Potential risks to freshwater resources as a result of leakage from CO<Subscript>2</Subscript> geological storage: a batch-reaction experiment

In assessing the feasibility of widespread deployment of CO₂ geological storage, it is prudent to first assess potential consequences of an error or accident that could lead to CO₂ leakage into groundwater resources above a sequestration interval. Information about the sensitivity of the groundwater system to introduction of CO₂ is needed in order to design groundwater monitoring program. A laboratory-batch experiment was conducted to explore the range of CO₂ impact on groundwater quality of a spectrum of representative aquifers, in the Gulf Coast region, USA. Results show that CO₂ elevated concentrations of many cations within hours or days. Two types of cations were recognized according to their concentration trends. Type I cations—Ca, Mg, Si, K, Sr, Mn, Ba, Co, B, Zn—rapidly increased following initial CO₂ flux and reached stable concentrations before the end of the experiment. Type II cations—Fe, Al, Mo, U, V, As, Cr, Cs, Rb, Ni and Cu—increased at the start of CO₂ flux, but declined, in most cases, to levels lower than pre-CO₂ concentrations. Dissolution of dolomite and calcite caused the largest increase in concentrations for Ca, Mg, Mn, Ba and Sr. Cation release rates decreased linearly as pH increased during mineral buffering. Experiment results suggest that carbonate minerals are the dominant contributor of changes in groundwater quality. Risk assessments of potential degradation of groundwater and monitoring strategies should focus on these fast-reacting minerals. Mobilization risk of Type II cations, however, may be self-mitigated because adsorption occurs when pH rebounds.     

A pressure-monitoring method to warn CO2 leakage in geological storage sites

This paper proposes a pressure-monitoring method to warn any possible CO₂ leakage by monitoring pressure change at the upper layer of storage reservoirs within injection wells. The monitoring method is tested with two problems under various scenarios. With a current pressure detection limit, the proposed pressure-monitoring technique can be widely applicable wherever a permeable upper formation exists above the CO₂ storage reservoir and is effective even in offshore storage sites wherever conventional monitoring methods for onshore sites cannot be applied. Meanwhile, the method is limited to apply during injection and is subject to any possible pressure dampening.     

Pyrite of distinctive isotopic composition from the Hemlo deposit: A potential tool to identify this type of gold mineralization in Archean terrain

Most sulphides from various rock types and mineralization of Archean age exhibit sulphur isotope values (δ³⁴S) near 0‰. This is due to a general absence of conditions suitable for the oxidation-reduction reactions essential for isotopic fractionation. However, some important occurrences of Archean Au mineralization do display significant variations in δ³⁴S). One such occurrence with unusual isotopic compositions is the Hemlo gold deposit: pyrite from the ore typically has δ³⁴S < −6‰ to a minimum value of −17.5‰ The isotopic composition of the pyrite is correlated with the content of Au, indicating that they are genetically related.The sulphur isotope data suggest that sulphur compounds experienced redox reactions in the hydrothermal system at Hemlo and that sulphate was present prior to the Au mineralization. This sulphate may be of exogenic origin from a restricted basin, or of endogenic origin from magmatic-hydrothermal fluids. Other characteristic features of the deposit, such as enrichment in Sb, Tl and Hg, may also be explained by ore deposition under moderately oxidizing conditions.Distinctive δ³⁴S values were also observed in pyrite from Au mineralization at Heron Bay, 30 km west of Hemlo, and from baritic strata 21 to 27 km west and on approximate strike from Hemlo. These occurrences also represent sulphate-bearing hydrothermal systems and, as such, give distant information on the unusual environment of the mineralization at Hemlo. Since the isotopes of sulphur are sensitive to oxidation conditions they may be used to identify hydrothermal activities characteristic of this type of Au mineralization and to explore for other unusual areas of sulphate accumulation in Archean terrains.     

