Water in minerals? A peak in the infrared

The study of water in minerals with infrared spectroscopy is reviewed with emphasis on natural and synthetic quartz. Water can be recognized in minerals as fluid inclusions and as isolated molecules and can be distinguished from hydroxide ion. The distinction between very small inclusions and aggregates of structurally bound molecules is difficult. New studies of synthetic quartz using near-infrared spectroscopy are reported. These demonstrate that water molecules are the dominant hydrogen containing species in synthetic quartz but that this water is not in aggregates large enough to form ice when cooled

Solubility and diffusional uptake of hydrogen in quartz at high water pressures: Implications for hydrolytic weakening

Attempts to introduce molecular water into dry, natural quartz crystals by diffusive transport and thus weaken them hydrolytically at T = 700°–900°C and PH_2O = 400–1550 MPa have failed. Infrared spectroscopy of hydrothermally annealed single crystals of natural quartz reveals the diffusive uptake of interstitial hydrogen (resulting in hydroxyl groups) at rates similar to those previously proposed for intracrystalline water at high water pressures. The solubility of interstitial hydrogen at these conditions is independent of temperature and pressure; instead, it depends upon the initial aluminum concentration by the local charge neutrality condition [H_i·] = [Al_(Si)′]. The rate of interstitial hydrogen diffusion parallel to c is given by an Arrhenius relation with D_0 = 1.4 × 10^(−1) m^2/s and Q = 200 ± 20 kJ/mol, in close agreement with H diffusivities reported for much lower pressures (PH_2O = 2.5 MPa). Deformation experiments following hydrothermal annealing show no mechanical weakening, and the lack of any detectable broadband absorption associated with molecular water shows that the diffusion rates of structural water are much lower than those of hydrogen. These results are consistent with the available oxygen diffusion data for quartz and with the failure to observe weakening in previous studies of quartz deformation at pressures of 300–500 MPa; they call into question the rapid rates of diffusion originally suggested for the hydrolytic weakening defect. It is suggested that the observed weakening in many previous experiments was complicated by microcracking processes in response to nonhydrostatic stresses and low effective confining pressures. Extensive microcracking may provide a mechanism for molecular water to enter quartz and allow local plastic deformation to occur. It does not appear that molecular water can diffuse far enough into uncracked quartz to allow hydrolytic weakening over annealing times that are feasible in the laboratory

Integrated Geothermal-CO2 Reservoir Systems: Reducing Carbon Intensity through Sustainable Energy Production and Secure CO2 Storage

AbstractLarge-scale geologic CO2 storage (GCS) can be limited by overpressure, while geothermal energy production is often limited by pressure depletion. We investigate how synergistic integration of these complementary systems may enhance the viability of GCS by relieving overpressure, which reduces pore-space competition, the Area of Review, and the risks of CO2 leakage and induced seismicity, and by producing geothermal energy and water, which can defray parasitic energy and water costs of CO2 capture

Dynamic Data-Driven Event Reconstruction for Atmospheric Releases

Accidental or terrorist releases of hazardous materials into the atmosphere can impact large populations and cause significant loss of life or property damage. Plume predictions have been shown to be extremely valuable in guiding an effective and timely response. The two greatest sources of uncertainty in the prediction of the consequences of hazardous atmospheric releases result from poorly characterized source terms and lack of knowledge about the state of the atmosphere as reflected in the available meteorological data. In this report, we discuss the development of a new event reconstruction methodology that provides probabilistic source term estimates from field measurement data for both accidental and clandestine releases. Accurate plume dispersion prediction requires the following questions to be answered: What was released? When was it released? How much material was released? Where was it released? We have developed a dynamic data-driven event reconstruction capability which couples data and predictive models through Bayesian inference to obtain a solution to this inverse problem. The solution consists of a probability distribution of unknown source term parameters. For consequence assessment, we then use this probability distribution to construct a ''''composite'' forward plume prediction which accounts for the uncertainties in the source term. Since in most cases of practical significance it is impossible to find a closed form solution, Bayesian inference is accomplished by utilizing stochastic sampling methods. This approach takes into consideration both measurement and forward model errors and thus incorporates all the sources of uncertainty in the solution to the inverse problem. Stochastic sampling methods have the additional advantage of being suitable for problems characterized by a non-Gaussian distribution of source term parameters and for cases in which the underlying dynamical system is non-linear. We initially developed a Markov Chain Monte Carlo (MCMC) stochastic methodology and demonstrated its effectiveness by reconstructing a wide range of release scenarios, using synthetic as well as real-world data. Data for evaluation of our event reconstruction capability were drawn from the short-range Prairie Grass, Copenhagen, and Joint Urban 2003 field experiments and a continental-scale real-world accidental release in Algeciras, Spain. The method was tested using a variety of forward models, including a Gaussian puff dispersion model INPUFF, the regional-to-continental scale Lagrangian dispersion model LODI (the work-horse real-time operational dispersion model used by the National Atmospheric Release Advisory Center), the empirical urban model UDM, and the building-scale computational computational fluid dynamics code FEM3MP. The robustness of the Bayesian methodology was demonstrated via the use of subsets of the available concentration data and by introducing error into some of the measurements. These tests showed that the Bayesian approach is capable of providing reliable estimates of source characteristics even in cases of limited or significantly corrupted data. For more effective treatment of strongly time-dependent problems, we developed a Sequential Monte Carlo (SMC) approach. To achieve the best performance under a wide range of conditions we combined SMC and MCMC sampling into a hybrid methodology. We compared the effectiveness and advantages of this approach relative to MCMC using a set of synthetic data examples. Our dynamic data-driven event reconstruction capability seamlessly integrates observational data streams with predictive models, in order to provide the best possible estimates of unknown source term parameters, as well as optimal and timely situation analyses consistent with both models and data

