Characteristic water contents of a fine-grained soil-water system

This paper critically appraises the limitations of the liquid-limit water content of clayey soils determined conventionally either by percussion cup or by the cone penetration method. It is shown that the conventional liquid limit and plastic limit are arbitrary, strength-based water contents and that they cannot represent the plasticity limits, and that the state of the soil-water system at the conventional liquid limit does not correspond to a stress-free reference state. The present investigation identifies three characteristic limiting water contents for a soil-water system which have well-defined, unique mechanisms controlling them, namely the free swell limit, settling limit and shrinkage limit. Simple procedures for the determination of the free swell limit and settling limit of natural soils are presented. The settling limit is shown to be the 'real liquid limit' of any clayey soil. With a number of experimental illustrations, it is clearly shown that the settling limit represents the maximum water-holding capacity of clayey soils and that it corresponds to the stress-free reference state.

Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste

Bentonite clay is identified as potential buffer in deep geological repositories (DGR) that store high level radioactive wastes (HLW) as the expansive clay satisfies the expected mechanical and physicochemical functions of the buffer material. In the deep geological disposal of HLW, iodine-129 is one of the significant nuclides, attributable to its long half-life (half life 1⁄4 1:7 × 107 years). However, the negative charge on the basal surface of bentonite particles precludes retention of iodide anions. To render the bentonite effective in retaining hazardous iodide species in DGR, improvement of the anion retention capacity of bentonite becomes imperative. The iodide retention capac-ity of bentonite is improved by admixing 10 and 20% Ag-kaolinite (Ag-K) with bentonite (B) on a dry mass basis. The present study produced Ag-kaolinite by heating silver nitrate-kaolinite mixes at 400°C. Marginal release of iodide retained by Ag-kaolinite occurred under extreme acidic (pH 1⁄4 2:5) and alkaline (pH 1⁄4 12:5) conditions. The swell pressure and iodide etention results of the B-Ag-K specimens bring out that mixing Ag-K with bentonite does not chemically modify the expansive clay; the mixing is physical in nature and Ag-K presence only contributes to iodide retention of the admixture. DOI: 10.1061/(ASCE)HZ.2153-5515.0000121. © 2012 American Society of Civil Engineers.

Induced swelling of kaolinitic soil in alkali solution

Unexpected swelling induced in foundation soils can cause distress to structures founded on them. In this paper, the swelling of kaolinitic soils due to interaction with alkali solution has been reported. The induced swelling is attributed to the formation of new minerals, which has been confirmed by X-ray diffraction patters and SEM studies. To understand the effect of alkali concentration and duration of interaction, two series of consolidation experiments have been carried out. In series 1, the specimen were remoulded with water and inundated with alkali solutions and in series 2, the specimen were remoulded and inundated with same alkali solutions. A steep compression during loading cycle and no abnormal swelling during unloading cycle has been noticed for the specimen remoulded with water and inundated with 1 N NaOH solutions. The steep compression is due to the segregation or break down of clay minerals due to alkali interactions. In case of specimen inundated with 4 N NaOH solutions, abnormal swelling has been observed during unloading cycle of the consolidation test. New minerals are formed on interaction of soil with 4 N solution as confirmed by X-ray diffraction patterns. These minerals are known to have very fine pores and possess high water holding capacity. The differences in the amount of swelling of samples remoulded with water and remoulded with alkali solution are due to variations in the concentration of alkali and duration of interaction.

Parameter estimation of a two-horizon soil profile by combining crop canopy and surface soil moisture observations using GLUE

Estimation of soil parameters by inverse modeling using observations on either surface soil moisture or crop variables has been successfully attempted in many studies, but difficulties to estimate root zone properties arise when heterogeneous layered soils are considered. The objective of this study was to explore the potential of combining observations on surface soil moisture and crop variables - leaf area index (LAI) and above-ground biomass for estimating soil parameters (water holding capacity and soil depth) in a two-layered soil system using inversion of the crop model STICS. This was performed using GLUE method on a synthetic data set on varying soil types and on a data set from a field experiment carried out in two maize plots in South India. The main results were (i) combination of surface soil moisture and above-ground biomass provided consistently good estimates with small uncertainity of soil properties for the two soil layers, for a wide range of soil paramater values, both in the synthetic and the field experiment, (ii) above-ground biomass was found to give relatively better estimates and lower uncertainty than LAI when combined with surface soil moisture, especially for estimation of soil depth, (iii) surface soil moisture data, either alone or combined with crop variables, provided a very good estimate of the water holding capacity of the upper soil layer with very small uncertainty whereas using the surface soil moisture alone gave very poor estimates of the soil properties of the deeper layer, and (iv) using crop variables alone (else above-ground biomass or LAI) provided reasonable estimates of the deeper layer properties depending on the soil type but provided poor estimates of the first layer properties. The robustness of combining observations of the surface soil moisture and the above-ground biomass for estimating two layer soil properties, which was demonstrated using both synthetic and field experiments in this study, needs now to be tested for a broader range of climatic conditions and crop types, to assess its potential for spatial applications. (C) 2012 Elsevier B.V. All rights reserved.

