Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.     

Worldwide distribution and significance of secondary microbial methane formed during petroleum biodegradation in conventional reservoirs

Around half of world’s endowment of in-place oil and bitumen experienced biodegradation, which is now believed to be largely an anaerobic methanogenic process. However, the distribution and scale of methanogenic biodegradation in the world’s petroleum accumulations and the significance of its terminal product, secondary microbial methane, in the global gas endowment and carbon cycle are largely unknown. Here, I present geological and geochemical criteria to recognize secondary microbial methane in conventional petroleum reservoirs. These include the presence of biodegraded oil (as pools, legs or shows) in the reservoir or down-dip, the relatively dry (methane dominated) gas containing methane with δ¹³C values between −55‰ and −35‰ and, most importantly, CO₂ with δ¹³C > +2‰. Based on these criteria, the presence of secondary microbial methane is apparent in 22 basins, probable in 12 basins and possible in six basins worldwide. Reservoirs apparently containing secondary microbial methane are mostly Cenozoic and clastic and occur at depths of 37-1834 m below surface/mudline and temperatures of 12-71 °C. Using the current global endowment of in-place oil and bitumen and reasonable assumptions about conversion of oil into methane during biodegradation, I estimated that ∼65,500 tcf of secondary microbial methane could have been generated in existing worldwide accumulations of oil and bitumen through their geological history. From 1461-2760 tcf in-place (845-1644 tcf recoverable) of secondary microbial methane may be accumulated as free and oil-dissolved gas in petroleum reservoirs. I also updated the inventory of primary microbial methane and estimated that the global primary microbial gas endowment (free and oil-dissolved) is from 676-797 tcf in-place (407-589 tcf recoverable). Secondary microbial methane may account for ∼5-11% of the global conventional recoverable gas endowment and appears more abundant than primary microbial gas (∼3-4% of the global gas endowment). Most of the generated secondary microbial methane probably is aerobically and anaerobically oxidized to CO₂ in the overburden above petroleum reservoirs. However, some secondary microbial methane may escape from shallow reservoirs into the atmosphere and affect present and past global climate.     

Stable carbon isotope behaviour of natural seepage of deep underground C-rich methane detected along a fault zone and adsorbed in mudstone: Tokyo Bay area,Japan

Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ¹³C₁ = −44.3‰ was obtained for gas in the container and δ¹³C₁ = −36.3‰ for seeping gas in a fault zone. However, typical CH₄ in this dissolved-in-water gas-field is mainly depleted in ¹³C, and δ¹³C₁ values range from −66‰ to −68‰ owing to microbial degradation of organic material. ¹³C-rich CH₄ is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. ¹³C-rich CH₄ (adsorbed CH₄) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, ¹³C-rich CH₄ was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO₂ reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of ¹³C-rich CH₄, derived from thermogenic gas without oil components in strata. It is assumed that ¹²C-rich CH₄ is easily detached from core or pore water through gas production, whereas ¹³C-rich CH₄ is strongly adsorbed on the surfaces of particles. The ¹³C-rich CH₄ rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.     

Temperatures of aqueous alteration and evidence for methane generation on the parent bodies of the CM chondrites

Aqueous alteration of primitive meteorites was among the earliest geological processes during the evolution of our solar system. ‘Clumped-isotope’ thermometry of carbonates in the CM chondrites, Cold Bokkeveld, Murray, and Murchison, demonstrates that they underwent aqueous alteration at 20-71 °C from a fluid with δ¹⁸O_VSMOW of 2.0‰ to 8.1‰ and δ¹⁷O_VSMOW of −0.1‰ to 3.0‰. The δ¹³C_VPDB values of these carbonates exhibit a negative correlation with the δ¹⁸O_VSMOW of their formation waters, consistent with formation and escape of ¹³C-depleted CH₄ during aqueous alteration. Methane generation under these conditions implies that the alteration fluid was characterized by an Eh ? −0.67 and pH ? 12.5 (or lower at the highest alteration temperatures). Our findings suggest that methane generation may have been a widespread consequence of planetesimal and planetary aqueous alteration, perhaps explaining the occurrence of methane on Titan, Triton, Pluto, and other Kuiper-belt objects.     

Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones,northern Appalachian Basin

In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH₄ (0.01–50.55 mol%) with low δ¹³C–CH₄ values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ¹³C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH₄ to ethane and propane ratios (3–35 mol%; C₁/C₂ + C₃) and high δ¹³C and δD values of CH₄ (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH₄ was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ¹³C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO₄ values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ¹³C–DIC values (<−22‰) and relatively high SO₄ concentrations (up to 12.31 mmole/L) in many brine samples point to SO₄ reduction, which likely limits microbial CH₄ generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH₄ in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH₄ are present at shallow depths along Lake Erie and in western NY.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ¹³C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ¹³C_DIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO₂ fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO₂ and precipitated CaCO₃(1000lnα_{[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2}) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of ¹⁴C mass balance and paired ¹⁴C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from ¹⁴C-dead dolomite cap while the remainder of ∼77% is derived from ¹⁴C-live biomass. δ¹³C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ¹³C values calculated using the shallow pool summer/early fall data thus confirming the δ¹³C seasonality in both drips and coeval aragonite. δ¹³C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ¹³C records of stalagmites at DeSoto Caverns with resolving power >10⁻¹ year will likely carry the imprints of drip annual means that record climate-driven δ¹³C seasonal biases.     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ¹³C values of phytoliths from a C₄ grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r² < 0.3) between climate variables and the δ¹³C values of C. longifolia tissues (average δ¹³C_tissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ¹³C values are lower for grasses collected in populated areas where the δ¹³C value of atmospheric CO₂ is expected to be lower because of fossil fuel burning. Phytolith δ¹³C values are more variable (δ¹³C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ¹³C values. The strongest correlations are obtained between the δ¹³C values of stem or sheath phytoliths and humidity (r² = 0.3), latitude (r² = 0.4) and amount of precipitation (r² = 0.5). However, use of these relationships is limited by the wide spread in δ¹³C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ¹³C values of phytoliths and expected variations in the δ¹³C values of atmospheric CO₂. The C. longifolia phytoliths are depleted of ¹³C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C₃ plants. This observation may further limit the usefulness of soil-phytolith assemblage δ¹³C values for identifying shifts in grassland C₃:C₄ ratios.     

Carbon-isotopic analysis of individual pollen grains from C3 and C4 grasses using a spooling-wire microcombustion interface

Pollen grains from grasses using the C₃ and C₄ photosynthetic pathways have distinct ranges of δ¹³C values that may be used to estimate their relative abundance in paleorecords. We evaluated a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer (SWiM-IRMS) for δ¹³C analysis of individual grass-pollen grains. Pollen from four C₃ and four C₄ grass species was isolated through micromanipulation and analyzed as single grains suspended in water. A carbon yield greater than the 2σ range of the carbon content of blanks containing only water was used to distinguish samples containing pollen (“pollen present”) from those not containing pollen. This criterion resulted in the exclusion of ∼45% of the 946 samples applied to the wire. The average δ¹³C values (±1σ) of the remaining samples were −26.9‰ (±6.3‰) and −11.5‰ (±9.6‰) for C₃ grasses and C₄ grasses, respectively, after blank-correcting the δ¹³C data. These results suggest that the SWiM-IRMS system can be used to distinguish C₃ from C₄ grass pollen. The high variability in measured δ¹³C values is likely caused by a combination of factors. These include natural isotopic variability among individual pollen grains; the relatively poor precision that can be obtained when determining δ¹³C values of such small samples; and the uncertainty in the magnitude, isotopic composition, and stability of the analytical blank. Nonetheless, high percentages of individual pollen grains were correctly classified as being of either C₃ or C₄ origin. On average, 90% (range = 78-100%) of pollen grains from C₃ grasses had δ¹³C values more negative than the cutoff threshold of −19.2‰; while 84% (range = 77-90%) of pollen grains from C₄ grasses had δ¹³C values more positive than −19.2‰. Compared with analysis using an elemental analyzer interfaced with an IRMS (EA-IRMS), the number of pollen grains required for δ¹³C-based evaluation of C₃/C₄ grass composition is many times lower with the SWiM-IRMS. Additionally, δ¹³C data from the SWiM-IRMS does not need to be incorporated into a mixing model to derive estimates of the abundance of C₃ and C₄ grass pollen. Carbon-isotopic analysis of individual grass-pollen grains using the SWiM-IRMS system may help improve our understanding of the evolutionary and ecological significance of grass taxa in the paleorecord.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Cl,N, C isotopic analysis of common agro-chemicals for identifying non-point source agricultural contaminants

The isotopic compositions of commercially available herbicides were analyzed to determine their respective ¹⁵N, ¹³C and ³⁷Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ³⁷Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ¹⁵N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ¹³C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.     

