcanoes in the Azerbaijan region is more than 90%. The amount of CH4 in the mud volcanoes of the Shamakhi-Gobustan trough ranges from 78.5% to 97.56%. The minimum amount of methane is found in North Gobustan (Gizmeydan 86.8%, Malikchobanli 78.5%), while relatively high amounts are mainly noted in Central (Kushchu 97.55%) and South Gobustan (including Dashgil 97.57%, Goturdag 96.55%, Bahar 96.78%). Mud vol- canoes are less developed in the North Gobustan region and are small in size. In the Central zone, both the size and the number of volcanic cones increase significantly compared to North Gobustan. The largest and most active volcanoes have developed in the southern zone of the trough. Huge mud volcanoes such as Dashmerdan, Solakhay, Ayrantoken, Goturdag, Kirdag, and other volcanoes have developed along the Alat range. The mud volcanoes of North and Central Gobustan are mainly confined to Cretaceous and Paleogene sediments, and due to the low occurrence of plastic clay rocks in these sediment sections, mud volcanoes are rare and weakly active. On the contrary, to the south of these zones, that is, in South Gobustan, they are located in Pliocene sediments, and due to the presence of very thick plastic rocks in their section, mud volcanoes are widespread, and they are active volcanoes that are morphologically sharply reflected. It should be noted that in areas where plastic clay rocks with significant thickness and rheologically active properties are developed, large cones of mud volcanoes that erupt frequently are observed. The calculated gas production of mud volcanoes increases from the northern zone towards South Gobustan. Thus, while the calculated gas production of the Nabur volcano located in the Northern zone is 1500 m3/day, the calculated gas production of the Dashgil mud volcano located in South-Eastern Gobustan is 40,000 m3/day. In the central and south- ern zones of the Shamakhi-Gobustan trough, the presence of ancient rock fragments from the Oligocene-Miocene (Maykop) age rocks forming their roots in the solid waste of mud volcanoes (Cretaceous, Paleocene, Eocene), a large percentage of methane gas (97.57%), transverse elevations, and the presence of an intersection zone of longitudinal faults suggests that there is a tectonic rupture zone rich in natural gas below the base of the volcano. This is proven once again by the occurrence of gas flows in Anart (110,000 m3/day), Utalgi (50,000 m3/day), and the Touragay field (20,000 m3/day). The presence of oil films in the eruption products of mud volcanoes indicates the accumulation of oil alongside gas.

Geochemical Characteristics and Origin of Natural Gas in the Middle of Shuntuoguole Low Uplift, Tarim Basin: Evidence from Natural Gas Composition and Isotopes

Multiple types of reservoirs, including volatile oil reservoirs, condensate gas reservoirs, and dry gas reservoirs, have been discovered in ultra-deep layers buried at depths greater than 7500 m. Understanding the genetic types of natural gas is of utmost importance in evaluating oil and gas exploration potential. The cumulative proved reserves of the super deep layer in the Shuntuoguole low uplift area of the Tarim Basin exceed 1 × 108 t (oil equivalent). The origin, source, and accumulation characteristics of natural gas still remain a subject of controversy. By analyzing the composition and carbon isotope of natural gas, a detailed investigation was conducted to examine the unique geochemical and reservoir formation characteristics of the Ordovician ultra-deep natural gas within different fault zones in the middle region of the Shuntuoguole low uplift. It was determined that most of the natural gas in this area is displaying a characteristic of wet gas with a drying coefficient ranging from 0.41 to 0.99. The carbon isotope composition of methane in the gas reservoir shows relatively light values, ranging from −49.4‰ to −42‰. The carbon and hydrogen isotopes of the components are distributed in a positive order. The natural gas is oil type gas, which is derived from marine sapropelic organic matter and has a good correspondence with the lower Yuertusi formation. The maturity of natural gas in Shunbei No. 1 and No. 5 fault zones is about 1.0%, which is the associated gas of normal crude oil, while the maturity of No. 4 and No. 8 fault zones is higher than 1.0%, which is the mixture of kerogen pyrolysis gas and crude oil pyrolysis gas. The variations in the drying coefficient and carbon isotope composition of the natural gas provide evidence for the migration patterns within the Shuntuoguole low uplift central region. It indicates that the Shunbei No. 5 and No. 8 fault zones have likely migrated from south to north, while the No. 4 fault zone has migrated from the middle to both the north and south sides. These migration patterns are primarily controlled by high and steep strike-slip faults, which facilitate the vertical migration of natural gas along fault planes. Consequently, the gas accumulates in fractured and vuggy reservoirs within the Ordovician formation.

