Engineered organoclays are 2:1 phyllosilicate soils that have been synthesized with a controlled interlayer organic phase to exhibit enhanced strength, lower compressibility, and stronger retention of organic compounds. Engineered organoclays are highly sorptive, and have a variety of potential engineering applications as sorbents or amendments in engineered earthen barrier systems. Previous studies examined the impact of the organic coating on a soil's physical properties; however, the geochemical behaviors of organoclays, especially their interaction with organic compounds at the micro-scale, remained relatively unquantified. This study investigated the engineering behavior of montmorillonite modified with a variety of quaternary ammonium cations (QAC clays) with controlled structure and density of loading. Molecular dynamics simulations were used to model the surfactant arrangement, geochemical processes in the QAC-clay interlayer, including organic compound sorption and mass transport, as well as the surface electrokinetics of suspended QAC-clay particles. All simulations were carried out based on the combined force field of ClayFF and the Consistent-Valence Force Field to ensure the accuracy of the simulation results, and results yielded insight into the prediction of synthesized QAC-clay behaviors as sorptive material for non-polar organic compounds.

A literature review of municipal solid waste landfill design was conducted to provide the knowledge base for development of an environmental decision support system (Landfill Advisor). Landfill Advisor integrates the current knowledge of barrier systems into a software program to assist in landfill design. The choices available for each liner component (e.g., drainage layer, geomembrane liner, compacted clay liner, geosynthetic clay liner) and their suitability for different situations (e.g., final cover, base liner, lagoon liner) are presented. Landfill Advisor covers both the design and related operational issues for municipal solid waste landfills, with consideration given to the interactions between components, operating conditions, and the natural environment with a view to maximization of long-term system performance. Unique to Landfill Advisor, the service life of each engineered component is estimated based on results from the latest research. Original research is also presented on the risk of geosynthetic clay liner (GCL) desiccation in low stress applications such as solar ponds. Numerical modelling was undertaken using a thermo-hydro-mechanical model with parameters that were developed and verified by comparison to previously reported laboratory data. A parametric study was performed to establish recommendations for future investigation. The water retention curve of the GCL was found to have a significant effect on the conditions that are expected to cause desiccation. The temperature coefficient of the water retention curve was also found to have a significant effect, yet this parameter is not well defined. Poisson’s ratio was found to affect the risk of desiccation in proportion to the applied stress. As reported by previous researchers, the initial degree of saturation of a GCL was found to be important to desiccation; however, the effect is diminished at low applied stress. / Thesis (Master, Civil Engineering) -- Queen's University, 2012-09-28 18:52:20.106

Thermal power station in most countries is saddled with the problem of fly ash disposal and unless suitable avenues are found for its proper use, this would pose a gigantic problem to the power sector. Disposal of huge quantities of fly ashes without proper care causes considerable impact on the environment particularly the one leading to soil and groundwater contamination. On the other hand, fly ashes have many desirable properties which can find applications in civil engineering, especially in geotechnical engineering. The pozzolanic reactivity is one of the important properties of fly ashes that enhance its application. Thought the fly ashes with self – pozzolanic property are well utilized, fly ashes with insufficient free lime, such as class F fly ashes are being grossly underutilized and they form a considerable portion of fly ashes that are disposed. Yet another factor restricting the use of fly ash is the concern about the leachability of lime under field conditions particularly under saturated or partially saturated conditions. Hence an attempt is made in this thesis, to reduce the lime leachability of class F fly ashes with different additives. Thus, selection of right amounts of additives to reduce the lime leacability is an important aspect studied in this thesis. Effect of such as strength, compressibility, and CBR value is also investigated. Another simple way to reduce the problem of disposal of fly ash is to utilize it for the construction of waste disposal sites particularly for lining solid waste disposal facilities in place of the natural clay materials which are very often procured by excavating and transporting from far off places. Also, the capacities of fly ashes to sorb heavy metal that are likely to be present in the leachates generated from the industrial wastes have been studied. Of the other factors limiting the generous use of fly ashes is the leachability of several trace elements present in them. Hence the leachability of trace metals from fly ashes under different practical situations, before and after incorporating the selected additives for improving the engineering properties of fly ashes, has been studied. The thesis is presented in 10 chapters. The relevant background for the studies and scope of the work is given Chapter 1. Sources of the fly ashes collected for the investigating along with their physical and chemical properties are presented in chapter 2. Two low line fly ashes are collected directly from the electronic precipitators of the thermal power plants located at Neyvelli town of the Tamil nadu and Maddanur town of Andhra Pradesh, India, named NFA and MFA respectively. MFA has greater finer particle content than NFA. The particles of MFA Have rougher surface compared to those of NFA. Both of fly ashes have predominantly quartz and mullite phase in them. The silica, total lime and carbon contents which have major influence on the pozzolanic reactivity of fly ashes vary considerably in the both the fly ashes. Lime leachability is taken as the amount of lime that is converted into soluble form (by dissociation into calcium and hydroxyl ions) under a standardized condition. It can be used to asses the long term sustainability of the strength achieved in fly ashes with lime. Lime leachability studies have been conducted on the fly ashes stabilized with different additives in specially designed moulds. Results presented in Chapter 3 showed that leachability of lime in fly ashes increases with the increase in lime content though it is not in proportion to the increase in lime content. This is because the solubility of lime is less and is independent of the total lime present. The marginal reduction in leachability is mainly due to cemented matrix of fly ash inhibiting the leaching of time. The higher the strength of the matrix the lower is the leachability. Further it is made clear that at any lime content presence of gypsum reduces the time leachability which has been attributed to the transformation of pozzolanic compounds into less soluble form than the compounds formed with lime alone. With the increase in curing period, the amount