Numerical simulation of double-diffusion driven convective flow and rock alteration in three-dimensional fluid-saturated geological fault zones

Numerical methods are used to simulate the double-diffusion driven convective pore-fluid flow and rock alteration in three-dimensional fluid-saturated geological fault zones. The double diffusion is caused by a combination of both the positive upward temperature gradient and the positive downward salinity concentration gradient within a three-dimensional fluid-saturated geological fault zone, which is assumed to be more permeable than its surrounding rocks. In order to ensure the physical meaningfulness of the obtained numerical solutions, the numerical method used in this study is validated by a benchmark problem, for which the analytical solution to the critical Rayleigh number of the system is available. The theoretical value of the critical Rayleigh number of a three-dimensional fluid-saturated geological fault zone system can be used to judge whether or not the double-diffusion driven convective pore-fluid flow can take place within the system. After the possibility of triggering the double-diffusion driven convective pore-fluid flow is theoretically validated for the numerical model of a three-dimensional fluid-saturated geological fault zone system, the corresponding numerical solutions for the convective flow and temperature are directly coupled with a geochemical system. Through the numerical simulation of the coupled system between the convective fluid flow, heat transfer, mass transport and chemical reactions, we have investigated the effect of the double-diffusion driven convective pore-fluid flow on the rock alteration, which is the direct consequence of mineral redistribution due to its dissolution, transportation and precipitation, within the three-dimensional fluid-saturated geological fault zone system. (c) 2005 Elsevier B.V. All rights reserved.

Pore structure characterisation of pillared clays using a modified MP method

The data of nitrogen adsorption on pillared clays (PILC) are converted to comparison plots (t-plots) to derive their pore size distribution (PSD). As in the MP method, the surface area of a group of pores having similar pore sizes is calculated from the slopes of tangent lines at two succeeding points on a comparison plot. By the modified MP method in this work, the tangent line is extrapolated to the adsorption axis on the t-plot, and the difference between intercepts is used to obtain the volume of the group of pores. From the information of surface area and pore volume, the average width of the pore group can be calculated and hence the PSDs of PILCs are obtained by carrying out such calculation procedures from high to low t. With this method, PSDs of several pillared clays are calculated over a wide pore size range, from micropores to mesopores. It is found that the modified MP method could result in the underestimation of the width of ultramicropores due to the enhancement in adsorption energy in these pores. Nevertheless, the method can be very useful in calculating the surface area and pore volume, as well as a mean width of these pores. For super-micropores and mesopores, pore size can also be underestimated, due to deviation of the pore shape from a slit. The principles of the improved MP method, as well as problems associated with it are thoroughly discussed in this paper. In general, this modified method provides practically meaningful results which are consistent with the pore dimension obtained from powder X-ray diffraction measurements, but involves no complicated theoretical treatment or assumptions.

Persistent activation of Akt or ERK prevents the toxicity induced by saturated and polyunsaturated fatty acids in RINm5F beta-cells

The aim of this study was to investigate whether the toxicity of saturated and polyunsaturated fatty acids (PUFA) on RINm5F cells is related to the phosphorylation state of Akt, ERK and PKC delta. The regulation of these kinases was compared in three experimental designs: (a) 4 h-exposure, (b) 4 h-exposure and a subsequent withdrawn of the FA for a 20 h period and (c) 24 h-exposure. Saturated and PUFA were toxic to RINm5F cells even at low concentrations. Also, evidence is provided for a late (i.e. the effect only appeared hours after the treatment) and a persistent regulation (i.e. maintenance of the effect for several hours) of Akt, ERK and PKC delta phosphorylation by the FA. Late activation of PKC delta seems important for palmitate cytotoxicity. Persistent activation of the survival proteins Akt and ERK by stearate, oleate and arachidonate might play an important role to prevent the toxic effect of posterior PKC delta activation. The results shown may explain why a short-period exposure to FA is not enough to induce cytotoxicity in pancreatic beta-cells, since survival pathways are activated. Besides, when this activation is persistent, it may overcome a posterior induction of death pathways. (c) 2008 Elsevier Ltd. All rights reserved.