Fluid origin and evolution of the Taolin Pb-Zn deposit in northeastern Hunan Province, South China: Insights from fluid inclusions and H-O-He-Ar isotopes

Situated in northeastern Hunan Province, the vein-type Pb-Zn orebodies at Taolin are mainly hosted in NE-/NEE-trending faults between Dayunshan-Mufushan pluton and Neoproterozoic metasedimentary rocks of the Lengjiaxi Group. Hydrothermal mineralization can be divided into five stages: (1) coarse-grained quartz stage, (2) quartz-fluorite-base metal stage, (3) quartz-barite-fluorite-base metal stage, (4) pale pink and colorless quartz stage, and (5) fine-grained quartz stage. In this research, fluid inclusions as well as stable (H-O) and noble gas (He-Ar) isotope compositions were performed to uncover the nature, origin, and evolution of the ore-forming fluids, ore precipitation mechanisms, and mineralization process of the Taolin deposit. Four types of fluid inclusions, i.e., liquid-rich two-phase inclusions (LV-type), pure liquid phase inclusions (PL-type), vapor-rich two-phase inclusions (VL-type), and pure vapor phase inclusions (PV-type), were distinguished in sphalerite, quartz, and fluorite. Microthermometric analysis of fluid inclusion assemblages in sphalerite, quartz, and fluorite from different stages indicates that from the Stage 1 to Stage 5, the homogenization temperatures vary between 168 and 211 °C, between 151 and 198 °C, between 131 and 180 °C, between 132 and 164 °C, and between 118 and 138 °C, respectively, whereas the fluid salinities vary from 12.4 to 16.9 wt% NaCl equivalent, from 9.7 to 14.6 wt% NaCl equivalent, from 5.6 to 10.3 wt% NaCl equivalent, from 3.6 to 9.7 wt% NaCl equivalent, and from 0.9 to 3.8 wt% NaCl equivalent, respectively. The H-O isotope data of quartz and the He-Ar isotopic compositions of sulfide crystals suggest that the ore-forming fluids were a mixture of crust-derived magmatic hydrothermal fluid and meteoric water. Fluid mixing and cooling were likely the crucial mechanisms for ore precipitation.

Noble gas characteristics of microbial gas in the Qaidam Basin, China: Implications for helium enrichment processes

Helium is a critical, strategic and nonrenewable resource with limited reserves and unstable supplies. However, the helium sources and migration processes in petroliferous basins remain unclear. The Qaidam Basin features multiple reservoir layers, multiple genetic types of natural gas, and varying helium concentrations, providing an ideal natural laboratory for understanding the helium enrichment processes. Here, we present the original noble gas isotopic compositions and major gas components of 11 microbial gas samples from three gas layers in the Sebei No.1 gas field, eastern Qaidam Basin, China. The helium isotopic ratios range from 0.007 to 0.057 Ra, reflecting a predominantly crustal source. The Quaternary Sebei microbial gas features much lower helium concentration (0.0003–0.001%), 21Ne/22Ne ratio (0.031–0.034), and 40Ar/36Ar ratio (292–380) than thermogenic natural gases in the Qaidam Basin. The middle gas layer (II) of the Sebei gas field features higher 21Ne/22Ne and 40Ar/36Ar ratios than the top and bottom gas layers, displaying positive correlations with higher 4He groundwater concentrations before degassing, as calculated from 4He/20Ne ratios and 20Ne concentrations in air-saturated water. However, the correlations between the 4He contents in natural gas and the 21Ne/22Ne and 40Ar/36Ar ratios are unclear, suggesting that 4He dissolves into the groundwater system before degassing into a gas reservoir and that the variations in the 4He concentration in the gas phase are caused by the different levels of hydrocarbon dilution. Quantitative calculations of helium production revealed an external helium flux from the crustal basement except for the in-situ production from sedimentary strata even in this broadly-defined self-generating and self-preserving natural gas system. The helium resources in the Qaidam Basin are mainly distributed in tectonically active zones with uplifted pre-Jurassic basement rocks (providing sufficient helium sources), ancient groundwater systems (accumulating more helium) and suitable hydrocarbon production (acting as a carrier gas but diluting helium as slightly as possible).

Geochemistry of Liquid Hydrocarbons and Natural Gases Combined with 1D Basin Modeling of the Oligocene Shale Source Rock System in the Offshore Nile Delta, Egypt.

