Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

Variation in ¹³C/¹²C-isotope ratios of fracture filling calcite was analyzed in situ to investigate carbon sources and cycling in fractured bedrock. The study was conducted by separating sections of fracture fillings, and analyzing the ¹³C/¹²C-ratios with secondary ion mass spectrometry (SIMS). Specifically, the study was aimed at fillings where previously published sulfur isotope data indicated the occurrence of bacterial sulfate reduction. The results showed that the δ¹³C values of calcite were highly variable, ranging from −53.8‰ to +31.6‰ (VPDB). The analysis also showed high variations within single fillings of up to 39‰. The analyzed calcite fillings were mostly associated with two calcite groups, of which Group 3 represents possible Paleozoic fluid circulation, based on comparison with similar dated coatings within the Baltic Shield and the succeeding Group 1–2 fillings represent late-stage, low temperature mineralization and are possibly late Paleozoic to Quaternary in age. Both generations were associated with pyrite with δ³⁴S values indicative of bacterial sulfate reduction. The δ¹³C values of calcite, however, were indicative of geochemical environments which were distinct for these generations. The δ¹³C values of Group 3 calcite varied from −22.1‰ to +11‰, with a distinct peak at −16‰ to −12‰. Furthermore, there were no observable depth dependent trends in the δ¹³C values of Group 3 calcite. The δ¹³C values of Group 3 calcite were indicative of organic matter degradation and methanogenesis. In contrast to the Group 3 fillings, the δ¹³C values of Group 1–2 calcite were highly variable, ranging from −53.8‰ to +31.6‰ and they showed systematic variation with depth. The near surface environment of <30 m (bsl) was characterized by δ¹³C values indicative of degradation of surface derived organic matter, with δ¹³C values ranging from −30.3‰ to −5.5‰. The intermediate depth of 34–54 m showed evidence of localized methanotrophic activity seen as anomalously ¹³C depleted calcite, having δ¹³C values as low as −53.8‰. At depths of ∼60–400 m, positive δ¹³C values of up to +31.6‰ in late-stage calcite of Group 1–2 indicated methanogenesis. In comparison, high CH₄ concentrations in present day groundwaters are found at depths of >300 m. One sample at a depth of 111 m showed a transition from methanogenetic conditions (calcite bearing methanogenetic signature) to sulfate reducing (precipitation of pyrite on calcite surface), however, the timing of this transition is so far unclear. The results from this study gives indications of the complex nature of sulfur and carbon cycling in fractured crystalline environments and highlights the usefulness of in situ stable isotope analysis.     

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin,Eastern United States

Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH₄) from deeper formations. This study compares concentrations and isotopic compositions of CH₄ sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH₄ ranging from 0.05 mg/L to 10 mg/L, thus, no immediate remediation is required. The δ¹³C values of CH₄ ranged from −66‰ to −16‰, and δ²H values ranged from −286‰ to −86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH₄ was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH₄ occurrence corresponded with groundwater abundant in Na⁺, Cl⁻, and HCO₃⁻, and with low concentrations of SO₄²⁻. The CH₄ and SO₄²⁻concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH₄ was abundant in more reducing waters, and SO₄²⁻ was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH₄ oxidation in shallow groundwater.     

Sources and flux of natural gases from Mono Lake,California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH₄ day⁻¹, and estimate total lakewide annual seep flux to be 2.1 × 10⁶ moles CH₄. Geochemical parameters (δ¹³CH₄,δDCH₄,CH₄/[C₂H₆+ C₃H₈]) andδ¹⁴CH₄measurements revealed that most of the seeps originate from a paleo-biogenic (δ¹³CH₄ = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2–3 mM at 50 cm; δ₁₃CH₄ = about −85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 μM in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1–1.3μM) were supersaturated with respect to the atmosphere. The δ¹³CH₄ (range = −21.8 to −71.8%.) of this unoxidized residual methane was enriched in ¹³C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 × 10⁷ moles yr⁻¹. A fourth, but minor source of methane (δ¹³CH₄ = −55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

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

Methane (CH₄) 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 CH₄ 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 CH₄, C₂H₆ and CO₂, and nitrogen isotopes in N₂ 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 δ¹³C_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 CH₄, and in the H₂S concentrations which are likely caused by mixing of the deep oxidized CH₄–N₂–H₂S–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.     