Evaluating the impact of caprock and reservoir properties on potential risk of CO2 leakage after injection

Numerical models are essential tools in fully understanding the fate of injected CO₂ for commercial-scale sequestration projects and should be included in the life cycle of a project. Common practice involves modeling the behavior of CO₂ during and after injection using site-specific reservoir and caprock properties. Little has been done to systematically evaluate and compare the effects of a broad but realistic range of reservoir and caprock properties on potential CO₂ leakage through caprocks. This effort requires sampling the physically measurable range of caprock and reservoir properties, and performing numerical simulations of CO₂ migration and leakage. In this study, factors affecting CO₂ leakage through intact caprocks are identified. Their physical ranges are determined from the literature from various field sites. A quasi-Monte Carlo sampling approach is used such that the full range of caprock and reservoir properties can be evaluated without bias and redundant simulations. For each set of sampled properties, the migration of injected CO₂ is simulated for up to 200 years using the water–salt–CO₂ operational mode of the STOMP simulator. Preliminary results show that critical factors determining CO₂ leakage rate through caprocks are, in decreasing order of significance, the caprock thickness, caprock permeability, reservoir permeability, caprock porosity, and reservoir porosity. This study provides a function for prediction of potential CO₂ leakage risk due to permeation of intact caprock and identifies a range of acceptable seal thicknesses and permeability for sequestration projects. The study includes an evaluation of the dependence of CO₂ injectivity on reservoir properties.     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

An isotopic study on the volcanics of the Rooiberg Group: age implications and a potential exploration tool

Many geochronological studies on silicic magmatic rocks associated with the Bushveld Complex (rhyolitic lavas of the Rooiberg Group and granites of the Lebowa Granite Suite) have shown evidence of open-system behaviour of the Rb-Sr and Pb-Pb isotopic systems until 1600–1000 Ma, many hundreds of million years after crystallisation of these rocks. This pervasive open-system behaviour has been attributed to sustained hydrothermal circulation driven by the high heat productivity of the Bushveld granites. New Sr and Pb isotopic data are presented for basaltic to rhyolitic volcanics from the Rooiberg Group of the Transvaal Sequence in the Dullstroom-Loskop Dam area of the eastern Transvaal. These data show little evidence of open-system behaviour after about 1950 Ma and many sample suites retain ages which could reflect the formation of the Rooiberg Group i.e. older than 2070 Ma. It is argued that this preservation is due to the absence of fractionated, fluid/vapour-rich Bushveld granites in the immediate vicinity of the volcanic occurrences. Rooiberg Group volcanics with extensively perturbed Rb-Sr and particularly Pb-Pb isotopic systems reflect the action of granite-derived hydrothermal fluids. As a consequence, the isotope systematics in these volcanics could prove a useful exploration tool for sites of granite-derived metal deposits.     

伟晶岩型锂矿中矿物原位微区元素和同位素示踪与定年研究进展

锂是重要的战略性关键金属,伟晶岩型锂矿是锂资源的主要来源之一。伟晶岩的成因及锂等关键金属在花岗质岩浆-热液演化过程中是如何富集成矿的,是人们十分关注的重要科学问题。多种方法可对伟晶岩的成岩成矿年龄进行限定,除锆石外,其他副矿物和矿石矿物如磷灰石、铌铁矿族矿物、锡石等的原位微区U-Pb定年己得到广泛应用,但需根据定年矿物的共生关系、结晶学及矿物化学特征进行系统研究,合理解释所获年龄的地质意义;伟晶岩型锂矿的成岩成矿一般具有同时性,个别存在多期成矿。伟晶岩的地球化学类型主要有LCT型(富集Li-Cs-Ta)和NYF型(富集Nb-Y-F)及它们的混合类型;成因有"母体花岗岩浆的结晶分异"和"源岩直接部分熔融"两种主要模型;多种矿物学和地球化学方法可用于区分这两种成因。伟晶岩型锂矿床的成矿机制研究包括成矿元素在源区的初始富集,成矿元素在岩浆过程中的富集和沉淀,以及在岩浆-热液过程中的行为和富集作用。伟晶岩中贯通性矿物和矿石矿物的原位微区分析是研究锂等关键金属成矿过程的重要方法。     

Assessing the extent of induced leakage to an urban aquifer using environmental tracers: an example from Bishkek, capital of Kyrgyzstan, Central Asia

A groundwater residence time study of the deep fluvioglacial aquifer supplying Bishkek, capital of Kyrgyzstan, has found evidence of deep infiltration of recent recharge both in the main periurban wellfield and below the city. Commonly-employed hydrochemical markers detected urban influence in the city-centre to depths of 65–100 m, but gave no indication of the important role of induced river/canal bed leakage, either upgradient in the periurban wellfield or within the city. This was revealed by O and H stable isotope measurements, which showed that local rainfall/snowfall play little part in the aquifer water balance. More remarkably, the universal detection of CFCs and SF₆, including in boreholes with 140–220 m deep upper screens, demonstrated that induced leakage of water just a few decades old had penetrated much deeper into the aquifer system than other hydrochemical markers indicated. A two-dimensional flow model set up to test whether such deep pumping-induced leakage could occur below the periurban wellfield confirmed its feasibility. The results imply vertical infiltration rates of 5–10 m/year and demonstrate that in this not-uncommon intergranular aquifer setting, deep boreholes with deep screen settings do not necessarily abstract old water. Hence, there are major implications for urban groundwater management and protection in such settings.