The current study aims to integrate the geochemical characteristics of the Oligocene shale source rock system, oil, condensate, and natural gas samples in the Oligocene sandstone reservoirs from three exploration wells located in the offshore Nile Delta, East Mediterranean Sea, using organic geochemistry and a 1D basin modeling scheme. The Tineh shales exhibit total organic carbon values ranging between 0.90 and 1.89 wt %, along with hydrogen index values in the range of 54-240 mg hydrocarbon/g rock. The geochemical characterization suggests that the shale intervals of the Oligocene Tineh Formation contain type II-III and type III kerogens and, thereby, could be regarded as promising oil- and gas-prone source rocks with high contributions of gas generation potential. The study also reconstructs the 1D thermal and burial history models, showing that the Oligocene Tineh source rock system is in the main oil and wet gas generation phases from the late Miocene to the present time. The simulated basin models reveal the transformation (TR) of 10-50% kerogen to oil during the late Miocene-early Pliocene period and that the Oligocene Tineh source rock system has larger oil generation and expulsion competency, with a TR value of up to 65% during the early Pliocene-Pleistocene time period. The thermogenic gas was also formed during this time and continued to the present day. This study also investigated the presence of oil and condensate in the Oligocene sandstone reservoir samples and revealed that they were generated from mature source rock, ranging from moderately to highly mature stages. This source rock unit was deposited in fluvial to fluvial-deltaic environments under oxic mixed organic conditions and accumulated during the Tertiary time, as evidenced by the presence of the oleanane biomarker dating indicator. The molecular and isotope compositions of natural gases revealed that most of the natural gases in the Oligocene sandstone reservoir are mainly thermogenic methane gases that were generated from mainly mixed organic matter. The thermogenic methane gases were formed mainly from secondary cracking of oil and gas, with small contributions of primary kerogen cracking. The properties of natural gases together with oil and condensate in the Oligocene reservoir rocks suggest that most of the thermogenic methane gases and associated liquid hydrocarbons are derived primarily from the Oligocene shale source rock system and formed by primary kerogen cracking and secondary oil and oil/gas cracking in different thermal maturity stages. Therefore, the Oligocene Tineh Formation can be regarded as self-source generation and self-reservoir rock; hence, an intensive oil exploration and production program can be recommended whenever the Tineh source rock system is is well developed and deeply buried.

Inter-laboratory re-determination of the atmospheric 22Ne/20Ne

Accurate knowledge of the Ne isotopic composition of air is essential for planetary science. While the uncertainty of the noble gas isotopic composition of air has been drastically reduced to the level of ∼0.1% in the last few years thanks to modern techniques, the most widely accepted value of the 22Ne/20Ne ratio of air (0.102 ± 0.0008, Eberhardt et al., 1965) has an uncertainty of ±0.78% (1σ). Here we present the first multi-laboratory re-determination of the atmospheric 22Ne/20Ne. An artificial, high purity mixture of 20Ne and 22Ne was prepared and the 22Ne/20Ne (0.11888 ± 0.00001, 1σ) and 20Ne/22Ne (8.4118 ± 0.0007, 1σ) determined gravimetrically. This gas was used to determine the mass fractionation of five mass spectrometers allowing the air 22Ne/20Ne to be determined (n = 234 analyses). Each laboratory sampled their own local air, used a different gas preparation system and analysis procedure as well as doing their own expansion of the high-pressure artificial Ne gas. Individual air 22Ne/20Ne determinations have uncertainties in the range of 0.01–0.08%. The overall reproducibility of the calculated 22Ne/20Ne of air between the laboratories shows no overdispersion with respect to the individual uncertainties. We report a global value for the atmospheric 22Ne/20Ne of 0.10196 ± 0.00007 (0.07%, 1σ), equivalent of 20Ne/22Ne of 9.808 ± 0.007. This is almost identical to the Eberhardt et al. (1965) value although its uncertainty shows a 12 times reduction. Our study did not verify any of the other previous determinations of atmospheric 22Ne/20Ne. This highly accurate and precise atmospheric 22Ne/20Ne value provides a new reference for atmospheric 21Ne/20Ne determinations and we recalculate (21Ne/20Ne)air of five recent determinations. While this exercise resulted in no significant change to the absolute values, it gives more confidence with respect to the correctness of (21Ne/20Ne)air. We suggest that the revised value for atmospheric 22Ne/20Ne be used routinely in all geoscience applications.

