Standardisation of Rock–Eval pyrolysis for the analysis of recent sediments and soils

Rock–Eval 6 analysis, a well established screening tool for petroleum geochemistry, is being increasingly used to characterise the varying species of organic matter (OM) in the bulk samples of recent aquatic sediments. This is particularly important due to recent scientific attention on the role of OM in biogeochemical distribution of environmentally hazardous compounds (e.g., trace metals) in recent sediment archives. Rock–Eval’s automated use, low sample volume requirements and its high analytical accuracy and precision makes it an ideal tool for relatively rapid screening of OM in sediment cores. However, to date, there has been no broad scale standardisation to determine what may be contributing to each signal (e.g., S1, S2, S3, RC). We have selected a wide variety of representative, pure biochemicals (proteins, lipids, carbohydrates and lignins) and biological standards (phytoplankton, copepods, tree bark and conifer needles) to better understand the Rock–Eval 6’s measured organic matter parameters in the unconventional environmental samples. These data have been corroborated with organic petrographical and elemental (CHNS/O) data. Our results show that small organic molecules (<500 Da) are largely responsible for the S1 hydrocarbon peak while lipids and aquatic biological standards are contributing most in the S2 signal, and in particular the more labile “S2a” signal. Furthermore, carbohydrates, lignins and terrigenous plant standards are most responsible for the S3 signal. We also note that the S3 signals (CO/CO₂ ratios: OICO, OICO₂ and OIRE6) are the best discriminants for the source of OM. Finally, step wise pyrolysis of biological standards coupled with elemental analysis (CHNS/O) suggests that S2 and, to a lesser extent, S3 (S3CO and/or S3CO₂), would be most responsible for metal-binding elements such as S and N, with implications for element biogeochemical cycles.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

The structural evolution of organic matter during maturation of coals and its impact on petroleum potential and feedstock for the deep biosphere

The structural evolution of coals during coalification from peat to the end of the high volatile bituminous coal rank (VR_r = 0.22–0.81%) has been studied using a natural maturity series from New Zealand. Samples were studied using a range of standard coal analyses, Rock–Eval analysis, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and pyrolysis gas chromatography (Py-GC). The structural evolution of coal during diagenesis and moderate catagenesis is dominated by defunctionalisation reactions leading to the release of significant amounts of oxygen and thereby to an enrichment of aromatic as well as aliphatic structures within the residual organic matter. Based on the evolution of pyrolysis yields and elemental compositions with maturity it can be demonstrated that oxygen loss is the major cause for increasing Hydrogen Index values or hydrocarbon generating potentials of coals at such maturity levels. For the first time, the loss of oxygen in form of CO₂ has been quantified. During maturation from peat to high volatile bituminous coal ranks ∼10–105 mg CO₂/g TOC has been released. This is equivalent to 2.50E−4 to 1.25E−3 mg CO₂ generated from every litre of sediment per year falling into the range of deep biosphere utilisation rates. Immature coals, here New Zealand coals, therefore manifest the potential to feed deep terrestrial microbial life, in contrast to more mature coals (VR_r > ∼0.81%) for which defunctionalisation processes become less important.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Simulation of thermal stress influence on the Boom Clay kerogen (Oligocene,Belgium) in relation to long-term storage of high activity nuclear waste: I. Study of generated soluble compounds

Closed pyrolyses were performed on the Boom Clay kerogen to simulate the weak thermal stress applied during the in situ CERBERUS heating experiment (80 °C for 5 a). Two stronger thermal stresses, encompassing the range generally considered for the long-term disposal of high-activity nuclear waste (80 °C for 1 ka and 120 °C for 3 ka), were also simulated. Quantitative and qualitative studies were carried out on the products thus generated with a focus on the C₁₂₊ fraction, especially on its polar components. It thus appeared that the soluble C₁₂₊ fractions generated during these simulation experiments comprise a wide variety of polar O- and/or N-containing compounds, including carboxylic acids and phenols. The nature and/or the relative abundance of these polar compounds exhibit strong variations, with the extent of the thermal stress, reflecting the primary cracking of different types of structures with different thermal stability and the occurrence of secondary degradation reactions. These observations support the idea that the compounds, generated upon exposure of the Boom Clay kerogen to a low to moderate thermal stress, may affect the effectiveness of the geological barrier upon long-term storage of high-activity nuclear waste.     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Contact metamorphism of organic-rich mudstones and carbon release around a magmatic sill in the Basque-Cantabrian Basin,western Pyrenees