Pseudo-Static and Pseudo-Dynamic Stability Analysis of Tailings Dam Under Seismic Conditions

In this paper the seismic slope stability analyses are performed for a typical section of 44 m high water retention type tailings earthen dam located in the eastern part of India, using both the conventional pseudo-static and recent pseudo-dynamic methods. The tailings earthen dam is analyzed for different upstream conditions of reservoir like filled up with compacted and non-compacted dumped waste materials with different water levels of the pond tailings portion. Phreatic surface is generated using seepage analysis in geotechnical software SEEP/W and that same is used in the pseudo-static and pseudo-dynamic analyses to make the approach more realistic. The minimum values of factor of safety using pseudo-static and pseudo-dynamic method are obtained as 1.18 and 1.09 respectively for the chosen seismic zone in India. These values of factor of safety show clearly the demerits of conventional pseudo-static analysis compared to recent pseudo-dynamic analysis, where in addition to the seismic accelerations, duration, frequency of earthquake, body waves traveling during earthquake and amplification effects are considered.

Effect of catchment characteristics on the relationship between past discharge and the power law recession coefficient

This study concerns the relationship between the power law recession coefficient k (in - dQ/dt = kQ(alpha), Q being discharge at the basin outlet) and past average discharge Q(N) (where N is the temporal distance from the center of the selected time span in the past to the recession peak), which serves as a proxy for past storage state of the basin. The strength of the k-Q(N) relationship is characterized by the coefficient of determination R-N(2), which is expected to indicate the basin's ability to hold water for N days. The main objective of this study is to examine how R-N(2) value of a basin is related with its physical characteristics. For this purpose, we use streamflow data from 358 basins in the United States and selected 18 physical parameters for each basin. First, we transform the physical parameters into mutually independent principal components. Then we employ multiple linear regression method to construct a model of R-N(2) in terms of the principal components. Furthermore, we employ step-wise multiple linear regression method to identify the dominant catchment characteristics that influence R-N(2) and their directions of influence. Our results indicate that R-N(2) is appreciably related to catchment characteristics. Particularly, it is noteworthy that the coefficient of determination of the relationship between R-N(2) and the catchment characteristics is 0.643 for N = 45. We found that topographical characteristics of a basin are the most dominant factors in controlling the value of R-N(2). Our results may be suggesting that it is possible to tell about the water holding capacity of a basin by just knowing about a few of its physical characteristics. (C) 2015 Elsevier B.V. All rights reserved.

Combined Effect of Cryogel Matrix and Temperature-Reversible Soluble-Insoluble Polymer for the Development of in Vitro Human Liver Tissue

Hepatic cell culture on a three-dimensional (3D) matrix or as a hepatosphere appears to be a promising in vitro biomimetic system for liver tissue engineering applications. In this study, we have combined the concept of a 3D scaffold and a spheroid culture to develop an in vitro model to engineer liver tissue for drug screening. We have evaluated the potential of poly(ethylene glycol)-alginate-gelatin (PAG) cryogel matrix for in vitro culture of human liver cell lines. The synthesized cryogel matrix has a flow rate of 7 mL/min and water uptake capacity of 94% that enables easy nutrient transportation in the in vitro cell culture. Youngs modulus of 2.4 kPa and viscoelastic property determine the soft and elastic nature of synthesized cryogel. Biocompatibility of PAG cryogel was evaluated through MTT assay of HepG2 and Huh-7 cells on matrices. The proliferation and functionality of the liver cells were enhanced by culturing hepatic cells as spheroids (hepatospheres) on the PAG cryogel using temperature-reversible soluble-insoluble polymer, poly(N-isopropylacrylamide) (PNIPAAm). Pore size of the cryogel above 100 mu m modulated spheroid size that can prevent hypoxia condition within the spheroid culture. Both the hepatic cells have shown a significant difference (P < 0.05) in terms of cell number and functionality when cultured with PNIPAAm. After 10 days of culture using 0.05% PNIPAAm, the cell number increased by 11- and 7-fold in case of HepG2 and Huh-7 cells, respectively. Similarly, after 10 days of hepatic spheroids culture on PAG cryogel, the albumin production, urea secretion, and CYP450 activity were significantly higher in case of culture with PNIPAAm. The developed tissue mass on the PAG cryogel in the presence of PNIPAAm possess polarity, which was confirmed using F-actin staining and by presence of intercellular bile canalicular lumen. The developed cryogel matrix supports liver cells proliferation and functionality and therefore can be used for in vitro and in vivo drug testing.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.