Engineering the structures of nanoporous clays with micelles of alkyl polyether surfactants

Composite clay nanostructures (CCNs) were observed in intercalating Laponite clay with alumina in the presence of alkyl polyether surfactants which contain hydrophobic alkyl chains and ether groups. Such nanostructured clays are highly porous solids consisting of randomly orientated clay platelets intercalated with alumina nanoparticles. The pores in the product solids are larger than the dimension of the surfactant molecules, ranging from 2 to 10 nm. This suggests that the micelles of the surfactant molecules, rather than the molecules, act as templates in the synthesis. Interestingly, it is found that the size of the framework pores was directly proportional to the amount of the surfactants in terms of moles, but shows no evident dependence on the size of the surfactant molecules. Broad pore size distributions were observed for the product CCNs. This study demonstrates that introducing surfactants in the pillaring process of clays is a powerful strategy for tailoring the pore structures of nanoporous clays. With this new technique, it is possible to design and engineer such composite clay nanostructures with desired pore and surface properties by the proper choice of surfactant amounts and preparation conditions.

Characterization of pore structure and coordination of titanium in TiO2 and SiO2-TiO2 sol-pillared clays

Titania sol-pillared clay (TiO2 PILC) and silica-titania sol-pillared clay (SiO2-TiO2 PILC) were synthesized by the sol-gel method. Supercritical drying (SCD) and treatment with quaternary ammonium surfactants were used to tailor the pore structure of the resulting clay. It was found that SCD approach increased the external surface area of the PILCs dramatically and that treatment with surfactants could be used to tailor pore size because the mesopore formation in the galleries between the clay layers follows the templating mechanism as observed in the synthesis of MCM-41 materials. Highly mesoporous solids were thus obtained. In calcined TiO2 PILC, ultrafine crystallites in anatase phase, which are active for photocatalytic oxidation of organics, were observed. In SiO2-TiO2 PILCs and their derivatives, titanium was highly dispersed in the matrix of silica and no crystal phase was observed. The highly dispersed titanium sites are good catalytic centers for selective oxidation of organic compounds. (C) 2001 Academic Press.

Molecular engineered porous clays using surfactants

Quaternary ammonium surfactants were used to control the pore structure of bentonite intercalated with a mixed hydro-sol of silicon and titanium. Porous clay heterostructures of alumina and laponite were prepared in the presence of polyethylene oxide (PEO) surfactants. Participation of the surfactants in the synthesis results in significant changes in the structure of porous clay products. Surfactants are involved in different mechanisms, In the case of bentonite, the mean size of the framework pores was directly proportional to the chain length of the quaternary ammonium surfactants. This indicates a molecular templating mechanism, similar to that observed in the synthesis of MCM41. However, in the case of laponite, the size and volume of the mesopores were related to the amount of PEO surfactants used. By using an appropriate surfactant, we can obtain highly porous clays with various pore structures. Introducing surfactants during intercalation is an efficient strategy for the molecular engineering of porous clay adsorbents and catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.

Porous solids from layered clays by combined pillaring and templating approaches

The pore structure formation in bentonite, pillared with a mixed sol of silicon and titanium hydroxides and treated subsequently with quaternary ammonium surfactants, is investigated. The surfactant micelles act as a template, similar to their role in MCM41 synthesis. Because both the surfactant micelles and the sol particles are positively charged, it is greatly favorable for them to form meso-phase assembles in the galleries between the clay layers that bear negative charges. Besides, the sol particles do not bond the clay layers strongly as other kinds of pillar precursors do, so that the treatment with surfactants can result in radical structure changes in sol-pillared clays. This allows us to tailor the pore structure of these porous clays by choice of surfactant. The surfactant treatment also results in profound increases in porosity and improvement in thermal stability. Therefore, the product porous clays have great potential to be Used to deal with large molecules or at high operating temperatures. We also found that titanium in these samples is highly dispersed in the silica matrix rather than existing in the form of small particles of pure titania. Such highly dispersed Ti active centers may offer excellent activities for catalytic oxidation reactions such as alkanes into alcohols and ketones.