Recent studies have documented the expulsion of methane and oil to the Albian paleoseabed in the Basque-Cantabrian Basin. They interpret that hydrocarbon generation and expulsion were triggered by seismically recorded magmatic intrusions which metamorphosed organic-rich host sediments. An outcrop within the basin was selected to investigate organic matter evolution and sediment degassing due to an igneous body. This intrusion is a 5 m thick Late Albian basaltic sill that intruded mudstones of the Black Flysch Group, near Gorliz (north Iberia). Vitrinite and bitumen reflectance profiles and metamorphic mineral distribution in the overburden indicate that the sill produced a thermal effect that increases toward the intrusion, defining a 2 m thick (minimum) contact aureole.Geochemical profiles of TOC, S1, S2, HI and PC show a gradual decrease toward the sill indicating organic carbon loss and increase in the thermal maturity of the organic matter in the same direction. Concordantly, gas chromatograms show a loss of n-alkanes and a predominance of the shorter chain length homologues adjacent to the sill. Tmax and PI (S1/S1 + S2) values increase toward the sill which suggests an increase in the thermal stress and in the extent of kerogen pyrolysis, respectively.Organic carbon loss in the aureole was the result of carbon devolatilization and formation of CO₂ and CH₄ gases. The newly formed CO₂ reacted with pore waters to precipitate ¹³C depleted carbonate minerals in the aureole and in sill fractures. CH₄ escaped from the aureole via hydrofractures to the paleoseabed, where methane-derived authigenic carbonates were formed.     

Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen

In mine soil, quantification of soil organic carbon (OC) derived recently from biomass decomposition is complicated by the presence of fossil (geogenic) C derived from coal, oil shale, or similar material in the overburden. The only reliable method for such measurement is ¹⁴C analysis (i.e. radiocarbon dating) using instrumentation such as accelerator mass spectrometry, which is too expensive for routine laboratory analysis. We tested two previously used and two new methods for recent C quantification and compared them with ¹⁴C AMS radiocarbon dating as a reference using a set of soil samples (n = 14) from Sokolov, Czech Republic: (i) ¹³C isotope ratio composition, (ii) cross polarization magic angle spinning ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy, (iii) near infrared spectroscopy (NIRS) coupled with partial least squares regression and (iv) Rock–Eval pyrolysis. Conventional methods for OC determination (dry combustion, wet dichromate oxidation, loss-on-ignition) were also compared to quantify any bias connected with their use. All the methods provided acceptable recent carbon estimates in the presence of mostly aliphatic fossil C from kerogen. However, the most accurate predictions were obtained with two approaches using Rock–Eval pyrolysis parameters as predictors, namely (i) S₂ curve components and (ii) oxygen index (OI). The S₂ curve approach is based on the lower thermal stability of recent vs. fossil organic matter. The OI approach corresponded well with ¹³C NMR spectra, which showed that samples rich in recent C were richer in carboxyl C and O-alkyl C. These two methods showed the greatest potential as routine methods for recent C quantification.     

