An improved understanding about CO2 EOR and CO2 storage in liquid-rich shale reservoirs

During the past decade, enhanced oil recovery (EOR) by CO2 in shale oils has received substantial attention. In shale oil reservoirs, CO2 diffusion into the resident oil has been considered as the dominant interaction between the CO2 in fractures and the oil in the matrices. CO2 diffusion will lead to oil swelling and improvement in oil viscosity. However, despite two-way mass transfer during CO2 EOR in conventional oil reservoirs, one-way mass transfer into shale oils saturated with live oils is controlled by an additional transport mechanism, which is the liberation of light oil components in the form of a gaseous new-phase. This in-situ gas formation could generate considerable swelling, which could improve the oil recovery significantly. This mechanism has been largely overlooked in the past. This study is aimed to better understand the role of this evolving gas phase in improving hydrocarbon recovery. Taking account of Bakken shale oil reservoir data, numerical simulations were performed to identify efficiencies of EOR by CO2 at the laboratory and field scales. Equation of state parameters between CO2 and oil components were adjusted to optimize the calculations and a sensitivity analysis was performed to identify the role of gas formation and consequent EOR efficiencies. At the laboratory scale, in-situ gas formation can increase oil recovery by 20% depending on the amount of gas saturation. Also, the CO2 storage capacity of the shale matrix can be enhanced by 25%, due to CO2 trapping in the gas phase. At the field scale, an additional oil recovery of 9.1% could be attained, which is notably higher than previous studies where this gas evolution mechanism was ignored. Furthermore, the results suggest that a six-weeks huff period would be sufficient to achieve substantial EOR if this new mechanism is incorporated. On the other hand, the produced fluid in the early period was primarily composed of CO2, which would make it available for subsequent cycles. The produced gas of the well under CO2 EOR was used in an adjacent well, which resulted in similar additional oil recovery and hence, impurities in CO2 injection stream would not undermine efficiency of this EOR method. The results of this study, therefore, could potentially be used to substantially improve the evaluations of CO2 EOR in liquid-rich shale reservoirs

SNARE-mediated membrane fusion trajectories derived from force-clamp experiments.

Fusion of lipid bilayers is usually prevented by large energy barriers arising from removal of the hydration shell, formation of highly curved structures, and, eventually, fusion pore widening. Here, we measured the force-dependent lifetime of fusion intermediates using membrane-coated silica spheres attached to cantilevers of an atomic-force microscope. Analysis of time traces obtained from force-clamp experiments allowed us to unequivocally assign steps in deflection of the cantilever to membrane states during the SNARE-mediated fusion with solid-supported lipid bilayers. Force-dependent lifetime distributions of the various intermediate fusion states allowed us to propose the likelihood of different fusion pathways and to assess the main free energy barrier, which was found to be related to passing of the hydration barrier and splaying of lipids to eventually enter either the fully fused state or a long-lived hemifusion intermediate. The results were compared with SNARE mutants that arrest adjacent bilayers in the docked state and membranes in the absence of SNAREs but presence of PEG or calcium. Only with the WT SNARE construct was appreciable merging of both bilayers observed

Evidence for the super Tonks-Girardeau gas

We provide evidence in support of a recent proposal by Astrakharchik at al. for the existence of a super Tonks-Girardeau gas-like state in the attractive interaction regime of quasi-one-dimensional Bose gases. We show that the super Tonks-Giradeau gas-like state corresponds to a highly-excited Bethe state in the integrable interacting Bose gas for which the bosons acquire hard-core behaviour. The gas-like state properties vary smoothly throughout a wide range from strong repulsion to strong attraction. There is an additional stable gas-like phase in this regime in which the bosons form two-body bound states behaving like hard-core bosons.Comment: 10 pages, 1 figure, 2 tables, additional text on the stability of the super T-G gas-like stat

Ground-state properties of the attractive one-dimensional Bose-Hubbard model

We study the ground state of the attractive one-dimensional Bose-Hubbard model, and in particular the nature of the crossover between the weak interaction and strong interaction regimes for finite system sizes. Indicator properties like the gap between the ground and first excited energy levels, and the incremental ground-state wavefunction overlaps are used to locate different regimes. Using mean-field theory we predict that there are two distinct crossovers connected to spontaneous symmetry breaking of the ground state. The first crossover arises in an analysis valid for large L with finite N, where L is the number of lattice sites and N is the total particle number. An alternative approach valid for large N with finite L yields a second crossover. For small system sizes we numerically investigate the model and observe that there are signatures of both crossovers. We compare with exact results from Bethe ansatz methods in several limiting cases to explore the validity for these numerical and mean-field schemes. The results indicate that for finite attractive systems there are generically three ground-state phases of the model.Comment: 17 pages, 12 figures, Phys.Rev.B(accepted), minor changes and updated reference