Hydraulic conductivity in response to exchangeable sodium percentage and solution salt concentration

Hydraulic conductivity is determined in laboratory assays to estimate the flow of water in saturated soils. However, the results of this analysis, when using distilled or deionized water, may not correspond to field conditions in soils with high concentrations of soluble salts. This study therefore set out to determine the hydraulic conductivity in laboratory conditions using solutions of different electrical conductivities in six soils representative of the State of Pernambuco, with the exchangeable sodium percentage adjusted in the range of 5-30%. The results showed an increase in hydraulic conductivity with both decreasing exchangeable sodium percentage and increasing electrical conductivity in the solution. The response to the treatments was more pronounced in soils with higher proportion of more active clays. Determination of hydraulic conductivity in laboratory is routinely performed with deionized or distilled water. However, in salt affected soils, these determinations should be carried out using solutions of electrical conductivity different from 0 dS m-1, with values close to those determined in the saturation extracts.

Lime mortars with heat treated clays and ceramic waste: A review

The formulation and use of lime mortars with ceramic particles has, in the past, been a very common technique. Knowledge of such used techniques and materials is fundamental for the successful rehabilitation and conservation of the built heritage. The durability that these mortars have shown encourages the study of the involved mechanisms, so that they may be adapted to the current reality. The considerable amount of waste from old ceramics factories which is sent for disposal might present an opportunity for the production of reliable improved lime mortars. In this paper a number of studies that characterize old building mortars containing ceramic fragments are reviewed. The most important research undertaken on laboratory prepared mortars with several heat treated clays types is presented, specifically with incorporated ceramic waste. Some studies on the pozzolanicity of heat treated clays are examined and the heating temperatures that seem most likely to achieve pozzolanicity are presented. It was verified that some heating temperatures currently used by ceramic industries might correspond to the temperatures that will achieve pozzolanicity.

Conversion of Cn-unsaturated into Cn-2-saturated LCFA can occur uncoupled from methanogenesis in anaerobic bioreactors

Fat, oils, and grease present in complex wastewater can be readily converted to methane, but the energy potential of these compounds is not always recyclable, due to incomplete degradation of long chain fatty acids (LCFA) released during lipids hydrolysis. Oleate (C18:1) is generally the dominant LCFA in lipid-containing wastewater, and its conversion in anaerobic bioreactors results in palmitate (C16:0) accumulation. The reason why oleate is continuously converted to palmitate without further degradation via β-oxidation is still unknown. In this work, the influence of methanogenic activity in the initial conversion steps of unsaturated LCFA was studied in 10 bioreactors continuously operated with saturated or unsaturated C16- and C18-LCFA, in the presence or absence of the methanogenic inhibitor bromoethanesulfonate (BrES). Saturated Cn-2-LCFA accumulated both in the presence and absence of BrES during the degradation of unsaturated Cn-LCFA, and represented more than 50\% of total LCFA. In the presence of BrES further conversion of saturated intermediates did not proceed, not even when prolonged batch incubation was applied. As the initial steps of unsaturated LCFA degradation proceed uncoupled from methanogenesis, accumulation of saturated LCFA can be expected. Analysis of the active microbial communities suggests a role for facultative anaerobic bacteria in the initial steps of unsaturated LCFA biodegradation. Understanding this role is now imperative to optimize methane production from LCFA.