An improved cubic model for the mutual solubilities of CO2–CH4–H2S–brine systems to high temperature,pressure and salinity

The phase behavior of CO₂–CH₄–H₂S–brine systems is of importance for geological storage of greenhouse gases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play a major role in assisting decision makings, while modeling the phase behavior of the relevant CO₂–CH₄–H₂S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for such system which is accurate, with wide application range (pressure, temperature and aqueous salinity), computationally efficient and easy for implementation in a reservoir simulator.In this study, an improved cubic EOS model of the system CO₂–CH₄–H₂S–brine is developed based on the modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely implemented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoir simulators.The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brine are carefully reviewed and compared with the new model. From the comparison, the new model can accurately reproduce (1) the CO₂–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0 to 6 molal, (2) CH₄–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 2000 bar and NaCl molality from 0 to 6 molal, (3) H₂S–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has good accuracy for gas mixture solubility in brine.     

Reconstruction of burial history of eroded Mesozoic strata using kimberlite shale xenoliths,volcaniclastic and crater facies,Northwest Territories,Canada

Reconstruction of Mesozoic and Cenozoic sedimentary ‘cover’ on the Precambrian shield in the Lac de Gras diamond field, Northwest Territories, Canada, has been achieved using Cretaceous and early Tertiary sedimentary xenoliths and contemporaneous organic matter preserved in volcaniclastic sediments associated with late Cretaceous to early Tertiary kimberlite pipe intrusions, and in situ, Eocene crater lake, lacustrine and peat bog strata. Percent reflectance in oil (%Ro) of vitrinite within shale xenoliths for: (i) Albian to mid-Cenomanian to Turonian ranges from > 0.27 to 0.42 %Ro (mean = 0.38 %Ro), (ii) Maastrichtian to early Paleocene from 0.24 to < 0.30%; (iii) latest Paleocene to early middle Eocene 0.15 to < 0.23 %Ro (mean = 0.18 %Ro). These levels of thermal maturity are corroborated by Rock Eval pyrolysis T_max (°C) and VIS region fluorescence of liptinites, with wavelengths of maximum emission for sporinite, prasinophyte alginite and dinoflagellates consistent with vitrinite reflectance of 0.20 to < 0.50 %Ro. Burial–thermal history modeling, constrained by measured vitrinite reflectance and porosity of shale xenoliths, predicts a maximum burial temperature for Mid to Late Albian strata (∼115 Ma) of 60 °C with ∼1.2 to 1.4 km of Cretaceous strata in the Lac de Gras kimberlite field region prior to major uplift and erosion, which began at 90 Ma. Late Paleocene to middle Eocene volcanic crater lake lacustrine to peat bog strata were only buried to a few hundreds of meters and are in a peat-brown coal stage of thermal maturation.     

Modeling of coal bed methane (CBM) production and CO2 sequestration in coal seams

A mathematical model was developed to predict the coal bed methane (CBM) production and carbon dioxide (CO₂) sequestration in a coal seam accounting for the coal seam properties. The model predictions showed that, for a CBM production and dewatering process, the pressure could be reduced from 15.17 MPa to 1.56 MPa and the gas saturation increased up to 50% in 30 years for a 5.4 × 10⁵ m² of coal formation. For the CO₂ sequestration process, the model prediction showed that the CO₂ injection rate was first reduced and then slightly recovered over 3 to 13 years of injection, which was also evidenced by the actual in seam data. The model predictions indicated that the sweeping of the water in front of the CO₂ flood in the cleat porosity could be important on the loss of injectivity. Further model predictions suggested that the injection rate of CO₂ could be about 11 × 10³ m³ per day; the injected CO₂ would reach the production well, which was separated from the injection well by 826 m, in about 30 years. During this period, about 160 × 10⁶ m³ of CO₂ could be stored within a 21.4 × 10⁵ m² of coal seam with a thickness of 3 m.     

Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site,Saskatchewan, Canada

The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO₂ injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO₂ and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO₂.Using 43 Baseline samples collected in August 2000, before CO₂ injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH_{3 (aq)} increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H₂S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H₂S is interpreted to result from bacterial SO₄ reduction. After 6 months of injection of CO₂, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO₂. The Baseline samples varied from −22 to −12‰ δ¹³C (V-PDB) for CO₂ gas. The injected CO₂ has an isotope ratio of −20‰. The Monitor-1 samples of produced CO₂ ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO₂ to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO₂ relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO₂ to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO₂ to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage.     