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Resumen Un estudio sobre el tiempo de residencia del agua subterránea, en un acuífero fluvioglacial profundo que abastece a Bishkek, capital de Kyrgyzstan, ha encontrado evidencias de infiltración profunda a partir de recarga reciente, tanto en el campo de pozos de las afueras de la ciudad, como también por debajo de la ciudad. Los indicadores hidroquímicos comúnmente usados, detectaron influencia urbana en el centro de la ciudad hasta profundidades de 65–100 m, pero no dieron indicación del papel importante del goteo inducido en el lecho del canal/río, tanto aguas arriba en el campo de pozos de los suburbios, como también dentro de la ciudad. Esto se reveló mediante mediciones de isótopos estables de O y H, las cuales mostraron que las precipitaciones/nevadas de tipo local, tienen una pequeña contribución en el balance de agua del acuífero. De manera más notoria, la detección universal de CFCs y SF6, incluidos en las rejillas superiores de pozos profundos con 140–220 m de profundidad, demostraron que un goteo inducido de agua, de solo unas pocas décadas de antigüedad, ha penetrado mucho más profundo dentro del sistema acuífero, de lo que los otros marcadores hidroquímicos indicaban. Un modelo bidimensional de flujo, realizado para probar si el goteo inducido—bombeo profundo podía suceder debajo del campo de pozos suburbano, confirmó su factibilidad. Los resultados implican tasas de infiltración vertical de 5 a 10 m/año, y demuestran que los pozos profundos con tramos de rejilla también profundos, no necesariamente extraen aguas antiguas, en estos ambientes acuíferos con porosidad intergranular. Por lo tanto, hay implicaciones importantes para la gestión y protección en zonas urbanas, y para esos ambientes de las aguas subterráneas.

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Résumé Lanalyse du temps de résidence des eaux souterraines dans un aquifère fluvial profond, dorigine glaciaire, qui alimente en eau Bishek, la capitale de Kyrgyzstan a mis en évidence une recharge récente tant dans le captage en eau que sous la ville même. Les traceurs chimiques ont indiqué linfluence urbaine dans le centre de la ville, à une profondeur de 65–100 m, mais ils nont pas mis en évidence le rôle important de lalimentation induite par la couche du fleuve, tant en amont, dans le captage que en aval, dans la ville. Ces effets ont été relevés par des isotopes stables, comme O et h qui ont montré linfluence récente des précipitations dans le bilan hydrique de laquifère. De plus, la détection universelle de CFC et de SF6, y compris dans les forages ayant une profondeur de 140–220 m, montre que lalimentation en eau induite de plusieurs décennies a pénétré à des profondeurs plus grandes que celles indiqués par des traceurs chimiques. Les possibilités dune drainance verticale induite par les pompages dans le puits profonds du captage ont été vérifiées par un modèle bidimensionnel découlement. Les résultats de la modélisation ont conduit à une infiltration verticale de 5–10 m/an et ont démontré aussi que leau extraite par des puits profonds dans un aquifère granulaire nest pas nécessairement dage ancienne. Il sagit donc des implications majeures concernant la gestion et la protection des captages urbaines en eaux souterraines

     

Vision 2020: Towards an environmentally sound and sustainable development of freshwater resources in Malaysia

Malaysia has a climate of high humidity, high temperature and abundant rainfall. Rivers supply about 97% of the country's total water needs while ground water accounts for the rest. About 40% of the treated water is lost through man-caused leakages. With a population of 18.3 million people, the total annual domestic, industrial and irrigation water demand is about 11.6 x 106 MI. This figure is projected to rise to 15.2 x 106 MI by year 2000. At present, the total daily water demand is about 4,979 MI and the production capacity is 6,513 MI. Water use and misuse now strain the nation's fragile aquatic environment and natural ecosystems. Current water resource management priorities include water quality improvement, river rehabilitation to restore over-channalized or polluted rivers and development of the inland fisheries potential especially in large man-made reservoirs. A River Basin Information System has been developed to provide integrated information on catchment characteristics, landuse, population and socio-economic profile, river flow, pollution sources, water quality classification, and aquatic biota. Vision 2020 challenges call for a long-term perspective in inland water resource management. Critical post-audits of largescale development and strategic research aimed at alternative and interacting patterns of landwater use are urgently needed.     