Derivation of soil-specific streaming potential electrical parameters from hydrodynamic characteristics of partially saturated soils

Water movement in unsaturated soils gives rise to measurable electrical potential differences that are related to the flow direction and volumetric fluxes, as well as to the soil properties themselves. Laboratory and field data suggest that these so-called streaming potentials may be several orders of magnitudes larger than theoretical predictions that only consider the influence of the relative permeability and electrical conductivity on the self potential (SP) data. Recent work has improved predictions somewhat by considering how the volumetric excess charge in the pore space scales with the inverse of water saturation. We present a new theoretical approach that uses the flux-averaged excess charge, not the volumetric excess charge, to predict streaming potentials. We present relationships for how this effective excess charge varies with water saturation for typical soil properties using either the water retention or the relative permeability function. We find large differences between soil types and the predictions based on the relative permeability function display the best agreement with field data. The new relationships better explain laboratory data than previous work and allow us to predict the recorded magnitudes of the streaming potentials following a rainfall event in sandy loam, whereas previous models predict values that are three orders of magnitude too small. We suggest that the strong signals in unsaturated media can be used to gain information about fluxes (including very small ones related to film flow), but also to constrain the relative permeability function, the water retention curve, and the relative electrical conductivity function.

Optimal 3-T MRI for depiction of the finger A2 pulley: comparison between T1-weighted, fat-saturated T2-weighted and gadolinium-enhanced fat-saturated T1-weighted sequences

OBJECTIVE: To compare three spin-echo sequences, transverse T1-weighted (T1WI), transverse fat-saturated (FS) T2-weighted (T2WI), and transverse gadolinium-enhanced (Gd) FS T1WI, for the visualisation of normal and abnormal finger A2 pulley with magnetic resonance (MR) imaging at 3 tesla (T). MATERIALS AND METHODS: Sixty-three fingers from 21 patients were consecutively investigated. Two musculoskeletal radiologists retrospectively compared all sequences to assess the visibility of normal and abnormal A2 pulleys and the presence of motion or ghost artefacts. RESULTS: Normal and abnormal A2 pulleys were visible in 94% (59/63) and 95% (60/63) on T1WI sequences, in 63% (40/63) and 60% (38/63) on FS T2WI sequences, and in 87% (55/63) and 73% (46/63) on Gd FS T1WI sequences when read by the first and second observer, respectively. Motion and ghost artefacts were higher on FS T2WI sequences. Seven among eight abnormal A2 pulleys were detected, and were best depicted with Gd FS T1WI sequences in 71% (5/7) and 86% (6/7) by the first and the second observer, respectively. CONCLUSION: In 3-T MRI, the comparison between transverse T1WI, FS T2WI, and Gd FS T1WI sequences shows that transverse T1WI allows excellent depiction of the A2 pulley, that FS T2WI suffers from a higher rate of motion and ghost artefacts, and transverse Gd FS T1WI is the best sequence for the depiction of abnormal A2 pulley.

Athletic injuries of the extensor carpi ulnaris subsheath: MRI findings and utility of gadolinium-enhanced fat-saturated T1-weighted sequences with wrist pronation and supination

Purpose: To report the magnetic resonance imaging (MRI) findings in athletic injuries of the extensor carpi ulnaris (ECU) subsheath, assessing the utility of gadolinium-enhanced (Gd) fat-saturated (FS) T1-weighted sequences with wrist pronation and supination. Methods and Materials: Sixteen patients (13 males, 3 females; mean age 30.3 years) with athletic injuries of the ECU subsheath sustained between January 2003 and June 2009 were included in this retrospective study. Initial and follow‑up 1.5-T wrist MRIs were performed with transverse T1-weighted and STIR sequences in pronation, and Gd FS T1-weighted sequences with wrist pronation and supination. Two radiologists assessed the type of injury (A to C), ECU tendon stability, associated lesions and rated pulse sequences using a three-point scale: 1 = poor, 2 = good and 3 = excellent. Results: Gd-enhanced FS T1-weighted transverse sequences in supination (2.63) and pronation (2.56) were most valuable, compared with STIR (2.19) and T1 weighted (1.94). Nine type A, one type B and six type C injuries were found. There were trends towards diminution in size, signal intensity and enhancement of associated pouches on follow‑up MRI and tendon stabilisation within the ulnar groove. Conclusion: Gd-enhanced FS T1-weighted sequences with wrist pronation and supination are most valuable in assessing and follow‑up athletic injuries of the ECU subsheath on 1.5-T MRI.