火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明:加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为“自生自储“,成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

火山岩吸附CO_2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明:加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关。松辽盆地北部昌德东CO2气藏成藏模式为“自生自储”,成藏CO2气主要来自深部被火山岩吸附的气。随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏。     

松辽盆地北部火山岩CO2脱气参数及其对CO2资源量估算的意义

为了定量评价火山岩脱CO2气量的潜力，选择松辽盆地北部火山岩进行了低温脱气实验。将火山岩加热到250℃时，脱出挥发份总量为0.0299～0.0790ml/g；其中CO2脱出量为0.0218～0.0706 ml/g（0.429～1.387wt％）。脱挥发份总量与其中CO2量具有良好的正线性相关；挥发份以CO2气为主，其次是Ｎ2气，还伴有H2、CO、CH4等还原性气体，以及更少量的低碳烷烃；基性火山岩比中、酸性火山岩脱出CO2数量较多。火山岩吸附大量CO2气，成为充足气源，火山岩脱出的吸附气主要是辗转而来的深源气，火山岩成为探索幔源气成藏的主要源岩，尤其是基性火山岩。估算CO2资源量，可将250℃时火山岩挥发份含量作为岩石挥发份及残余CO2量的下限值，而全岩分析的总碳含量可作为CO2脱出量的上限值。     

松辽盆地北部昌德东CO2气藏的自生自储成藏模式

松辽盆地北部昌德东CO₂气藏的“自生自储“成藏模式指成藏气体主要是无机成因的幔源火山岩吸附气，后期的构造运动使裂缝连通、天然气汇聚成藏。证据有：火山岩含有WB为0.429%~1.387%的吸附CO₂，具有孔隙和缝隙相互组合的双孔介质，说明火山岩既可作为CO₂气的源岩，亦可作为储层；昌德东CO₂气藏中存在近距离不均一的CO₂含量空间分布、下贫上富的储层CO₂含量和上高下低的CH₄-CO₂平衡温度等特征。中国东部幔源—岩浆成因的CO₂气藏地区均发育幔源火山岩，说明该成藏模式具有现实的可能性和普遍性。     

山东济阳坳陷二氧化碳气成藏模式分析

山东济阳坳陷CO2气藏类型众多,成藏模式存在多样性。根据CO2气藏组分含量和同位素的分析结果,发现济阳坳陷CO2气藏以幔源成因为主,岩浆气源体是最重要的CO2气源体,火山岩体、火山通道和岩浆气源体附近的断裂对CO2气的运移成藏起关键作用。通过卸压条件下CO2的运移、CO2在断裂(裂缝)中的运移、CO2在孔隙—裂缝双重介质中的运移、CO2在砂质沉积物中的运移等一系列实验模拟,研究岩浆释出CO2气的运移成藏过程。结合已知气藏的运移成藏地质过程,建立济阳坳陷CO2气藏的3种地质模式,即侵入体—断裂—储集层转折成藏模式、侵入体—储集层直接成藏模式和埋藏火山通道—储集层直接成藏模式,为济阳坳陷CO2气成藏研究及其综合勘探奠定基础。     

济阳坳陷CO2气藏同位素地球化学特征及成因

济阳坳陷CO2气藏主要发育在高青-平南深断裂中南段和阳信次级凹陷西北缘及商店火山岩穹隆构造内.气藏中CO2气体浓度为69%～97%,δ13CCO2值为-5.67‰～-3.35‰,CH4/3He值为(1.01～5.65)×108,3He/4He值为(2.80～4.49)×10-6,即R/Ra为2.00～3.21,40Ar/36Ar值为317～1791,CO2/3He值为(0.25～2.61)×109.以上地球化学数据表明,济阳坳陷气藏中CO2主要来源于地幔,且幔源CO2在成藏过程中有损失,或者有壳源CO2的加入,特别是部分碳酸盐岩变质成因CO2的加入.在对CO2气来源定性分析的基础上,还需要在各来源的定量区分和CO2气藏的成藏及其与岩浆活动的时空匹配关系等方面作进一步的研究.     