AUSTRALIS: A new tool for the study of isotopic systems and geochronology in mineral systems

AUSTRALIS (AMS for Ultra Sensitive TRAce eLement and Isotopic Studies) is a microbeam accelerator mass spectrometry (AMS) system designed for in situ microanalysis of geological samples for trace elements and radiogenic and stable isotope data. The AMS method eliminates molecular and isobaric interferences in in situ mass spectrometric measurements, opening up new opportunities in geochronology and tracer applications. Tests have been carried out for measurements of Pb, S and Os isotopes, conducted mainly at 1.5 MV accelerating voltage. In Pb and S tests, precision as high as 0.3‰ has been obtained, made possible by a fast isotope switching system to counter the effect of instabilities in the ion source and beam transport system. In trace‐element analysis, a detection limit for Au at the sub‐ppb level was obtained.     

Evaluation of carbon isotope fractionation of soil CO2 under an advective-diffusive regimen: A tool for computing the isotopic composition of unfractionated deep source

A physical model based on the advective-diffusion theory was developed in order to describe the mixing between a deep gas source and the atmosphere. The model was used to predict the isotopic fractionation of carbon in soil CO₂. Gas samples were collected at different depths in areas characterized by different geological settings and CO₂ fluxes. The relative theoretical and experimental isotopic profiles were compared and a good agreement was found. These profiles show how the isotopic composition of CO₂ changes through the upper few decimeters of soil and how the amount of the isotopic fractionation is strongly influenced by soil CO₂ flux. Finally, the model was used to derive the carbon isotopic composition of unfractioned deep CO₂ source for all the investigated sites.     

Application of Pb isotopic tracing technique to constraining the source of Pb in the West Lake Longjing tea

This paper dealt with the Pb contents and Pb isotopic composition of the West Lake Longjing tea. The results showed that in the tea leaves, from young leaf →old leaf →tea limb, the Pb contents tend to increase gradu-ally from 1.63 →4.84 →6.07×10-6, wich revealed that the Pb was accumulated gradually in the tea. After cleaned, the Pb contents of tea leaves were significantly reduced. This indicated that the deposits on the surface of tea leaves made a great contributuion to Pb contents. The survey results for soils in the relevant tea gardens showed that soil from the Longjing tea garden has higher Pb contents, with an average level of 49.6×10-6, two times those of common soils (24×10-6) in China. Results of the systematic analysis for tea, tea garden soil and the samples with the relevant background of the Pb isotopic composition displayed that the Pb isotopic ratio of tea is 206Pb/207Pb=1.164±0.005 (2σ). The ratio of 206Pb/207Pb for the soil gradually decreased from residue phase, soil dilute acid extract phase, and then to urban topsoil, i.e., 1.175 →1.171 →1.170. The 208Pb/(206Pb+207Pb) ratios also show a similar variation trend. 206Pb/207Pb ratios in the samples with the relevant background were: vehicle exhaust, 1.124; coal-combustion, 1.156; atmosphere, 1.168; and water, 1.166. Comparative studies have shown that Pb pollution is popular in the environ-mental media (soil, atmosphere, water) in Hangzhou. With the aggravation of Pb pollution, the Pb isotopic composi-tion gradually changed from the natural background (soil residues) to the direction of automobile exhaust. This phe-nomenon could illustrate that the pollution source was the vehicle exhaust, while the coal-combustion contributed little to environmental pollution in Hangzhou. The Pb of the Longjing tea came mostly from soluble phase Pb in the polluted soil. Moreover, secondary pollution was caused by vehicle exhaust.     