Enrichment of nitrogen and 13C of methane in natural gases from the Khuff Formation,Saudi Arabia,caused by thermochemical sulfate reduction

Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N₂/CH₄, CO₂/CH₄ and H₂S/CH₄ suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ¹³C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ¹³C between −3‰ and 0‰ VPDB. As H₂S/CH₄ increases, methane δ¹³C increases to as much as −3‰ and carbon dioxide δ¹³C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150 °C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N₂/CH₄ of the residual gas and leave δ¹⁵N unaltered. δ¹⁵N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N₂/CH₄ in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ¹⁵N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ¹³C versus log(N₂/CH₄). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).     

Water column methane oxidation adjacent to an area of active hydrate dissociation,Eel river Basin

The role of methane clathrate hydrates in the global methane budget is poorly understood because little is known about how much methane from decomposing hydrates actually reaches the atmosphere. In an attempt to quantify the role of water column methanotrophy (microbial methane oxidation) as a control on methane release, we measured water column methane profiles (concentration and δ¹³C) and oxidation rates at eight stations in an area of active methane venting in the Eel River Basin, off the coast of northern California. The oxidation rate measurements were made with tracer additions of ³H-CH₄.Small numbers of instantaneous rate measurements are difficult to interpret in a dynamic, advecting coastal environment, but combined with the concentration and stable isotope measurements, they do offer insights into the importance of methanotrophy as a control on methane release. Fractional oxidation rates ranged from 0.2 to 0.4% of ambient methane per day in the deep water (depths >370 m), where methane concentration was high (20–300 nM), to near-undetectable rates in the upper portion of the water column (depths <370 m), where methane concentration was low (3–10 nM). Methane turnover time averaged 1.5 yr in the deep water but was on the order of decades in the upper portion of the water column. The depth-integrated water column methane oxidation rates for the deep water averaged 5.2 mmol CH₄ m⁻² yr⁻¹, whereas the upper portion of the water column averaged only 0.14 mmol CH₄ m⁻² yr⁻¹; the depth-integrated oxidation rate for deep water in the 25-km² area encompassing the venting field averaged 2 × 10⁶ g CH₄ yr⁻¹. Stable isotope values (δ¹³C-CH₄) for individual samples ranged from −34 to −52‰ (vs. PDB, Peedee belemnite standard) in the region. These values are isotopically enriched relative to hydrates in the region (δ¹³C-CH₄ about −57 to −69‰), further supporting our observations of extensive methane oxidation in this environment.     

Atmospheric palaeo-CO2 estimates based on the carbon isotope and stomatal data of Cheirolepidiaceae from the Lower Cretaceous of the Jiuquan Basin,Gansu Province

The stable carbon isotope compositions and the stomatal parameters (stomatal density and stomatal index) of four Cheirolepidiaceae species, Brachyphyllum ningxiaensis, Brachyphyllum obtusum, Pseudofrenelopsis dalatzensis and Pseudofrenelopsis gansuensis, were analyzed to recover the late Early Cretaceous atmospheric CO₂ levels. The fossil plants were collected from 5 consecutive sedimentary members of the uppermost Zhonggou Formation. Based on the stomatal data, the estimated palaeo-atmospheric CO₂ concentrations in the Jiuquan Basin during the late Early Cretaceous were 1060–882 ppmv based on the carboniferous standardization and were 641–531 ppmv based on the recent standardization; the pCO₂ values present at first a decreasing and then an increasing trend within the sedimentary time of the five members. The δ¹³Cp values based on the 21 Brachyphyllum specimens showed a large variation, which ranged from −20.98‰ to −25.69‰, with an average of −24.2‰. The values also identified a C3 photosynthetic pathway for the Brachyphyllum specimens. The predicted δ¹³Ca values varied from −2.1‰ to −6.38‰, with an average of −5.03‰. These two proxies were irregular within the different members; therefore, the correlation with the change in atmospheric CO₂ concentrations was not significant. Moreover, a water-stressed environment was proposed based on the δ¹³C values of the present fossil plants, a proposal that was also supported by the previous palaeobotanical, palynological and stratigraphical evidence. In the present study, an inconsistent relationship between the stable carbon isotope and the stomata values was apparent, which most likely indicated that the stomata numbers of the plant were more sensitive to the variation in the concentration of the atmospheric CO₂, whereas the δ¹³C values were sensitive to the moisture conditions.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Carbon-Isotope Characteristics of CO2 and CH4 in Geothermal Springs from the Central Andes