Integrable models and quantum spin ladders: comparison between theory and experiment for the strong coupling ladder compounds

(abbreviated) This article considers recent advances in the investigation of the thermal and magnetic properties of integrable spin ladder models and their applicability to the physics of real compounds. The ground state properties of the integrable two-leg spin-1/2 and the mixed spin-(1/2,1) ladder models at zero temperature are analyzed by means of the Thermodynamic Bethe Ansatz. Solving the TBA equations yields exact results for the critical fields and critical behaviour. The thermal and magnetic properties of the models are investigated in terms of the recently introduced High Temperature Expansion method, which is discussed in detail. It is shown that in the strong coupling limit the integrable spin-1/2 ladder model exhibits three quantum phases: (i) a gapped phase in the regime $H<H_{c1}$, (ii) a fully polarised phase for $H>H_{c2}$, and (iii) a Luttinger liquid magnetic phase in the regime $H_{c1}<H<H_{c2}$. The critical behaviour in the vicinity of the critical points is of the Pokrovsky-Talapov type. The temperature-dependent thermal and magnetic properties are directly evaluated from the exact free energy expression and compared to known experimental results for a range of strong coupling ladder compounds. Similar analysis of the mixed spin-(1/2,1) ladder model reveals a rich phase diagram, with a 1/3 and a full saturation magnetisation plateau within the strong antiferromagnetic rung coupling regime. For weak rung coupling, the fractional magnetisation plateau is diminished and a new quantum phase transition occurs. The phase diagram can be directly deduced from the magnetisation curve obtained from the exact result derived from the HTE. The thermodynamics of the spin-orbital model with different single-ion anisotropies is also investigated.Comment: 90 pages, 33 figures, extensive revisio

A collective effort to identify and quantify geo-energy risks

The increasing global demand for energy and the imminent need to reduce carbon emissions in our planet has led mankind to find new solutions. Some in the energy industry have taken special interest in geothermal reservoirs, a resource with the potential to provide large amounts of renewable energy. Meanwhile, the storage of carbon dioxide in underground geological formations presents a fantastic opportunity to discard CO2 and mitigate global warming. This study links efforts from academic institutions, industry energy operators, industrial partners and research institutes to answer fundamental scientific questions that can help us understand the subsurface and generate better exploitation practices. We examine the geology of reservoirs used for geothermal energy extraction and carbon dioxide capture. We use a combination of field geology, photogrammetry, mineral analysis and experimental rock mechanics to understand fracture networks and fluid flow paths of two geologically diverse reservoirs in Europe: 1) the Hengill geothermal system in south-west Iceland, and 2) the Carnmenellis granite geothermal system in Cornwall (UK). These results aim to provide experimental data to refine numerical models predicting fluid flow and contribute to the quantification of the associated risks of exploiting the subsurface

Effect of solution saturation state and temperature on diopside dissolution

Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields [Formula: see text] where the Mg-H exchange coefficient, n = 1.39, the apparent activation energy, E(a )= 332 kJ mol(-1), and the apparent rate constant, k = 10(41.2 )mol diopside cm(-2 )s(-1). Fits to the data with the pit nucleation model suggest that diopside dissolution proceeds through retreat of steps developed by nucleation of pits created homogeneously at the mineral surface or at defect sites, where homogeneous nucleation occurs at lower degrees of saturation than defect-assisted nucleation. Rate expressions for each mechanism (i) were fit to [Formula: see text] where the step edge energy (α) for homogeneously nucleated pits were higher (275 to 65 mJ m(-2)) than the pits nucleated at defects (39 to 65 mJ m(-2)) and the activation energy associated with the temperature dependence of site density and the kinetic coefficient for homogeneously nucleated pits (E(b-homogeneous )= 2.59 × 10(-16 )mJ K(-1)) were lower than the pits nucleated at defects (E(b-defect assisted )= 8.44 × 10(-16 )mJ K(-1))