Methane microseepage from different sectors of the Yakela condensed gas field in Tarim Basin,Xinjiang, China

Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in commercial petroleum fields. While the role of microseepage as a pathfinder in petroleum exploration has been known for about 80 a, its significance as an atmospheric CH₄ source has only recently been studied, and flux data are currently available only in the USA and Europe. With the aim of increasing the global data-set and better understanding flux magnitudes and variabilities, microseepage is now being extensively studied in China. A static flux chamber method was recently applied to study microseepage emissions into the atmosphere in four different sectors of the Yakela condensed gas field in Tarim Basin, Xinjiang, China, and specifically in: (a) a faulted sector, across the Luntai fault systems; (b) an oil–water interface sector, at the northern margin of the field; (c) an oil–gas interface sector, in the middle of the field; (d) an external area, outside the northern gas field boundaries. The results show that positive CH₄ fluxes are pervasive in all sectors and therefore, only part of the CH₄ migrating from the deep oil–gas reservoirs is consumed in the soil by methanotrophic oxidation. The intensity of gas seepage seems to be controlled by subsurface geologic settings and lateral variabilities of natural gas pressure in the condensed gas field. The highest CH₄ fluxes, up to ∼14 mg m⁻² d⁻¹ (mean of 7.55 mg m⁻² d⁻¹) with higher spatial variability (standard deviation, σ: 2.58 mg m⁻² d⁻¹), occur in the Luntai fault sector. Merhane flux was lower in the oil–water area (mean of 0.53 mg m⁻² d⁻¹) and the external area (mean of 1.55 mg m⁻² d⁻¹), and at the intermediate level in the gas–oil sector (mean of 2.89 mg m⁻² d⁻¹). These values are consistent with microseepage data reported for petroleum basins in the USA and Europe. The build-up of methane concentration in the flux chambers is always coupled with an enrichment of ¹³C, from δ¹³C₁ of −46‰ to −42.5‰ (VPDB), which demonstrates that seeping methane is thermogenic, as that occurring in the deep Yakela reservoir. Daily variations of microseepage are very low, with minima in the afternoon, corresponding to higher soil temperature (and higher methanotrophic consumption), and maxima in the early morning (when soil temperatures are lowest). A preliminary and rough estimate of the total amount of CH₄ exhaled from the Yakela field is in the order of 10² tonnes a⁻¹.     

Application of carbon isotopes to detect seepage out of coalbed natural gas produced water impoundments

Coalbed natural gas (CBNG) production from coal bed aquifers requires large volumes of produced water to be pumped from the subsurface. The produced water ranges from high quality that meets state and federal drinking water standards to low quality due to increased salinity and/or sodicity. The Powder River Basin of northeastern Wyoming is a major coalbed natural gas producing region, where water quality generally decreases moving from the southeastern portion of the basin towards the center. Most produced water in Wyoming is disposed into impoundments and other surface drainages, where it may infiltrate into shallow groundwater. Groundwater degradation caused by infiltration of CBNG produced water holding impoundments into arid, soluble salt-rich soils is an issue of immense importance because groundwater is a major source for stock water, irrigation, and drinking water for many small communities in these areas. This study examines the potential of using stable C isotope signatures of dissolved inorganic C (δ¹³C_DIC) to track the fate of CBNG produced water after it is discharged into the impoundments. Other geochemical proxies like the major cations and major anions were used in conjunction with field water quality measurements to understand the geochemical differences between CBNG produced waters and ambient waters in the study area. Samples were collected from the CBNG discharge outfalls, produced water holding impoundments, and monitoring wells from different parts of the Powder River Basin and analyzed for δ¹³C_DIC. The CBNG produced waters from outfalls and impoundments have positive δ¹³C_DIC values that fall within the range of +12‰ to +22‰, distinct from the ambient regional surface and groundwaters with δ¹³C_DIC values ranging from −10‰ to −14‰. The results from the study demonstrate that these contrasting δ¹³C_DIC signatures can be used to trace seepage out of CBNG produced water impoundments into shallow groundwaters.     