Enhanced adsorption capacity of activated alumina by impregnation with alum for removal of As(V) from water

Alum-impregnated activated alumina (AIAA) was investigated in the present work as an adsorbent for the removal of As(V) from water by batch mode. Adsorption study at different pH values shows that the efficiency of AIAA is much higher than as such activated alumina and is suitable for treatment of drinking water. The adsorption isotherm experiments indicated that the uptake of As(V) increased with increasing As(V) concentration from 1 to 25 mg/l and followed Langmuir-type adsorption isotherm. Speciation diagram shows that in the pH range of 2.8–11.5, arsenate predominantly exists as H2AsO4− and HAsO42− species and hence it is presumed that these are the major species being adsorbed on the surface of AIAA. Intraparticle diffusion and kinetic studies revealed that adsorption of As(V) was due to physical adsorption as well as through intraparticle diffusion. Effect of interfering ions revealed that As(V) sorption is strongly influenced by the presence of phosphate ion. The presence of arsenic on AIAA is depicted from zeta potential measurement, scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX) mapping study. Alum-impregnated activated alumina successfully removed As(V) to below 40 ppb (within the permissible limit set by WHO) from water, when the initial concentration of As(V) is 10 mg/l.

Improved Algorithms for Reservoir Capacity Calculation Incorporating Storage-Dependent Losses and Reliability Norm

Two algorithms that improve upon the sequent-peak procedure for reservoir capacity calculation are presented. The first incorporates storage-dependent losses (like evaporation losses) exactly as the standard linear programming formulation does. The second extends the first so as to enable designing with less than maximum reliability even when allowable shortfall in any failure year is also specified. Together, the algorithms provide a more accurate, flexible and yet fast method of calculating the storage capacity requirement in preliminary screening and optimization models.

Contribution of different physical forces to the disjoining pressure of a thin water film being pressed by an oil droplet

With an objective to understand the nature of forces which contribute to the disjoining pressure of a thin water film on a steel substrate being pressed by an oil droplet, two independent sets of experiments were done. (i) A spherical silica probe approaches the three substrates; mica, PTFE and steel, in a 10 mM electrolyte solution at two different pHs (3 and 10). (ii) The silica probe with and without a smeared oil film approaches the same three substrates in water (pH = 6). The surface potential of the oil film/water was measured using a dynamic light scattering experiment. Assuming the capacity of a substrate for ion exchange the total interaction force for each experiment was estimated to include the Derjaguin-Landau-Verwey-Overbeek (DLVO) force, hydration repulsion, hydrophobic attraction and oil-capillary attraction. The best fit of these estimates to the force-displacement characteristics obtained from the two sets of experiment gives the appropriate surface potentials of the substrates. The procedure allows an assessment of the relevance of a specific physical interaction to an experimental configuration. Two of the principal observations of this work are: (i) The presence of a surface at constant charge, as in the presence of an oil film on the probe, significantly enhances the counterion density over what is achieved when both the surfaces allow ion exchange. This raises the corresponding repulsion barrier greatly. (ii) When the substrate surface is wettable by oil, oil-capillary attraction contributes substantially to the total interaction. If it is not wettable the oil film is deformed and squeezed out. (C) 2010 Elsevier Inc. All rights reserved.

Ce0.78Sn0.2Pt0.02O2-delta: A new non-deactivating catalyst for hydrogen production via water-gas shift reaction

We demonstrate the activity of Ce0.78Sn0.2Pt0.02O2-delta, a new catalyst, towards water-gas shift (WGS) reaction. Over 99.5% CO conversion to H-2 is observed at 300 +/- 25 degrees C. Based on different characterization techniques we found that the present catalyst is resistant to deactivation due to carbonate formation and sintering of Pt on the surface when subjected to longer duration of reaction conditions. The catalyst does not require any pre-treatment or activation between start-up/shut-down reaction operations. Formation of side products such as methane, methanol, formaldehyde, coke etc. was not observed under the WGS reaction conditions indicating the high selectivity of the catalyst for H-2. Temperature programmed reduction of the catalyst in hydrogen (H-2-TPR) shows reversible reduction of Ce4+ to Ce3+, Sn4+ to Sn2+ and Pt4+ to Pt-0 oxidation state with oxygen storage capacity (OSC) of 3500 mu mol g(-1) at 80 degrees C. Such high value of OSC indicates the presence of highly activated lattice oxygen. CO oxidation in presence of stoichiometric O-2 shows 100% conversion to CO2 at room temperature. The catalyst also exhibits 100% selectivity for CO2 at room temperature towards preferential oxidation (PROX) of residual CO in presence of excess hydrogen in the feed. (C) 2010 Elsevier B.V. All rights reserved.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

Fly ash as a pre-filter material for the retention of lead ions

Clay liners have been widely used to contain toxic and hazardous waste materials. Clays absorb contaminant cations due to their exchange capacity. To improve the performance of the clay liner, fly ash, a waste material arising from the combustion of coal has been studied as a pre-filter material. In particular, the retention of lead by two different fly ashes was studied. The influence of pH on retention as well as leaching characteristics are also examined. The results obtained from the retention experiments by the permeameter method indicate that fly ash retains the lead ions through precipitation in the pores as well as onto the surface when the ambient pH value is more than 5.5, and through adsorption when the pH value is less than 5.5. It has been observed that fly ash did not release the retained lead ions when the pH value is between 3.5 and 10.0. Hence, the retention of lead ions by fly ash is likely to be permanent since the pH of most of the municipal landfill leachates are within 3.7 to 8.8. However, for highly acidic or alkaline leachates, the retained ions can get released.