Effects of CO2 on the zeta potential of hematite

Zeta potential is an important factor in affecting filtration rates of iron ore slurries. Two methods of zeta potential control investigated during this study were (1) pH adjustments and (2) surface modifications by reagent addition. It was originally hypothesized that adding CO₂ to a hematite slurry, would form a carbonic acid, leading to lower pH levels, lower zeta potentials and increased filtration rates. Samples under both ideal (1 mM KCl as background electrolyte solution) and plant (plant water as background electrolyte) conditions were tested during this study. Through zeta potential testing of hematite slurries under ideal conditions (with and without CO₂ sparging), it was observed that CO₂ sparging achieved both (1) pH reduction and (2) surface modification of the hematite particles. While the shapes of the zeta potential curves were different for samples taken from the operating plant under plant conditions, the same downward shift in the entire zeta potential curve was observed after CO₂ sparging. The surface modification phenomenon was attributed to the possible formation of complexes between carbonate/bicarbonate ions and the surface of the hematite particles. The possibility of double layer compression was also investigated. While some variations in conductance were observed, these variations did not entirely explain the changes in zeta potential, therefore providing even stronger evidence of surface modification through hematite/carbonate (or bicarbonate) surface complexing. In the event of a hematite/carbonate (or bicarbonate) complex forming, its exact composition is still unknown, but the surfaces showed zeta potential properties similar to that of a siderite (iron carbonate) sample analyzed during this study.     

Assessment of soil moisture influence on CO2 flux: a laboratory experiment

Accurate measurements to assess the influence of soil moisture on CO₂ flux requires the absolute estimates of soil CO₂ flux. Thus, it was constructed a calibration system where CO₂ with fixed concentration flowed through the different porous material. Previous to measurement, in order to verify the performance and reliability of a closed dynamic chamber, different discontinuous air-mixing rates and times were tested. The CO₂ flux was estimated through sequential lectures and the best fit for flux measurements was obtained taking short readings every 3 min, during a total time of 12 min (R ² = 0.99). The best mixing rate was attained for 250 mL min⁻¹, allowing 25 s of mixing previous to CO₂ extraction for an infrared gas analyzer. The deviation of the measured values for dry sand from the reference CO₂ flux (0.097 and 0.071 g m⁻² min⁻¹) was 5 and 7%. On dry sandy loam soil (SLS) the deviation was 2%. The measured fluxes decreased 73 and 22% with content moisture of 20 and 10% (sand), and 78% with content moisture of 31% (SLS). This work allowed to estimate how much the measured emission rates deviate from the true ones for the specified chamber and sampling conditions.     

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (?34.9 ‰ to 3.58 ‰) at 32.0 °C and from ～7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰?1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from ?7.5 ‰ to ?9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from ?13.5 ‰ to ?18.5 ‰ for CO₂ inclusions in zone 1 and from ?16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.     

Aquifer disposal of CO2-rich greenhouse gases: Extension of the time scale of experiment for CO2-sequestering reactions by geochemical modelling

Summary In previous work,Gunter et al. (1993), suggested water-rock reactions in deep aquifers in sedimentary basins could sequester injected-CO₂-waste from industry, thereby reducing greenhouse gas emissions. Experiments, carried out at 105°C and 90 bars CO₂ pressure, to test the validity of this mineral-trapping of CO₂ were unsuccessful due to sluggish kinetics of reaction. The most significant change recorded by the reaction products from these experiments was a large increase in alkalinity, which was attributed to very small amounts of water-mineral reaction. A computer model, PATHARC.94, was used to interpret this change in alkalinity and to predict the path and time necessary to reach equilibrium. Substantial trapping of CO₂ by formation of siderite, calcite and aqueous bicarbonate ions was predicted to occur in 6 to 40 years.Potential errors as high as two orders of magnitude were estimated based on a thorough examination of the kinetic data used in the modelling. In order to achieve reasonable time estimates, reactive surface areas were approximated by 100 micron spherical grains in the computer model. This represents a smaller cumulative surface area than actually present in the experiment. When these results are extrapolated to the field, where the aquifers are at lower temperatures,Perkins andGunter (1995a), concluded that CO₂-trapping reactions are expected to take 100s of years to complete. This is sufficient time for the trapping to occur as the residence time of a packet of fluid in a deep low-permeability aquifer in a sedimentary basin is measured in 10,000s to 100,000s of years.