An Assessment of Deep Borehole Disposal Post-Closure Safety

Around the world, deep borehole disposal is being evaluated for intermediate level-waste (ILW), high-level waste, and spent nuclear fuel. To facilitate a disposal concept options analysis for ILW in Australia, desktop and lab-based geoscientific investigations, together with generic post-closure safety assessments of deep borehole disposal of long-lived ILW, have been undertaken. This paper reports on geoscientific data obtained on crystalline rock and rock salt as model rocks for geological disposal. Petrophysical and mineralogical properties for these rocks have been investigated to provide realistic data for evaluation and input to post-closure safety assessments. For crystalline rock samples originating from depths between 700 to 1900 m, very low hydraulic conductivity (2 × 10−12 to 3 × 10−11 m/s) and very low porosity (0.02% to 1.2%) were obtained. The noble gas isotopic composition of fluid inclusions from the same depth interval confirmed the rock had been devoid of recent interaction with meteoric water, thus providing potentially suitable conditions for geological disposal. Rock salt from a 802-m (heterogeneous sample with 40% halite) and a 1100-m (sample with 98% halite) depth also had a low hydraulic conductivity (5 × 10−10 to 5 × 10−9 m/s at 802 m and 10−11 to 2 × 10−10 m/s at 1100 m) and very low porosity (~0.8% for the heterogenous sample and ~0.2% for the pure halite sample). Post-closure safety assessments based on numerical modeling provided bounding conditions around the thermal evolution of the disposal environment in crystalline rock for low heat generating ILW (50 W per 180-L vitrified waste canister), including exploring the sensitivity of temperature evolution within the borehole and rock environment to parameters such as heat load, borehole depth, geothermal gradients, and rock thermal conductivity. The coupling of heat transport with radionuclide migration to account for buoyancy-driven transport was shown to have a limited impact on radionuclide migration. For a disposal borehole in crystalline rock, the radionuclide concentrations and annual dose rates from key radionuclides (99Tc and 79Se) for a 500-m, 1000-m, or 3000-m deep borehole were negligible (i.e., many orders of magnitude smaller than the threshold dose the International Atomic Energy Agency considers insignificant for humans, 0.01 mSv/year). For disposal in rock salt, a suite of numerical model scenarios explored the effectiveness of the engineered barriers, including the glass matrix, primary package, and overpack, assuming diffusion-dominated transport. These scenarios illustrated that the performance of the disposal system was insensitive to the presence or absence of engineered barriers, as dose rates at late time (>105 years) were nearly identical for all scenarios. These results indicate that the natural barrier provided by the salt is very effective at containing radionuclides, while the engineered barriers serve mainly to delay the arrival of the peak dose. While the results are preliminary, the post-closure safety assessments, supported by measured data from crystalline rock and rock salt, give confidence that deep borehole disposal of long-lived ILW would result in dose rates considered insignificant for humans within a few meters from the borehole.

Isotope Composition of Gases of Magmatic and Sedimentary Volcanic Systems: A Review and Comparative Analysis

Isotope Composition of Gases of Magmatic and Sedimentary Volcanic Systems: A Review and Comparative Analysis

Unravelling the pre-eruptive conditions of the rhyolitic Šumovit Greben lava dome from clinopyroxene-dominant glomeroporphyritic clots

Detailed analyses of mineral composition and whole-rock geochemical data helped to unravel the volcanic plumbing system beneath the rhyolitic Šumovit Greben lava dome, the westernmost member of the Kožuf-Voras volcanic system (N. Macedonia). It is characterized by high SiO2 content (> 70 wt%) coupled with low MgO (< 1 wt%) and Sr (< 500 ppm) suggesting fractionation of clinopyroxene and plagioclase at depth forming a crystal mush and a crystal-poor rhyolitic lens by fractional crystallization and melt extraction on top of it. The crystal mush is composed of mainly clinopyroxene, biotite and plagioclase, whereas sanidine and plagioclase are the most abundant phenocrysts of the rhyolitic lens. The main dome forming event occurred at ca. 2.9 Ma, which sampled the crystal-poor rhyolitic lens. After a short quiescence time, an explosive eruption occurred depositing a massive lapilli tuff layer northwest of the lava dome, and an extrusion of a small-volume lava flow on the northern side of the lava dome at ca. 2.8 Ma. This latter sampled also the crystal mush, as it contains abundant glomeroporphyritic clots of clinopyroxene ± plagioclase ± biotite. The clinopyroxene phenocrysts are chemically homogeneous, their crystallization temperature is ca. 900 °C representing the crystal mush, whereas the plagioclase and the sanidine crystallized at a lower temperature (ca. 790 °C) representing the rhyolitic lens. Noble gas isotopic composition of the clinopyroxene indicate no mantle-derived fluids (< 0.5%) having an R/Ra of ca. 0.04 Ra. The rejuvenation of the system probably occurred due to implementation of mafic magma at depth leading to a heat transfer and partial melting of the cumulate. This led to crystallization of Ba-rich rims of the sanidine and An- and Sr-rich rims of the plagioclase. The crystal mush zone beneath Šumovit Greben might be connected to the nearby, more mafic volcanic centers, and the eruption of Šumovit Greben could have been the start of the last cycle in the lifetime of the Kožuf-Voras volcanic system.