Carbon stable-isotope compositions of coexisting carbon dioxide and methane from geothermal springs across the Central Andes of northern Chile and Bolivia are reported. A total of 60 samples were analyzed for δ¹³C_CO2 and, of these, 10 were selected for δ¹³C_CH4 analyses. The Central Andes are characterized by an active volcanic arc and an unusually thick (up to 75 km) continental crust behind the arc, beneath the high plateau region of the Altiplano. Furthermore, helium-isotope evidence suggests active mantle degassing in a 350-km-wide zone beneath the thick continental crust in the Central Andes (Hoke et al., 1994).

The present results show a wide range of δ¹³C_CO2 (-14.9 to -0.6‰) and a surprisingly heavy δ¹³C_CH4 (?20.9 to ?12.3‰). The difference between δ¹³C_CO2 and δ¹³C_CH4 (δ¹³C_CO2-CH4 ) for individual samples varies between 1.5‰ and 13.5‰. The δ¹³C_CO2 results show wide and overlapping ranges in the samples collected from the Precordillera, the Volcanic Arc (or Western Cordillera), the Altiplano, and the Eastern Cordillera. The widest ranges occur in the Eastern Cordillera (?15.0 to ?4.8‰) and the Altiplano (?20 to ?6‰). The δ¹³C_CO2 results for geothermal samples from the Volcanic Arc range between ?8.0‰ (Surire) and ?0.6‰ (Abra de Nappa), whereas δ¹³C_CO2 measured in gases collected from geothermal springs in the Precordillera range from ?10 to ?5‰.

The relationships between 3He/4He, δ¹³C_CO2 , and δ¹³C_CH4 are used to distinguish between crustal and mantle origins. The wide (21‰) range in the is interpreted to reflect contributions from different CO₂ sources that include organic and inorganic crustal and mantle carbon. Assuming isotopic equilibrium between coexisting methane and carbon dioxide, Δ¹³C_CO2-CH4 suggests very high equilibrium temperatures, in excess of 530°C, for some geothermal systems that also are characterized by a high (up to 63%) mantle-derived helium component.

δ¹³C_CH4 results suggest that methane has not formed by bacteriogenic processes or by thermal decomposition of organic matter, but rather abiogenically through the high-temperature reaction between H₂ and CO₂. The δ¹³C_CH4 results for the samples from the Volcanic Arc and from two CO₂-rich geothermal springs in the Altiplano (Coipasa-2 and Belen de Andamarca) are similar to those reported from hydrothermal fluids emitted from the East Pacific Rise (Welhan, 1988) and White Island, New Zealand (Hulston and McCabe, 1962), suggesting a mantle-derived carbon component in the methane.     

Nickel isotope fractionation during laterite Ni ore smelting and refining: Implications for tracing the sources of Ni in smelter-affected soils