Encapsulation of 2-amino-2-methyl-1-propanol with tetraethyl orthosilicate for CO2 capture

Carbon capture is widely recognised as an essential strategy to meet global goals for climate protection. Although various CO2 capture technologies including absorption, adsorption and membrane exist, they are not yet mature for post-combustion power plants mainly due to high energy penalty. Hence researchers are concentrating on developing non-aqueous solvents like ionic liquids, CO2-binding organic liquids, nanoparticle hybrid materials and microencapsulated sorbents to minimize the energy consumption for carbon capture. This research aims to develop a novel and efficient approach by encapsulating sorbents to capture CO2 in a cold environment. The conventional emulsion technique was selected for the microcapsule formulation by using 2-amino-2-methyl-1-propanol (AMP) as the core sorbent and silicon dioxide (SiO2) as the shell. This paper reports the findings on the formulated microcapsules including key formulation parameters, microstructure, size distribution and thermal cycling stability. Furthermore, the effects of microcapsule quality and absorption temperature on the CO2 loading capacity of the microcapsules were investigated using a self-developed pressure decay method. The preliminary results have shown that the AMP microcapsules are promising to replace conventional sorbents.Engineering and Physical Sciences Research Council (EPSRC

Signatures of the post-hydration heating of highly aqueously altered CM carbonaceous chondrites and implications for interpreting asteroid sample returns

The CM carbonaceous chondrites have all been aqueously altered, and some of them were subsequently heated in a parent body environment. Here we have sought to understand the impact of short duration heating on a highly aqueously altered CM through laboratory experiments on Allan Hills (ALH) 83100. Unheated ALH 83100 contains 83 volume per cent serpentine within the fine-grained matrix and altered chondrules. The matrix also hosts grains of calcite and dolomite, which are often intergrown with tochilinite, Fe(Ni) sulphides (pyrrhotite, pentlandite), magnetite and organic matter. Some of the magnetite formed by replacement of Fe(Ni) sulphides that were accreted from the nebula. Laboratory heating to 400 °C has caused partial dehydroxylation of serpentine and loss of isotopically light oxygen leading to an increase in bulk δ18O and fall in Δ17O. Tochilinite has decomposed to magnetite, whereas carbonates have remained unaltered. With regards to infrared spectroscopy (4000–400 cm-1; 2.5–25 µm), heating to 400 °C has resulted in decreased emissivity (increased reflectance), a sharper and more symmetric OH band at 3684 cm-1 (2.71 µm), a broadening of the Si—O stretching band together with movement of its minimum to longer wavenumbers, and a decreasing depth of the Mg—OH band (625 cm-1; 16 µm). The Si—O bending band is unmodified by mild heating. With heating to 800 °C the serpentine has fully dehydroxylated and recrystallized to ∼Fo60/70 olivine. Bulk δ18O has further increased and Δ17O decreased. Troilite and pyrrhotite have formed, and recrystallization of pentlandite has produced Fe,Ni metal. Calcite and dolomite were calcined at ∼700 °C and in their place is an un-named Ca-Fe oxysulphide. Heating changes the structural order of organic matter so that Raman spectroscopy of carbon in the 800 °C sample shows an increased (D1 + D4) proportional area parameter. The infrared spectrum of the 800 °C sample confirms the abundance of Fe-bearing olivine and is very similar to the spectrum of naturally heated stage IV CM Pecora Escarpment 02010. The temperature-related mineralogical, chemical, isotopic and spectroscopic signatures defined in ALH 83100 will help to track the post-hydration thermal histories of carbonaceous chondrite meteorites, and samples returned from the primitive asteroids Ryugu and Bennu

Application of EQ3/6 to modeling of nuclear waste glass behavior in a tuff repository

Modeling of glass degradation based on sound geochemical principles appears to be possible with revisions to EQ3/6. Realistic source terms for several repository scenarios may be generated with such a model. One scenario which appears very likely and which is also amenable to modeling using EQ3/6 is that in which an intact but perforated canister holds water in contact with waste glass. The water overflows continuously or periodically, allowing radionuclides to come in contact with repository rock. This isolated-type scenario will be the first realistic modeling effort because it limits complex interactions between rock and glass. However, EQ3/6 modeling should be possible even for very complicated scenarios if sufficient experimental data are available on rates and thermodynamics. This will be the limiting factor in progress toward modeling the complete system