Light noble gases in 11 achondrites: Cosmic ray exposure ages, gas retention ages, and preatmospheric sizes

AbstractWe report light noble gas (He, Ne, and Ar) concentrations and isotopic ratios in 11 achondrites, Tafassasset (unclassified primitive achondrite), Northwest Africa (NWA) 12934 (angrite), NWA 12573 (brachinite), Jiddat al Harasis (JaH) 809 (ureilite), NWA 11562 (ungrouped achondrite), four lodranites (NWA 11901, NWA 7474, NWA 6685, and NWA 6484), NWA 2871 (acapulcoite), and Sahara 02029 (winonaite), most of which have not been previously studied for noble gases. We discuss their noble gas isotopic composition, determine their cosmogenic nuclide content, and systematically calculate their cosmic ray exposure (CRE) and gas retention ages. In addition, we estimate their preatmospheric radii and preatmospheric masses based on the shielding parameter (22Ne/21Ne)cos. None of the studied meteorites shows evidence of contribution from solar cosmic rays (SCRs). JaH 809 and NWA 12934 show evidence of 3He diffusive losses of &gt;90% and 40%, respectively. The winonaite Sahara 02029 has lost most of its noble gases, either during or before analysis. The average CRE age of Tafassasset of ~49 Ma is lower than that reported by Patzer et al. (2003), but is consistent with it within the uncertainties; this confirms that Tafassasset and CR chondrites are not source paired, CR chondrites having CRE ages from 1 to 25 Ma (Herzog &amp; Caffee, 2014). The ureilite JaH 809 has a CRE age of ~5.4 Ma, which falls into the typical range of exposure ages for ureilites; the angrite NWA 12934 has a CRE age of ~49 Ma, which is within the main range of exposure ages reported for angrites (0.2–56 Ma). We calculate a CRE age of ~2.4 Ma for the brachinite NWA 12573, which falls into a possible “cluster” in the brachinite CRE age histogram around ~3 Ma. Three lodranites (NWA 11901, NWA 7474, and NWA 6685) have CRE ages higher than the average CRE ages of lodranites measured so far, NWA 11901 and NWA 6685 having CRE ages far higher than the CRE age already reported by Li et al. (2019) on NWA 8118. The measured 40K‐40Ar gas retention ages fit well into established systematics. The gas retention age of Tafassasset is consistent, within respective uncertainties, with that previously calculated by Patzer et al. (2003). Our study indicates that Tafassasset originates from a meteoroid with a preatmospheric radius of ~20 cm, however discordant with the radius of ~85 cm inferred in a previous study (Patzer et al., 2003).

Origin of CO2 in Upper Devonian Duperow Formation and the Bakken Petroleum System at Kevin Dome, Northwest Montana

Carbon capture and storage (CCS) is a key mitigation strategy in achieving global net-zero emissions. It is therefore essential to identify and characterize potential subsurface storage repositories. Natural CO2 accumulations provide an opportunity to understand the behavior of CO2 in the subsurface. Here, we investigate the source(s), migration, and storage of CO2 in the Upper Devonian Duperow Formation at Kevin Dome, northwest Montana, USA within the Bakken Petroleum System. We report, major gas, stable and noble gas isotopic compositions in bulk gas samples (n = 19) produced from nearby hydrocarbon-bearing reservoirs at Kevin Dome and compare with CO2 bearing fluid inclusions (n = 24) from the Duperow Formation. Using the same methods, bulk gas samples (n = 9) from the adjacent Ferguson Field, (Exshaw/Bakken Petroleum System) in southern Alberta, Canada, and fluid inclusions from the Sweetgrass Hills igneous complex (n = 2) were analyzed to understand CO2 generation and the subsequent processes affecting CO2 regionally. We find that CO2 in the Upper Devonian Duperow Formation is magmatic in origin, likely related to the nearby Sweetgrass Hills igneous complex intrusion (∼52 Ma), whereas CH4 and N2 gases are generated predominantly by thermogenic processes associated with hydrocarbon generation during burial. Since emplacement, most CO2 in the hydrocarbon-bearing reservoirs of the Bakken petroleum system at Kevin Dome (∼98%) and the Ferguson Field (∼82%) has subsequently been dissolved into the groundwater. We employ a solubility model to calculate minimum gas/water ratios in Kevin Dome and the Ferguson Field, which are consistent with more groundwater interaction and more dissolution at Kevin Dome. Understanding the subsurface processes affecting CO2 is critical for future CO2 storage site selection.