Nickel isotope ratios were measured in ores, fly ash, slags and FeNi samples from two metallurgical plants located in the Goiás State, Brazil (Barro Alto, Niquelândia). This allowed investigating the mass-dependent fractionation of Ni isotopes during the Ni-laterite ore smelting and refining. Feeding material exhibits a large range of δ⁶⁰Ni values (from 0.02 ± 0.10‰ to 0.20 ± 0.05‰, n = 7), explained by the diversity of Ni-bearing phases, and the average of δ⁶⁰Ni_{feeding materials} was found equal to 0.08 ± 0.08‰ (2SD, n = 7). Both δ⁶⁰Ni values of fly ash (δ⁶⁰Ni = 0.07 ± 0.07‰, n = 10) and final FeNi produced (0.05 ± 0.02‰, n = 2) were not significantly different from the feeding materials ones. These values are consistent with the very high production yield of the factories. However, smelting slags present the heaviest δ⁶⁰Ni values of all the smelter samples, with δ⁶⁰Ni ranging from 0.11 ± 0.05‰ to 0.27 ± 0.05‰ (n = 8). Soils were also collected near and far from the Niquelândia metallurgical plant, to evaluate the potential of Ni isotopes for tracing the natural vs anthropogenic Ni in soils. The Ni isotopic composition of the non-impacted topsoils developed on ultramafic rocks ranges from −0.26 ± 0.09‰ to −0.04 ± 0.05‰ (n = 20). On the contrary, the Ni isotopic composition of the non-ultramafic topsoils, collected close to the plant, exhibit a large variation of δ⁶⁰Ni, ranging from −0.19 ± 0.13‰ up to 0.10 ± 0.05‰ (n = 4). This slight but significant enrichment in heavy isotopes highlights the potential impact of smelting activity in the surrounding area, as well as the potential of Ni isotopes for discerning anthropogenic samples (heavier δ⁶⁰Ni values) from natural ones (lighter δ⁶⁰Ni values). However, given the global range of published δ⁶⁰Ni values (from −1.03 to 2.5‰) and more particularly those associated to natural weathering of ultramafic rocks (from −0.61 to 0.32‰), the use of Ni isotopes for tracing environmental contamination from smelters will remain challenging.     

Natural seabed gas seeps as sources of atmospheric methane

Microbial and thermogenic methane migrates towards the seabed where some is utilised during microbially-mediated anaerobic oxidation. Excess methane escapes as gas seeps, which occur in a variety of geological contexts in every sea and ocean, from inter-tidal zones to deep ocean trenches. Some seeps are localised, gentle emanations; others are vigorous covering areas of >1 km²; the most prolific seeps reported (offshore Georgia) produce ~40 t CH₄ per year. Gas bubbles lose methane to the water as they rise, so deep water seeps are unlikely to contribute to the atmosphere. However, bubbles break the surface above some shallow water seeps. Estimates of the total methane contribution to the atmosphere are poorly constrained, largely because the data set is so small. 20 Tg yr^–1 is considered a realistic first approximation. This is a significant contribution to the global budget, particularly as methane from seeps is ¹⁴C-depleted. A seep measurement programme is urgently required.GEM     

Modelling the effects of climate change on methane emission from a northern ombrotrophic bog in Canada

Peatlands are a large potential source of methane (CH₄) to the atmosphere. In order to investigate the effects of climate change on CH₄ emission from northern ombrotrophic peatlands, a simulation model coupling water table dynamics with methane emission was developed for the Mer Bleue Bog in Ontario, Canada. The model was validated against reported values of CH₄ flux from field measurements and the model outputs exhibited high sensitivity to acrotelm thickness, leaf area index, transmissivity and slope of water table. With a 2–4°C temperature rise over the 4-year simulation period, the rate of CH₄ release dropped significantly to under 0.1 mg m⁻² day⁻¹. On the other hand, mean CH₄ emission increased by >26-fold when the increase in precipitation was >15%. When looking at the combined effects, the highest CH₄ release (13.3 mg m⁻² day⁻¹) was attained under the scenario of 2°C temperature rise and 25% precipitation increase. Results obtained in this study highlight the importance of avoiding more extreme climate change, which would otherwise lead to enhanced methane release from peatlands and further atmospheric warming through positive feedback.     

