Carbonate cements in Miller field of the UK North Sea: a natural analog for mineral trapping in CO<Subscript>2</Subscript> geological storage

Miller field of the North Sea has had high concentrations of natural CO₂ for ~70 Ma. It is an ideal analog for the long-term fate of CO₂ during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO₂ in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO₂ charge. Margins of the concretions are corroded, probably because of reduced pH due to CO₂ influx. Dispersed calcite cements are also present, some of which postdate the CO₂ charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO₂ in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO₂ emplacement. Most of the CO₂ accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO₂ storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

A model for estimating the value of sampling programs and the optimal number of samples for contaminated soil

A model is presented for estimating the value of information of sampling programs for contaminated soil. The purpose is to calculate the optimal number of samples when the objective is to estimate the mean concentration. A Bayesian risk–cost–benefit decision analysis framework is applied and the approach is design-based. The model explicitly includes sample uncertainty at a complexity level that can be applied to practical contaminated land problems with limited amount of data. Prior information about the contamination level is modelled by probability density functions. The value of information is expressed in monetary terms. The most cost-effective sampling program is the one with the highest expected net value. The model was applied to a contaminated scrap yard in Göteborg, Sweden, contaminated by metals. The optimal number of samples was determined to be in the range of 16–18 for a remediation unit of 100 m². Sensitivity analysis indicates that the perspective of the decision-maker is important, and that the cost of failure and the future land use are the most important factors to consider. The model can also be applied for other sampling problems, for example, sampling and testing of wastes to meet landfill waste acceptance procedures.     

Synthesis,characterization of CdS/rectorite nanocomposites and its photocatalytic activity

CdS/rectorite nanocomposite was synthesized via a cation-exchange reaction followed by a sulfurization process. The obtained samples were characterized by using X-ray diffraction (XRD), fourier transform infrared spectra (FTIR), transmission electron microscope (TEM), UV-Vis diffuse reflectance spectra (DRS), and thermal analysis. The measured results indicate that CdS species in the composites exist in the form of pillars and nanoparticles, the crystallized CdS particles are in the hexagonal symmetry. The photocatalytic activities of the pillared nanocomposite were enhanced significantly comparing with the bare rectorite and the pure CdS. Moreover, the photostabilities of the obtained nanocomposites are also better than that of the pure CdS due to the hosts retard the photocorrosion of the CdS.     

Collapse of caves at shallow depth in Gaziantep city center,Turkey: a case study

This paper focuses on an investigation of the possible causes for the collapse of limestone caves in Gaziantep, Turkey. The city contains a lot of man-made caves, at a shallow depth, of various width and length. These caves were mainly excavated to provide work or storage space. As the city has been growing fast with increased population, many structures were constructed over these caves. Recently, two caves collapsed and five houses were damaged. These caves are all made of limestone and it was observed after the collapse that the limestone was saturated with water due to sewer pipe leakage and surface water. Tests were carried out on the limestone and it was determined that the compressive strength of limestone decreases by about 50% and the tensile strength decreased by about 80% when saturated with water. It was concluded that the reduced strength of the limestone combined with additional loads due to the factors mentioned above seem to be the main reason for these collapses.     

Garnet reequilibration and growth in the eclogite facies and geodynamical evolution near peak metamorphic conditions

Caledonian eclogite-facies metamorphism partially reworking Grenvillian granulite-facies anorthosite allows us to study the processes of garnet reequilibration at high pressure and to reconstruct the evolution of the unit near metamorphic peak conditions. Our results indicate that eclogite-facies metamorphism happened in two successive phases: first, inherited granulitic garnet was fractured and reequilibrated from their boundaries (crystal or fracture rims); then eclogite-facies minerals were crystallised in the fractures as overgrowths on inherited garnets. The reequilibration of inherited garnets is achieved through Fe²⁺Mg⁻¹ exchange, whereas eclogite-facies garnets crystallised during the subsequent phase are notably richer in Ca than un- and re-equilibrated granulitic garnet. Pseudosection construction shows that this lack in Ca reequilibration cannot be related to variations in thermodynamic conditions (a _H2O, reacting system composition) between the two phases. From the compilation of the available data, the reequilibration of granulitic garnet seems to be controlled by the inefficient intra- and inter-granular transport properties of Ca compared to Fe²⁺ and Mg. While these kinetic factors confine garnet reequilibration to Fe²⁺Mg⁻¹ exchange, the extent of reequilibration along this exchange vector is controlled by partitioning with adjacent omphacite. On the contrary to the diffusional reequilibration of granulitic garnet that lasted for several My according to our modelling of the diffusional relaxation, the strong compositional gradients between eclogite-facies and reequilibrated garnets, which are almost unaffected by diffusional reequilibration, provide evidence that rapid exhumation followed the crystallisation of eclogite-facies minerals. We propose that the movement reversal itself, from burial to exhumation, and associated deformation and fluid flow, triggered this crystallisation event. The resulting evolution near metamorphic peak conditions is therefore strongly asymmetrical: on the one hand, the prograde diffusional relaxation profiles indicate slow movement during the last stages of burial, whereas the unaffected retrograde overgrowth indicates fast exhumation rates.     