Origin of Ag-Pb-Zn mineralization at Huanaote, Inner Mongolia, NE China: Evidence from fluid inclusion, H-O-S-Pb and noble gas isotope studies

The newly-discovered Huanaote Ag-Pb-Zn deposit, containing 1173 tons Ag with a grade of 154 g/t, is situated in the western part of the Great Xing’an Range metallogenic belt. The source of metals and the fluid evolution for this large metallogenic system are still ambiguous. Mineralized Ag-Pb-Zn veins are primarily hosted in Late Carboniferous monzogranite and Devonian slate. Three paragenetic stages of mineralization were recognized at Huanaote, including (stage I) early pyrite + arsenopyrite + quartz ± K-feldspar; (stage II) the main ore stage sulfide (sphalerite, galena, chalcopyrite and pyrite) + sulfosalt (freibergite, bournonite, wittichenite and tetrahedrite) + quartz + sericite + chlorite ± epidote ± fluorite; and (stage III) late pyrite + quartz + calcite. The homogenization temperatures of fluid inclusion assemblage for stages I and II range from 254 to 337 ℃ and 143 to 270 ℃, respectively, while the fluid salinity varied from 2.3 to 14.2 and 0.9 to 11.8 wt% NaCl equiv. for stages I and II, respectively. The fluid δ18OH2O and δDH2O values range from −0.4 to +6.2‰ and −116.8 to −104.8‰, respectively, indicating that the source of the fluids was primarily derived from a magma with less contribution from meteoric waters. Sulfur isotope analyses of sulfides exhibit δ34S values from −4.3 to +8.0‰, consistent with those observed in other Ag-Pb-Zn deposits in this region, suggesting the sulfur was mainly magmatic origin with minor sedimentary sulfur addition. Similarly, the Pb isotope compositions of sulfides resemble those of local Mesozoic magmatism, implying a Mesozoic magmatic source for the metals. Additionally, the noble gas isotope compositions, specifically the 3He/4He ratios (ranging from 4.41 to 7.18 Ra, mean of 5.56 Ra) for fluid inclusions,strongly support a deep magmatic fluid responsible for the formation of Huanaote deposit. Fluid cooling, mixing with meteoric waters and dilution are suggested to be important processes for Ag-Pb-Zn deposition at Huanaote.

Carbon isotope composition characteristics of light hydrocarbon gas from typical kerogen cracking and its application for gas source identification: A case study of the Sichuan Basin

The natural gas resources in the Sichuan Basin are abundant and exhibit various phenomena, for example, mixed sources, mixed maturities and overlapping combinations, resulting in great difficulties in identifying natural gas sources. In this study, several groups of thermal simulation experiments were conducted on various types of kerogens using closed and/or semi‐open systems to investigate the characteristics of the carbon isotope compositions of light hydrocarbon gases derived from different typical kerogens. The results showed that the carbon isotope compositions and variation trends of methane and ethane are controlled by the kerogen type, thermal simulation system and thermal evolution degree. The carbon isotope compositions of light hydrocarbon gases derived from different types of kerogens exhibit some differences with increased thermal evolution degree. When the thermal simulation temperature increases from 320 to 550°C, the methane carbon isotope of typically marine source rocks, mainly type I and type II1 kerogens, is slightly higher than or equivalent to that of ethane. However, the ethane carbon isotope of terrestrial source rocks, primarily types II2 and III kerogens, is significantly heavier than methane. By comparison, the evolution trend of carbon isotope compositions of actual natural gas is well consistent with that of light hydrocarbon gases cracked from thermal simulation experiments with increased thermal evolution degree. These findings are of great importance to identify the source rock of actual natural gas with high thermal maturities, as well as to determine the sources of deep shale gas in the southern Sichuan Basin, the Yuanba gas field and the Puguang gas field. Finally, a fitting method of carbon isotope values of methane and ethane of light hydrocarbon gases can be used to more finely differentiate the sources of natural gas in complex areas with mixed sources, mixed maturities and overlapping combinations.

Temporal dynamics and controlling factors of CO2 and CH4 variability in the urban atmosphere of Wroclaw, Poland