Geochemical Characteristics of the Upper Triassic Xujiahe Formation in Sichuan Basin, China and its Significance for Hydrocarbon Accumulation

The alternative development of coal-bearing hydrocarbon source rocks and low-porosity and low-permeability tight sandstone reservoirs of the Triassic Xujiahe Formation in the Sichuan Basin is favorable for near-source hydrocarbon accumulation. The natural gas composition of the Xujiahe Formation in the Sichuan Basin is dominated by hydrocarbon gases, of which the methane content is80.16%-98.67%. Typically, the C_2~+ content is larger than 5% in main wet gas. The dry gas is mainly distributed in the western and northern regions of the basin. The non-hydrocarbon gases mainly contain nitrogen, carbon dioxide, hydrogen, and helium, with a total content of 2%. The carbon isotope ranges of methane and its homologues in natural gas are: δ~(13)C_1 of-43.8‰ to-29.6‰, δ~(13)C_2 of-35.4‰ to-21.5‰, δ~(13)C_3 of-27.6‰ to-19.8‰,and δ~(13)C_4 of-27.7‰ to-18.8‰. δ~(13)C_3δ~(13)C_4 occurs in some natural gas with a low evolution degree; such gas is mainly coal-related gas from humic-type source rocks of the Xujiahe Formation. As for the natural gas, δ~2 H_(CH4) values ranged from-195‰ to-161‰,δ~2 H_(C2H6) values ranged from-154‰ to-120‰, and δ~2 H_(C3H8) values ranged from-151‰ to-108‰. The dry coefficient,δ~(13)C and δ~2 H_(CH4) are all positively correlated with the maturity of source rocks. The higher the maturity of source rocks is, the larger the natural gas dry coefficient is and the larger the δ~(13)C and δ~2 H_(CH_4) values are, indicative of the characteristic of near-source accumulation. The δ~2 H_(C2H6) value of natural gas is influenced by paleosalinity to a relatively large extent; the higher the paleosalinity is, the larger the δ~2 H_(C2H6) value is. The Pr/Ph value of the condensate oil ranged from 1.60 to 3.43, illustrating light oxidization-light reduction and partial-oxidization characteristics of the depositional environment of coal-bearing source rocks of the Xujiahe Formation. The natural gas light hydrocarbon(C_5-C_7) from the Xujiahe Formation presented two characteristics: the first was the relatively high aromatic hydrocarbon content(19%-32.1%), which reveals the characteristic of natural gas with humic substances of high-maturity; the second was the low content of aromatic hydrocarbon(0.4%-9.3%),reflecting water-washing during the accumulation of the natural gas. The reported research outcomes indicate a potential mechanism for natural gas accumulation in the Xujiahe Formation, which will further guide natural gas exploration in this region.     

The Paleoarchean Northern Mundo Novo Greenstone Belt,São Francisco Craton: Geochemistry,U–Pb–Hf–O in zircon and pyrite δ34S-Δ33S-Δ36S signatures

Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (³²S, ³³S, ³⁴S, and ³⁶S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with ε_Hf(t) =  ?2.47 to ?1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ¹⁸O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have ε_Hf(t) =  ?5.40 to ?0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ¹⁸O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ³³S between ?1.3‰ to +1.4‰) and a Δ³⁶S/Δ³³S slope of ?0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ³⁴S range (0 to +2‰), Δ³³S ~ 0‰, and Δ³⁶S ~ 0‰. A carbonaceous schist shows positive δ³⁴S (2.1‰–3.5‰) and elevated Δ³³S (1.2‰–1.4‰) values, with corresponding negative Δ³⁶S between ?1.2‰ to ?0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ³⁴S, Δ³³S, and Δ³⁶S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.     

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH₄) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH₄ and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH₄ up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH₄ included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments.Isotopic analyses included δ¹³C, δD, ¹⁴C, and ³H on select CH₄ samples and δD and δ¹⁸O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had δ¹³C values from −79 to −82‰, typical of natural “drift gas” generated by microbial CO₂-reduction. The CH₄ from the shallow lacustrine deposits had δ¹³C values from −63 to −76‰, interpreted as a mixture between CH₄ generated by microbial fermentation and the CO₂-reduction processes within the subsurface sediments. The δD values of all the CH₄ samples were quite negative ranging from −272 to −299‰. Groundwater sampled from the deeper zones also showed quite negative δD values that explained the light δD observed for the CH₄. Radiocarbon analyses of the CH₄ showed decreasing ¹⁴C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH₄ detected in the till deposits of this site was microbial CH₄ generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH₄ from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH₄ could not be completely ruled out.     