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Einlagerung von CO₂-Treibhaus-Gasen in einem Aquifer: Erweiterung des Zeitmaßstabes von Experimenten von CO₂-Aufnahme-Reaktionen durch geochemische Modellierung

Zusammenfassung In früheren Arbeiten habenGunter et al. (1993) Wasser-Gesteinsreaktionen in tiefen Aquiferen in Sedimentbecken vorgeschlagen, die injiziertes CO₂ aus industriellen Abgasen aufnehmen, und damit die Treibhausgasemissionen reduzieren könnten. Experimente wurden bei 105°C und 90 bar CO₂-Druck durchgeführt, um die Anwendbarkeit dieser mineralischen Fallen für CO₂ zu testen; wegen der langsamen Reaktions-Kinetik waren diese nicht erfolgreich. Die markanteste Änderung, die diese Experimente in den Reaktionsprodukten hervorriefen, war eine beträchtliche Zunahme der Alkalinität, die auf geringfügige Wasser-Mineralreaktionen zurückgehen dürfte. Ein Computermodell, PATHARC 94, wurde benützt, um diese Änderungen der Alkalinität zu interpretieren und die erforderlichen Zeiten und Pfade vorherzusagen, die notwendig sind, um Gleichgewicht zu erreichen. Signifikanter Einbau von CO₂ durch Bildung von Siderit, Calcit und Bikarbonat-tonen sollte dementsprechend in 6 bis 40 Jahren stattfinden.Mögliche Fehler, die bis in zwei Größenordnungen gehen können, wurden aufgrund einer sorgfältigen Überprüfung der kinetischen Daten, die hier benützt wurden, ermittelt. Um sinnvolle Zeitmaßstäbe zu erreichen, wurden im Computermodell reaktive Ober flächen durch 100 Mikron große kugelförmige Körner repräsentiert. Dies stellt eine kleinere Gesamtoberfläche dar, als die, die tatsächlich im Experiment vorhanden ist. Wenn diese Ergebnisse ins Gelände extrapoliert werden, wo die Aquifere niedrigere Temperaturen aufweisen, kommenPerkins undGunter (1995a) zu dem Schluß, daß ein vollständiger Einbau von CO₂ hunderte von Jahre benötigen würde. Diese Zeiträume sind ausreichend, da die Verweildauer einer Fluid-Menge in einem tief gelegenen Aquifer mit niedriger Permeabilität in einem sedimentären Becken in Größenordnungen von 10.000 bis 100.000 von Jahren gemessen wird.

     

A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids

Pyrolysates of high-molecular-weight sedimentary fractions of the Duvernay Formation (Western Canada Basin) are dominated by 1,2,3,4- and 1,2,3,5-tetramethylbenzene, which, generated via beta-cleavage, indicate the presence of diaromatic carotenoids in the macromolecular aggregates. This was substantiated by desulphurization of sulphur-rich aggregates of the polar fraction, which released (partly) hydrogenated carotenoids. Furthermore, these components were important constituents of the aromatic hydrocarbon fractions and related oils. Apart from renieratane and isorenieratane, 1H NMR analysis established the aromatic substitution pattern of the most abundant component present, which was identified as a diaromatic compound with an unprecedented 2,3,6-/3,4,5-trimethyl aromatic substitution pattern. Molecular and isotopic analyses of both soluble and insoluble fractions of organic matter revealed relationships between diagenetically-derived carotenoids found in bitumen and related oils and their precursors incorporated into high-molecular-weight fractions. Aryl isoprenoids, important components in extracts and oils, were apparently derived from thermal cracking of bound diaromatic carotenoids rather than cleavage of free carotenoids as previously suggested. Furthermore, products derived from diaromatic carotenoids were substantially enriched in 13C relative to n-alkanes of algal origin. Together with the characteristic carotenoids, this isotopic enrichment provides evidence of significant contributions from photosynthetic green sulphur bacteria (Chlorobiaceae), which fix carbon via the reversed tricarboxylic acid (TCA) cycle. In spite of the prominence of these molecular signals, the overall isotopic composition of the organic matter indicated that only a very small portion of the preserved organic carbon was derived from the biomass of photosynthetic green sulphur bacteria.     

Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Toward physical aspects affecting a possible leakage of geologically stored CO2 into the shallow subsurface

In geological formations, migration of CO₂ plume is very complex and irregular. To make CO₂ capture and storage technology feasible, it is important to quantify CO₂ amount associated with possible leakage through natural occurring faults and fractures in geologic medium. Present work examines the fracture aperture effect on CO₂ migration due to free convection. Numerical results reveal that fracture with larger-aperture intensify CO₂ leakage. Mathematical formulation and equations of state for the mixture are implemented within the object-oriented finite element code OpenGeoSys developed by the authors. The volume translated Peng–Robinson equation of state is used for material properties of CO₂ and water.