Temporal and spatial distribution of both biogenic and anthropogenic components of atmospheric carbon dioxide (CO2) and methane (CH4) is crucial for understanding the environmental impacts of climate change over urban areas. This research focuses on applying stable isotope source-partitioning studies to determine the interactions between biogenic and anthropogenic CO2 and CH4 emissions in an average-sized city environment. Study signifies the weight of instantaneous variability and diurnal averaging as compared with seasonal records of variations of the atmospheric CO2 and CH4 at a variety of typical urban sites in the city of Wroclaw, conducted during a one-year period from June 2017 to August 2018.The findings reveal distinct temporal variations in atmospheric CO2 and CH4 mole fractions and their isotopic composition. The average atmospheric CO2 and CH4 mole fractions during the study period were 416.4 ± 20.5 ppm, and 1.95 ± 0.09 ppm, respectively. The study highlights the high variability of driving forces, including current energy use patterns, natural carbon reservoirs, planetary boundary layer dynamics, and atmospheric transport. Additionally, the relationship between the evolution of the convective boundary layer depth and the CO2 budget was analyzed using the CLASS model with input parameters based on field observations, resulting in insights such as an increase in the range of 25–65 ppm of CO2 during stable nocturnal boundary layers.The observed changes in stable isotopic signatures of air samples allowed for the identification of two main source categories in the city area: fuel combustion and biogenic processes. The δ13C-CO2 values of collected samples suggest that biogenic emissions dominate (up to 60 % of CO2 excess mole fraction) during the growing season, but are reduced by plant photosynthesis during summer afternoons. In contrast, local fossil-fuel CO2 contribution (up to 90 % of excess CO2 mole fraction) from domestic heating, vehicle emissions, and heat and power plants predominantly influence the urban GHG budget during winter. The δ13C-CH4 values indicate anthropogenic sources related to fossil fuel combustion during winter, with values ranging from −44.2 ‰ to −51.4 ‰, while slightly more depleted values, between −47.1 ‰ and −54.2 ‰, reflect a larger input of biological processes in the methane urban budget during summer.Overall, instantaneous and hourly variability of the above-mentioned readings of gas mole fraction and isotopic composition, have shown higher variability than seasonal amplitudes. Hence, respecting this granularity is the key to alignment and understanding significance of such localized atmospheric pollution studies. Additionally, the changing overprint of the system's framework, such as variability of wind and atmospheric layering patterns, weather events, provides context of sampling and data analysis at different frequencies.

Geochemical assessment and hydrocarbon potential of Oligocene–Pliocene source rocks from northeast onshore Nile Delta, Egypt

Recent exploration in the Nile Delta Basin has led to major oil and gas discoveries; however, source–reservoir relationships in the onshore part of the basin are still ambiguous. This work involves a comprehensive geochemical assessment of possible Oligocene–Pliocene source rocks, using TOC/Rock-Eval pyrolysis and gas chromatography–mass spectrometry. The aim is to investigate quantity, quality, thermal maturity, sources, and depositional paleoenvironment of the disseminated organic matter, and to correlate rock samples with hydrocarbons retrieved from the study area. Moreover, the chemical and isotopic compositions of gases were employed to examine origin, maturity, mixing and secondary alteration processes.Results reveal fair to good organic richness (TOC ∼1 wt%) for the Oligocene–Pliocene rocks, with the highest TOC content from the Oligocene Tineh Formation. The kerogen is generally gas-prone Type-III and to a lesser extent Type-IV and Type-II/III. Molecular and biomarker results indicate mixed source facies with variable contributions from higher plants, algae, bacteria, and plankton, deposited under suboxic to anoxic nearshore marine or lacustrine depositional settings. Significant biomarkers include elevated C26/C25 tricyclic terpane ratios (0.82–3.62), low C31 homohopane (22R)/C30 hopane ratios (0.17–0.63), and low oleanane and gammacerane contents. Maturity-related biomarkers, Rock-Eval Tmax and vitrinite reflectance values are consistent and suggest immature to early mature rock samples.Molecular and isotopic compositions of mud gases indicate complex origins and mixing histories ranging from primary microbial to pure thermogenic, where thermogenic processes dominate the pre-Miocene intervals.Chemometric analysis of 18 source-related biomarker ratios for rock extracts revealed four genetic families. Hierarchical cluster analysis (HCA) of biomarker data for rock extracts and condensate oils from the onshore Nile Delta indicates no correlation between Miocene–Pliocene rocks and condensates or oils in the area. Therefore, pre-Miocene source rocks are suggested to be the most probable candidates for hydrocarbons in the onshore Nile Delta.

Characteristics and varieties of gases enclathrated in natural gas hydrates retrieved at Lake Baikal

Molecular and stable isotope compositions of hydrate-bound gases collected from 59 hydrate-bearing sites between 2005 to 2019 in the southern and central sub-basins of Lake Baikal are reported. The δ2H of the hydrate-bound methane is distributed between − 310‰ and − 270‰, approximately 120‰ lower than its value in the marine environment, due to the difference in δ2H between the lake water and seawater. Hydrate-bound gases originate from microbial (primary and secondary), thermogenic, and mixed gas sources. Gas hydrates with microbial ethane (δ13C: − 60‰, δ2H: between − 310‰ and − 250‰) were retrieved at approximately one-third of the total sites, and their stable isotope compositions were lower than those of thermogenic ethane (δ13C: − 25‰, δ2H: − 210‰). The low δ2H of ethane, which has rarely been reported, suggests for the first time that lake water with low hydrogen isotope ratios affects the formation process of microbial ethane as well as methane. Structure II hydrates containing enclathrated methane and ethane were collected from eight sites. In thermogenic gas, hydrocarbons heavier than ethane are biodegraded, resulting in a unique system of mixed methane-ethane gases. The decomposition and recrystallization of the hydrates that enclathrate methane and ethane resulted in the formation of structure II hydrates due to the enrichment of ethane.