中国东部及南海西部陆缘CO2气藏形成机理

以我国东部及南海西部陆缘众多CO2气葳为依据，分析了气藏中气体组分、同位素组成及分布特征，指出该地区从北至南分布着一巨型北东向岩浆幔源无机成因CO2气藏带，莺歌海盆地中具有壳幔混源特征，其形成机理与欧亚板块和太平洋板块碰撞俯冲带所形成的构造岩浆作用有关；靠近俯冲带，热源体以火山岩体、基性玄武岩为主，远离俯冲带则以泥底辟热流体为主；超壳断裂是幔源气和热源的输运通道。     

济阳坳陷CO0_2气藏同位素地球化学特征及成因

济阳坳陷CO2气藏主要发育在高青-平南深断裂中南段和阳信次级凹陷西北缘及商店火山岩穹隆构造内。气藏中CO2气体浓度为69%~97%,δ13CCO2值为-5.67‰~-3.35‰,CH4/3He值为(1.01~5.65)×108,3He/4He值为(2.80~4.49)×10-6,即R/Ra为2.00~3.21,40Ar/36Ar值为317~1791,CO2/3He值为(0.25~2.61)×109。以上地球化学数据表明,济阳坳陷气藏中CO2主要来源于地幔,且幔源CO2在成藏过程中有损失,或者有壳源CO2的加入,特别是部分碳酸盐岩变质成因CO2的加入。在对CO2气来源定性分析的基础上,还需要在各来源的定量区分和CO2气藏的成藏及其与岩浆活动的时空匹配关系等方面作进一步的研究。     

松南油伴生CO2气的成因及其对油气藏的影响

以松辽盆地南部长岭断陷油伴生气和含片钠铝石砂岩为对象,研究松南伴生CO2气的成因,并在此基础上,讨论幔源-岩浆CO2混入对油气动态成藏的影响。通过对伴生气组分,碳、氧及氦同位素数据的分析,发现松南油伴生CO2气的体积分数为1.57%～75.25%,主体在20%以上,δ13 CCO2值为-9.90‰～-4.00‰,R/Ra为0.95～4.46,说明松南油伴生气中CO2的体积分数很高,伴生CO2气主体为幔源-岩浆成因。如果幔源-岩浆CO2气大量混入油藏,将发生CO2驱油,形成次生油气藏。由松南油气藏的典型剖面特征及片钠铝石中原生烃类包裹体的发现,证实松南存在幔源-岩浆CO2驱油的事实。在幔源-岩浆CO2与油气混合成藏地区,寻找幔源-岩浆CO2充注驱油成因的次生油气藏已成为新的勘探思路。     

松辽盆地火山岩高含CO2气藏包裹体特征及成藏期次

在详细岩相学观察的基础上,充分利用包裹体的岩相学特征、均一温度特征、气体组分特征以及碳同位素特征等,确定了松辽盆地营城组火山岩中包裹体的类型、期次和成分特征,并对火山岩高含CO2气藏的成藏期次进行了分析。综合各种地质地化证据,确定松辽盆地火山岩高含CO2气藏中烃类气成藏特征是连续充注基础上的两期成藏,即泉头组—青山口组沉积时期和嫩江组沉积中后期;CO2充注发生在喜山期,CO2的充注晚于烃类气的充注。     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Melting relationships in the systems CaOCO2 and MgOCO2 to 33 kilobars

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine

Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO₂ (CO₂–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO₂ storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO₂ (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N₂, in order to mimic O₂-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO₂-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO₂ increased in all experiments. Release rates of Fe and SiO₂ were more pronounced in solutions reacted with CO₂–brine as compared to those reacted with CO₂-free brine. For samples reacted with the CO₂–brine, lower temperature reactions (80 °C) released much more Fe and SiO₂ than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO₂–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO₂-free brine; while no trace of analcime was observed in either of the samples reacted with CO₂–brine.     

Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.