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.     

Thermal history of the Krishna–Godavari basin,India: Constraints from apatite fission track thermochronology and organic maturity data

The Krishna–Godavari (KG) basin, a passive margin Late Carboniferous to Holocene basin along the rifted east coast of India, includes the deltaic and inter-deltaic regions of the Krishna and Godavari rivers onshore and extends into the offshore. It is one of India’s premier hydrocarbon-bearing basins. In an attempt to better understand the thermal history of the basin, apatite fission track (AFT) data has been obtained from six exploration wells (five onshore and one offshore). AFT thermal history models as well as other thermal indicators e.g. vitrinite reflectance (VR), Rock–Eval T_max data reveal that the host rocks are currently at their maximum post-depositional temperatures and that any possible heating related to small-scale tectonism or rifting episodes in the basin bears little significance on the maturation of the sediments. In the case of one borehole (M-1) however, the organic maturity data reveals a period of Oligocene cooling across an unconformity when ∼1000 m of section was eroded due to falling sea-level. This information offers the potential for improved basin modeling of the KG basin.     

Key factors controlling the gas adsorption capacity of shale: A study based on parallel experiments

This article performed a series of parallel experiments with numerical modeling to reveal key factors affecting the gas adsorption capacity of shale, including shale quality, gas composition and geological conditions. Adsorption experiments for shales with similar OM types and maturities indicate that the OM is the core carrier for natural gas in shale, while the clay mineral has limited effect. The N₂ and CO₂ adsorption results indicate pores less than 3 nm in diameter are the major contributors to the specific surface area for shale, accounting for 80% of the total. In addition, micropores less than 2 nm in diameter are generated in large numbers during the thermal evolution of organic matter, which substantially increases the specific surface area and adsorption capacity. Competitive adsorption experiments prove that shale absorbs more CO₂ than CH₄, which implies that injection CO₂ could enhance the CH₄ recovery, and further research into N₂ adsorption competitiveness is needed. The Langmuir model simulations indicate the shale gas adsorption occurs via monolayers. Geologically applying the adsorption potential model indicates that the adsorption capacity of shale initially increases before decreasing with increasing depth due to the combined temperature and pressure, which differs from the changing storage capacity pattern for free gases that gradually increase with increasing depth at a constant porosity. These two tendencies cause a mutual conversion between absorbed and free gas that favors shale gas preservation. During the thermal evolution of organic matter, hydrophilic NSO functional groups gradually degrade, reduce the shale humidity and increase the gas adsorption capacity. The shale quality, gas composition and geological conditions all affect the adsorption capacity. Of these factors, the clay minerals and humidity are less important and easily overshadowed by the other factors, such as organic matter abundance.     

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH₄) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH₄ pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R_o. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R_o.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P_L) and maximum sorption capacity (Γ_max). The lowest maturity sample (%R_o = 0.56) displayed a Langmuir pressure (P_L) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R_o > 2.01) sample at 50 °C.The value of the Langmuir pressure (P_L) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH₄ adsorption on organic rich shales were determined based on the experimental CH₄ isotherms. For the adsorption of CH₄ on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs⁰) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.     

Fluid geochemistry of the Sardinian Rift-Campidano Graben (Sardinia,Italy): fault segmentation,seismic quiescence of geochemically “active” faults,and new constraints for selection of CO2 storage sites