Noble gas insights into early impact delivery and volcanic outgassing to Earth's atmosphere: A limited role for the continental crust

Earth's atmosphere, crust and mantle have evolved together through continuous geochemical exchange throughout Earth's history. Constraints on the transport of volatile elements and compounds between these reservoirs are crucial for understanding how Earth could have stayed habitable for extended periods of time. Here we present a new forward model of He, Ne and Ar in the mantle, crust and atmosphere. We explore concentrations of noble gases at the end of accretion, bulk silicate Earth K/U ratios, crustal growth scenarios, and upper mantle processing rates throughout Earth's history. We search for parameter combinations that simultaneously satisfy observational constraints on present-day mantle 4He/3He and 40Ar/36Ar (sensitive to mantle outgassing and continental crust growth, which depletes the mantle of U, Th and K), atmospheric 20Ne/22Ne (which tracks the mix of outgassed vs. delivered Ne in the atmosphere), and atmospheric 40Ar/36Ar in the past and today (sensitive to volatile delivery, mantle outgassing and crustal growth). Leveraging this intertwined set of noble gas abundances and isotopic compositions yields new constraints on initial noble gas abundances in the mantle and on the proportions of atmospheric volatiles originating from delivery by impact degassing, mantle outgassing, and degassing of the continental crust. We find that atmospheric Ar isotopic evolution is primarily sensitive to the mantle processing rate history; the atmospheric Ar isotopic record should therefore not be used to reconstruct continental crust growth, but instead provides valuable insights into mantle processing rates. Our model predicts a measurably low 20Ne/22Ne ratio of ∼9.7 in Archean atmospheric samples. Most of atmospheric primordial 36Ar was directly delivered by chondritic bodies and not transferred to the atmosphere during an intense early episode of mantle outgassing. Nitrogen delivered by impact degassing could account for the present-day atmospheric nitrogen inventory.

Environment-Forming Effect of Bubble Gas Emissions in the Golubaya Bay, Black Sea: Oxygen Regime and Bacterial Mats

Gas seep and fluid flows from the seabed are an environment-forming factor of the aquatic environment, mainly due to their influence on the dissolved gases in the water, including dissolved oxygen. During the summer seasons from 2019 to 2021 in the area of shallow water gas emission site off the southern coast of the Heracles Peninsula, series of vertical probing profiles were carried out to determine hydrological parameters of the water: dissolved oxygen concentration (O2), temperature (T), salinity (S), and flow velocity (U). The study area is an underwater ledge with faults in the form of three canyons composed of dense limestones, two of which contained bubble gas emissions. Significant variability in O2 was identified in canyons where gas emissions are observed: from 1 to 80% saturation in the bottom layer, in contrast to normoxia at the background sites. Hypoxia was observed in the bottom layer above the emission sites in the absence of turbulence at temperature stratification. The values S decreased with depth, and the maximum difference reached 0.4‰. The bubble gas was dominated by methane (68.5–75.5%), and the carbon isotope composition of the bubble methane gas varied from –67.9 to –59.8‰ VPDB in 2019 and 2020, respectively. This generally indicates that the CH4 is of predominantly microbial genesis, was formed under different conditions, and matured in various periods of research during the monitoring period. Bacterial mats (mostly sulfur-oxidizing bacteria) were found in the areas of gas emissions.

Isotope Effects and the Atmosphere.

Chemical physics plays a large role in determining the isotopic compositions of gases in Earth's atmosphere, which in turn provide fundamental insights into the sources, sinks, and transformations of atmospheric gases and particulates and their influence on climate. This review focuses on the kinetic and photolysis isotope effects relevant to understanding the isotope compositions of atmospheric ozone, carbon dioxide, methane, nitrous oxide, and other gases and their historical context. The discussion includes non-mass-dependent isotope compositions of oxygen-containing species and a brief overview of the recent growth of clumped isotope measurements at natural isotopic abundances, that is, of molecules containing more than one rare isotope. The intention is to introduce chemistry researchers to the field of using isotope compositions as tracers of atmospheric chemistry and climate both today and back in time through ice and rock records and to highlight the outstanding research questions to which experimental and theoretical physical chemists can contribute. Expected final online publication date for the Annual Review of Physical Chemistry, Volume 74 is April 2023. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.