On the global hydration kinetics of tricalcium silicate cement

We reconsider a number of measurements for the overall hydration kinetics of tricalcium silicate pastes having an initial water to cement weight ratio close to 0.5. We find that the time dependent ratio of hydrated and unhydrated silica mole numbers can be well characterized by two power-laws in time, $x/(1-x)\sim (t/t_x)^\psi$. For early times $t < t_x$ we find an `accelerated' hydration ($\psi = 5/2$) and for later times $t > t_x$ a `deaccelerated' behavior ($\psi = 1/2$). The crossover time is estimated as $t_x \approx 16 hours$. We interpret these results in terms of a global second order rate equation indicating that (a) hydrates catalyse the hydration process for $t<t_x$, (b) they inhibit further hydration for $t > t_x$ and (c) the value of the associated second order rate constant is of magnitude 6x10^{-7} - 7x10^{-6} liter mol^{-1} s^{-1}. We argue, by considering the hydration process actually being furnished as a diffusion limited precipitation that the exponents $\psi = 5/2$ and $\psi = 1/2$ directly indicate a preferentially `plate' like hydrate microstructure. This is essentially in agreement with experimental observations of cellular hydrate microstructures for this class of materials.Comment: RevTeX macros, 6 pages, 4 postscript figure

Experimental determination of the solubility product of dolomite at 50–253 °C

The ‘dolomite problem’, the scarcity of present-day dolomite formation near the Earth’s surface, has attracted much attention over the past century. Solving this problem requires having reliable data on the stability and kinetics of formation of this mineral. Toward this goal, the solubility of natural dolomite (CaMg(CO3)2) has been measured from 50 to 253 °C in 0.1 mol/kg NaCl solutions using a hydrogen electrode concentration cell (HECC). The obtained apparent solubility products (Kapp-sp-dol), for the reaction: CaMg(CO3)2 = Ca2+ + Mg2+ + 2CO32−, were extrapolated to infinite dilution to generate the solubility product constants for this reaction (Ksp°-dol). The derived equilibrium constants were fit and can be accurately described by log10 Ksp°-dol = a + b/T (K) + cT (K) where a = 17.502, b = −4220.119 and c = −0.0689. This equation and its first and second derivatives with respect to T were used together with corresponding aqueous species properties to calculate the revised standard state thermodynamic properties of dolomite at 25 °C and 1 bar, yielding a Gibbs energy of formation (ΔfG298.15∘) equal to −2160.9 ± 2 kJ/mol, (log10 Ksp°-dol = −17.19 ± 0.3); an enthalpy of formation (ΔfH298.15∘) of −2323.1 ± 2 kJ/mol, an entropy (S298.15∘) of 156.9 ± 2 J/mol/K and heat capacity (Cp298.15∘) of 154.2 ± 2 J/mol/K (uncertainties are 3σ). The dolomite solubility product derived in this study is nearly identical to that computed using SUPCRT92 (Johnson et al., 1992) at 200 °C, but about one order of magnitude higher at 50 and 25 °C, suggesting that dolomite may be somewhat less stable than previously assumed at ambient temperatures

Accelerated recent warming and temperature variability over the past eight centuries in the central Asian Altai from blue intensity in tree rings

Funding: National Science Foundation (NSF). Grant Number: 1737788 and NOAA Climate and Global Change Postdoc Fellow Program. Grant Number: NA18NWS4620043B.Warming in Central Asia has been accelerating over the past three decades and is expected to intensify through the end of this century. Here, we develop a summer temperature reconstruction for western Mongolia spanning eight centuries (1269–2004 C.E.) using delta blue intensity measurements from annual rings of Siberian larch. A significant cooling response is observed in the year following major volcanic events and up to five years post-eruption. Observed summer temperatures since the 1990s are the warmest over the past eight centuries, an observation that is also well captured in Coupled Model Intercomparison Project (CMIP5) climate model simulations. Projections for summer temperature relative to observations suggest further warming of between ∼3°C and 6°C by the end of the century (2075–2099 cf. 1950–2004) under the representative concentration pathways 4.5 and 8.5 (RCP4.5 and RCP8.5) emission scenarios. We conclude that projected future warming lies beyond the range of natural climate variability for the past millennium as estimated by our reconstruction.Publisher PDFPeer reviewe