Stable isotopic evidence in support of active microbial methane cycling in low-temperature diffuse flow vents at 9°50′N East Pacific Rise

A unique dataset from paired low- and high-temperature vents at 9°50′N East Pacific Rise provides insight into the microbiological activity in low-temperature diffuse fluids. The stable carbon isotopic composition of CH₄ and CO₂ in 9°50′N hydrothermal fluids indicates microbial methane production, perhaps coupled with microbial methane consumption. Diffuse fluids are depleted in ¹³C by ∼10‰ in values of δ¹³C of CH₄, and by ∼0.55‰ in values of δ¹³C of CO₂, relative to the values of the high-temperature source fluid (δ¹³C of CH₄ =−20.1 ± 1.2‰, δ¹³C of CO₂ =−4.08 ± 0.15‰). Mixing of seawater or thermogenic sources cannot account for the depletions in ¹³C of both CH₄ and CO₂ at diffuse vents relative to adjacent high-temperature vents. The substrate utilization and ¹³C fractionation associated with the microbiological processes of methanogenesis and methane oxidation can explain observed steady-state CH₄ and CO₂ concentrations and carbon isotopic compositions. A mass-isotope numerical box model of these paired vent systems is consistent with the hypothesis that microbial methane cycling is active at diffuse vents at 9°50′N. The detectable ¹³C modification of fluid geochemistry by microbial metabolisms may provide a useful tool for detecting active methanogenesis.     

Gas seepage from Tokamachi mud volcanoes, onshore Niigata Basin (Japan): Origin, post-genetic alterations and CH4-CO2 fluxes

Methane and CO₂ emissions from the two most active mud volcanoes in central Japan, Murono and Kamou (Tokamachi City, Niigata Basin), were measured in from both craters or vents (macro-seepage) and invisible exhalation from the soil (mini- and microseepage). Molecular and isotopic compositions of the released gases were also determined. Gas is thermogenic (δ¹³C_CH4 from −32.9‰ to −36.2‰), likely associated with oil, and enrichments of ¹³C in CO₂ (δ¹³C_CO2 up to +28.3‰) and propane (δ¹³C_C3H8 up to −8.6‰) suggest subsurface petroleum biodegradation. Gas source and post-genetic alteration processes did not change from 2004 to 2010. Methane flux ranged within the orders of magnitude of 10¹-10⁴ g m⁻² d⁻¹ in macro-seeps, and up to 446 g m⁻² d⁻¹ from diffuse seepage. Positive CH₄ fluxes from dry soil were widespread throughout the investigated areas. Total CH₄ emission from Murono and Kamou were estimated to be at least 20 and 3.7 ton a⁻¹, respectively, of which more than half was from invisible seepage surrounding the mud volcano vents. At the macro-seeps, CO₂ fluxes were directly proportional to CH₄ fluxes, and the volumetric ratios between CH₄ flux and CO₂ flux were similar to the compositional CH₄/CO₂ volume ratio. Macro-seep flux data, in addition to those of other 13 mud volcanoes, supported the hypothesis that molecular fractionation (increase of the “Bernard ratio” C₁/(C₂ + C₃)) is inversely proportional to gas migration fluxes. The CH₄ “emission factor” (total measured output divided by investigated seepage area) was similar to that derived in other mud volcanoes of the same size and activity. The updated global “emission-factor” data-set, now including 27 mud volcanoes from different countries, suggests that previous estimates of global CH₄ emission from mud volcanoes may be significantly underestimated.     

The role of sulfur in chemical weathering and atmospheric CO2 fluxes: Evidence from major ions, δCDIC, and δSSO4 in rivers of the Canadian Cordillera

Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO₃⁻, SO₄²⁻, Cl⁻, Ca²⁺, Mg²⁺, K⁺, Na⁺), δ¹³C of dissolved inorganic carbon (δ¹³C_DIC), and δ³⁴S of dissolved sulfate (δ³⁴S_SO4) to quantify chemical weathering rates and exchanges of CO₂ between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ³⁴S_SO4 (−8.9 to 14.1‰_CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ¹³C_DIC values (−9.8 to −3.7‰ _VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ³⁴S_SO4 is negatively correlated with δ¹³C_DIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ¹³C_DIC of rivers. The negative correlation between δ³⁴S_SO4 and δ¹³C_DIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 10³ mol C · km⁻² · yr⁻¹) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 10³ mol C · km⁻² · yr⁻¹). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO₂ to carbonate rocks, sulfide-carbonate weathering can liberate CO₂ from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO₂ drawdown by silicate weathering in the region.     

Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ¹³C and δ¹⁸O values of carbonates from the Atacama are the highest of any desert in the world. δ¹³C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO₂ production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ¹³C value of soil carbonate in the Atacama, whereas the fraction C₃ to C₄ biomass at individual sites has a subordinate influence. The high average δ¹³C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO₂.δ¹⁸O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ¹³C values. δ¹⁸O values for soil carbonate predicted from local temperature and δ¹⁸O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ¹⁸O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.     

Water drives the deuterium content of the methane emitted from plants

The spatial distribution of the deuterium content of precipitation has a well-established latitudinal variation that is reflected in organic molecules in plants growing at different locations. Some laboratory and field studies have already shown that the deuterium content of methane emitted from methanogens can be partially related to δD variations of the water in the surrounding environment. Here we present a similar relation for the methane emitted from plant biomass under UV radiation. To show this relation, we determined the hydrogen isotopic composition of methane released from leaves of a range of plants grown with water of different deuterium content (δD = −130‰ to +115‰). The plant leaves were irradiated with UV light and the CH₄ isotopic composition was measured by continuous flow isotope ratio mass spectrometry (CF-IRMS). Furthermore, the deuterium content of bulk biomass and of the methoxyl (OCH₃) groups of the biomass was measured. The D/H ratio successively decreases from bulk biomass (δD = −106‰ to −50‰) via methoxyl groups (δD = −310‰ to −115‰) to the CH₄ emitted (δD = −581‰ to −196‰). The range of isotope ratios in bulk biomass and OCH₃ groups is smaller than in the water used to grow the plants. Methoxyl groups, which contain only non-exchangeable hydrogen, can be used to assess the fraction of external water that was incorporated before OCH₃ groups were formed. Surprisingly, the CH₄ formed under UV irradiation has a wider isotopic range than the OCH₃ groups. Although the precise production pathway cannot be fully determined, the presented experiments indicate that methoxyl groups are not the only source substrate for CH₄, but that other sources, including very depleted ones, must contribute. The main limitation to the interpretation of the data is the possible influence of exchangeable water, which could not be quantified. Future studies should include measurements of leaf water and avoid interaction between different plants via the gas phase. Despite these deficiencies, the results suggest that the deuterium content of the methane generated from plants under UV irradiation is closely linked to δD in precipitation. This dependency, which should also exist for other biogenic methane sources could be evaluated with global isotope models.     

Extraordinary C enrichment of diether lipids at the Lost City Hydrothermal Field indicates a carbon-limited ecosystem

Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ¹³C values of total organic carbon range from −21.5‰ vs. VPDB at an extinct carbonate chimney to −2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ¹³C > −15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in ¹³C lacked or contained lower amounts of these diethers.Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ¹³C values ranging from −2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ¹³C values between −11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in ¹³C, with δ¹³C as low as −28.7‰ in chimneys and −45‰ in fissures.The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of ¹³C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to ¹³C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ¹³C values typical of abiotic carbon.     

Paleoclimate record in the Nubian Sandstone Aquifer,Sinai Peninsula,Egypt

Sixteen groundwater samples collected from production wells tapping Lower Cretaceous Nubian Sandstone and fractured basement aquifers in Sinai were analyzed for their stable isotopic compositions, dissolved noble gas concentrations (recharge temperatures), tritium activities, and ¹⁴C abundances. Results define two groups of samples: Group I has older ages, lower recharge temperatures, and depleted isotopic compositions (adjusted ¹⁴C model age: 24,000–31,000 yr BP; δ¹⁸O: − 9.59‰ to − 6.53‰; δ²H: − 72.9‰ to − 42.9‰; < 1 TU; and recharge T: 17.5–22.0°C) compared to Group II (adjusted ¹⁴C model age: 700–4700 yr BP; δ¹⁸O: − 5.89‰ to − 4.84‰; δ²H: − 34.5‰ to − 24.1‰; < 1 to 2.78 TU; and recharge T: 20.6–26.2°C). Group II samples have isotopic compositions similar to those of average modern rainfall, with larger d-excess values than Group I waters, and locally measurable tritium activity (up to 2.8 TU). These observations are consistent with (1) the Nubian Aquifer being largely recharged prior to and/or during the Last Glacial Maximum (represented by Group I), possibly through the intensification of paleowesterlies; and (2) continued sporadic recharge during the relatively dry and warmer interglacial period (represented by Group II) under conditions similar to those of the present.