Investigation of NaCl deliquescence in porous substrates using RH-XRD

We report on the use of X-ray diffractometry under controlled conditions of temperature and relative humidity (RH-XRD) for the investigation of NaCl deliquescence in the pore space of glass filter frits, which were used as model substrates. The study confirms that RH-XRD is an appropriate experimental technique for the in situ observation of phase transformation in porous materials. It is used for an investigation of both the deliquescence kinetics and the deliquescence humidity within pores of different median pore diameter. Several major influences affecting deliquescence rates in the pore space close to the surface of a porous material are discussed. It appears that quite short-term variation of ambient relative humidity, e.g., typical daily fluctuations, might induce damaging deliquescence–crystallization cycles within the pore space of building materials. In agreement with theoretical considerations it was found that confinement of NaCl crystals in pores with median diameters in the range 1.4–70 μm does not affect the deliquescence humidity of the salt.     

Cumulating processes at the crust-mantle transition zone inferred from Permian mafic-ultramafic xenoliths (Puy Beaunit,France)

Ultramafic and mafic xenoliths of magmatic origin, sampled in the Beaunit vent (northern French Massif Central), derive from the Permian (257 Ma) Beaunit layered complex (BLC) that was emplaced at the crust-mantle transition zone (∼1 GPa). These plutonic xenoliths are linked to a single fractional crystallisation process in four steps: peridotitic cumulates; websteritic cumulates; Al-rich mafic cumulates (plagioclase, pyroxenes, garnet, amphibole and spinel) and finally low-Al mafic cumulates. This sequence of cumulates can be related to the compositional evolution of hydrous Mg basaltic magma that evolved to high-Al basalt and finally to andesitic basalt. Sr and Nd isotopic compositions confirm the co-genetic character of the various magmatic xenoliths and argue for an enriched upper mantle source comparable to present mantle wedges above subduction zones. LILE, LREE and Pb enrichment are a common feature of all xenoliths and argue for an enriched sub-alkaline transitional parental magma. The existence of a Permian magma chamber at 30 km depth suggests that the low-velocity zone observed locally beneath the Moho probably does not represent an anomalous mantle but rather a sequence of mafic/ultramafic cumulates with densities close to those of mantle rocks.     

Characterization of a chalcopyrite from Brazil by Mössbauer spectroscopy and other physicochemical techniques

We studied a chalcopyrite from a Cu ore deposit in Rio Grande do Sul, Brazil, by Mössbauer spectroscopy at room temperature and 110 K. Supporting methods to check for sample purity and to characterize further sample properties were slow-scanning X-ray powder diffraction and optical and microprobe analyses of polished sections of selected grains. Chemical analyses obtained using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer showed the sample to consist of homogeneous and essentially stoichiometric chalcopyrite (CuFeS₂). Mössbauer spectra taken at both the above temperatures consist of asymmetric magnetically ordered patterns with unequal intensities of the line pairs 1–6 and 2–5, pointing to the existence of non-equivalent or multiple Fe sites. Least-squares fittings evidenced that the resonance intensity ratio of subspectrum with lower quadrupole shift (indicative of a more symmetric environment) to that with higher shift is 69:31, at room temperature, and 68:32, at 110 K. Rietveld refinement of the XRD data indicates the existence of tetragonal [a = 0.52855(1) and c = 1.0412(1) nm] and cubic [a ₀ = 0.5273(2) nm] modifications in a proportion of 74:26, in good agreement with the Mössbauer data. The saturation magnetization of the sample was 32.7 J/(T kg), confirming the oxidation state of Fe as trivalent and pointing to little to no spin canting.