A rapid method for preparing low volume CH4 and CO2 gas samples for 14C AMS analysis

¹⁴C measurements of CH₄ in environmental samples (e.g. soil gas, lake water, gas hydrates) can advance understanding of C cycling in terrestrial and marine systems. The measurements are particularly useful for detecting the release of old C from climate sensitive environments such as peatlands and hydrate fields. However, because ¹⁴C CH₄ measurements tend to be complex and time consuming, they are uncommon. Here, we describe a novel vacuum line system for the preparation of CH₄ and CO₂ from environmental samples for ¹⁴C analysis using accelerator mass spectrometry (AMS). The vacuum line is a flow-through system that allows rapid preparation of samples (1 h for CH₄ and CO₂, 30 min for CH₄ alone), complete separation of CH₄ and CO₂ and is an easy addition to multipurpose CO₂ vacuum lines already in use. We evaluated the line using CH₄ and CO₂ standards with different ¹⁴C content. For CH₄ and CO₂, respectively, the total line blank was 0.4 ± 0.2 and 1.4 ± 0.6 μg C, the ¹⁴C background 51.1 ± 1.2 and 48.4 ± 1.5 kyr and the precision (based on pooled standard deviation) 0.9‰ and 1.3‰. The line was designed for sample volumes of ca. 180 ml containing 0.5–1% CH₄ and CO₂, but can be adjusted to handle lower concentration and larger volume samples. This rapid and convenient method for the preparation of CH₄ and CO₂ in environmental samples for ¹⁴C AMS analysis should provide more opportunities for the use of ¹⁴C CH₄ measurements in C cycle studies.     

Geochemical studies of pore fluid in surface sediment on the Daini Atsumi Knoll

We collected sediment samples and pore water samples from the surface sediment on the Daini Atsumi Knoll, and analyzed the sediments for CH₄, C₂H₆, and δ¹³C_CH4, and the pore fluids for CH₄, C₂H₆, δ¹³C_CH4, Cl⁻, SO₄²⁻, δ¹⁸O_H2O, and δD_H2O, respectively. A comparison of the measured concentration and isotopic composition of methane in pore water samples with those in sediment samples revealed that methane was present in the sediment samples at a higher concentration and was isotopically heavier than those in the pore water samples. It suggests that the effect of the release of a sorbed gas bound to organic particles when heated prior to analysis of hydrocarbons was larger than that of the degassing process. A large amount of a sorbed gas would be a significant source of natural gas. Two striking features are the chemical and isotopic composition of the pore water samples taken from the different sites around the Daini Atsumi Knoll. In the KL09, KL10, and KP07 samples, Cl⁻ concentrations in the pore water samples showed depletion to a minimum of 460 mmol/kg, correspond to  17% dilution of seawater, however the latter was not enriched in CH₄. The isotopic compositions of pore water samples suggested the low-Cl⁻ fluids in the pore water were not derived from dissociation of methane hydrate, but were derived from input of meteoric water. In contrast, in the KP05 samples from the north flank of the Daini Atsumi Knoll, pore water were characterized by CH₄ enrichment more than 370 μmol/kg, but not depleted in Cl⁻ concentrations. The observed methane concentration in the KP05 samples is not sufficient for methane hydrate to form in situ, indicating that the existence of methane hydrate in the surface sediment is negligible, as supported by Cl⁻ concentration. Based on the stable carbon isotope ratio of methane in the pore fluid from the KP05 site (δ¹³C_CH4 < − 50‰PDB), methane is thought to be of microbial origin. The pore waters in the surface sediments in the north flank of the Daini Atsumi Knoll were not directly influenced by upward fluid bearing methane of thermogenic origin from a deeper part of the sedimentary layer. However, extremely high methane concentration in the north flank site as compared with the concentration of pore water taken from the normal seafloor suggests that the north flank site is not the normal seafloor. We hypothesize that upward migration of chemically-reduced fluids from a deeper zone of the sedimentary layer reduces chemically-oxidized solutes in the surface sediment. As a consequence methane production replaced sulfate reduction as the microbial metabolism in the reduced environment of the surface sediment.