Sardinia is typically seismically quiescent, displaying an almost complete lack of historical earthquakes and instrumentally recorded seismicity. This evidence may be in agreement with the presence of a ductile layer in the northern sector of the island, as suggested by the He isotopic signature in fluids rising to the surface through quiescent fault systems. The fault systems have been found to be “segmented” and therefore isolated in fluid circulation. The study of fluid behaviour along fault systems becomes strategically important when applied to solve some geological risk assessments such as Rn-indoor, or to define geological structures like potential CO₂ storage sites. Both of these have been recently requested by the exploitation in Italy of the Euratom Directive and the evolution of the KyotoProtocol policy.Four water-dominated hydrothermal areas of Sardinia, located along regional fault systems, were considered: Campidano Graben, Tirso Valley, Logudoro and Casteldoria. A fluid geochemical survey was carried out taking into account physical–chemical and environmental parameters, major elements within gaseous and liquid phases, a few minor and trace elements, selected isotope ratios (²H, ¹⁸O, ¹³C, ³He/⁴He), ²²²Rn concentration, and some dissolved gases.Two different fluids have been recognised as regards both water chemistry and dissolved gases: (i) CO₂-rich gases, poor in He and Rn, with a relatively high ³He/⁴He ratio (up to R/R_a = 2.32), associated with Na–HCO₃–(Cl) thermal and cold groundwater; (ii) gases rich in He and N₂, poor in CO₂ and Rn, with a low ³He/⁴He ratio, associated with alkaline thermal and cold waters. The distribution of these two groups of fluids characterises the Sardinian tectonic systems. In fact, gas fluxes are not homogeneous, being mainly related to the different fault segments and to the areas where Quaternary basalts crop out. The underground geochemical evolution of the Sardinian fluids, as a function of the geological and tectonic systems, provides some suggestions for solving one of the most important problems: CO₂ geological sequestration. In order to reduce the CO₂ excess produced by human activity, the best geological disposal sites are reservoirs with low hydraulic conductivity, sealed to fluid movement, or aquifers characterised by maximum pH buffering capacity of their mineralogical matrix. The knowledge of the role of faults, as permeability barriers or as deep fluid uprising pathways, is prerequisite.     

Decarbonation of subducting slabs: Insight from petrological–thermomechanical modeling

Subduction of heterogeneous lithologies (sediments and altered basalts) carries a mixture of volatile components (H₂O ± CO₂) into the mantle, which are later mobilized during episodes of devolatilization and flux melting. Several petrologic and thermodynamic studies investigated CO₂ decarbonation to better understand carbon cycling at convergent margins. A paradox arose when investigations showed little to no decarbonation along present day subduction geotherms at subarc depths despite field based observations. Sediment diapirism is invoked as one of several methods for carbon transfer from the subducting slab. We employ high-resolution 2D petrological–thermomechanical modeling to elucidate the role subduction dynamics has with respect to slab decarbonation and the sediment diapirism hypothesis. Our thermodynamic database is modified to account for H₂O–CO₂ binary fluids via the following lithologies: GLOSS average sediments (H₂O: 7.29 wt.% & CO₂: 3.01 wt.%), carbonated altered basalts (H₂O: 2.63 wt.% & CO₂: 2.90 wt.%), and carbonated peridotites (H₂O: 1.98 wt.% & CO₂: 1.50 wt.%). We include a CO₂ solubility P–x[H₂O wt.%] parameterization for sediment melts. We parameterize our model by varying two components: slab age (20, 40, 60, 80 Ma) and convergence velocity (1, 2, 3, 4, 5, 6 cm year^− 1). 59 numerical models were run and show excellent agreement with the original code base. Three geodynamic regimes showed significant decarbonation. 1) Sedimentary diapirism acts as an efficient physical mechanism for CO₂ removal from the slab as it advects into the hotter mantle wedge. 2) If subduction rates are slow, frictional coupling between the subducting and overriding plate occurs. Mafic crust is mechanically incorporated into a section of the lower crust and undergoes decarbonation. 3) During extension and slab rollback, interaction between hot asthenosphere and sediments at shallow depths result in a small window (~ 12.5 Ma) of high integrated CO₂ fluxes (205 kg m^− 3 Ma^− 1).     

Greenhouse gas emissions from soils—A review

Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO₂e m⁻² h⁻¹ (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO₂e (CO₂e = CO₂ equivalents = total effect of all GHG normalized to CO₂). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO₂ are being emitted annually by fossil fuel combustion and the cement industry.