of lime that leaches from the lime-stabilized fly ashes as well as those treated with gypsum to a considerable extent. The nature of alteration does not seem to change with time as revealed by a good correlation between lime leachability ratios obtained after 7 days and 14 days of curing periods. Chapter 4 presents the results of unconfined compressive strength tests carried out on fly ashes with varying lime and gypsum contents, before soaking and also soaking in several heavy metal solutions, along with the durability to the cycle of wetting and drying. The results revealed that the strength of low lime fly ashes increases with lime content significantly up to the optimum lime content of about 2.5 – 5% and gradually thereafter. Addition of gypsum of 1 – 2.5% increases the strength of fly ashes further at any lime content. Increase in strength with gypsum, which is quite significant at lower lime contents initially, is observed for a considerable period (up to 180 days) at higher lime contents. The increase in strength is as high as 40-fold in some instances. This increase in strength which is also more durable has been attributed to the formation of calcium – sodium – aluminium - silicate hydrate along with calcium silicate hydrate. Further, it is observed that fly ash which responds better to lime stabilization shows accelerated gain in strength due to the addition of gypsum at early curing periods than the fly ash that responds solely to lime. Decrease in lime leachability ratio is a good indication of the increased strength along with the increased durability. California Bearing Radio (CBR) values are of great significance in the utilization of fly ashes in bulk quantities for the construction of road and railway embankments and pavements. Studies conducted to determine the CBR values of fly ashes with different lime and gypsum contents after curing for different time periods are described in chapter 5. The CBR values are observed to increase with lime alone significantly up to 2.5% and only marginally beyond. But the increase in CRB values is considerable with gypsum at any lime content. The increase in CBR value is particularly more with 2.5% gypsum for fly ashes with 2.5% lime. The CBR values of stabilized fly ashes are generally higher for 5 mm depth of penetration than those for 2.5 mm one due to the high stiffness of the matrix formed even at low strain levels. The loss in CBR values with soaking is relatively more at lower curing the periods due to the improper cementation of particles. Even after this significant loss in CBR values, fly ashes with 2.5% lime and 2.5% gypsum register the maximum values after curing under soaked condition. Unlike in the case of unconfined compressive strength, lime leachability values could not be well correlated with the CBR values of fly ashes with different lime and gypsum contents since many more factors influence the CBR values than those of unconfined compressive strength alone. Chapter 6.brings out the effects of addition of lime alone and lime along with gypsum on the compressibility behaviour of the fly ashes. Since the fly ashes when treated with additives develop strength and exhibit lower compression with the passage of time, consolidation testing with conventional duration of load increment may not be appropriate. Hence an attempt has been made to assess the minimum duration of load increment necessary to study the compressibility characteristics of such materials. Thus the compressibility behaviour of fly ashes with additives has been studied using conventional consolidation test with different durations of load increments varying from 30 minutes to 48 hours. The results indicated that 30 minutes of duration of load increment can be used to assess the compressibility behaviour of such materials. The effect of lime which reduces the compression is seen to be maximum from the results obtained with the load duration increment of 30 minutes but gradually reduce with higher duration of load increment. It has also been observed that the rate of decrease in the compressibility is maximum up to 2.5% lime and thereafter gradual. The compressibility of lime –treated fly ashes further reduces when gypsum is incorporated, the optimum gypsum percentage being 2.5. This reduction in the compressibility of fly ashes enhanced by incorporating lime and gypsum makes them versatile in the construction of embankments and for structural fills, particularly reducing the time required in between laying of each lift. It has been brought out that decrease in the lime leachability decreases the compressibility of fly ashes. Fly ash has potential application in the construction of base liners of waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of hydraulic conductivities they attain may often not meet the basic requirement of a liner material. Attempts to reduce the hydraulic conductivity by adding lime as gypsum along with lime to both the fly ashes are presented in chapter 7. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head methods. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the fly ashes containing gypsum is significantly more of sample with high amounts of lime contents (as high as 1000 times) than those with lower amounts of lime. However, there is relatively more increases in the strengths of the samples with the inclusion of gypsum to the fly ashes even at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted in to pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of gypsum is observed to produce more cementitious compounds which block the pores in the fly ash. Amount of lime leached in the found to be directly related to the hydraulic conductivity inspite of many –fold variations in the hydraulic conductivity achieved by curing fly ash with lime and gypsum. The consequent reduction on the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements in the fly ash when used as base liner. Fly ash contains trace metals and other substances in the sufficient quantities which may leach out over a period of time. The study has been extended to examine the leachability of a few selected trace metals viz., Cd, Cu, Cr, Mn, Pb and Zn from fly ash before and after incorporating additives has been reported in chapter 9. The standard laboratory leaching test for the combustion residues developed by Van der Sloot et al. has been employed to study the leachabilities of trace elements as a function of liquid to solid (L/S) ratio and pH. The leachability test were conducted on the powdered fly ash samples obtained from unconfined compressive strength tests, conducted after a curing period of 28 and 180 days. It observed that, there is a marked reduction in the relative leachabilities of trace elements present, at the end of 28 days which reduced only marginally at the end of 180 days. Chapter 9 reports the retention capacities of fly ashes for copper, lead and zinc metals ions. Various parameters like contact time, initial concentration and pH have been varied and their effect on retention mechanism studied. The retention order of metals ions, Cu+ 2 > Pb+2>Zn+2, is observed to be the same for both the fly ashes at all pH values. The dominant mechanisms responsible for the retention are precipitation at higher pH’s as hydroxides and adsorption at lower pH’s Due to presence of silica and alumina oxide surface in fly ash. First order kinetic plots have revealed that the rate constant value increases with increase in initial concentration and pH. Langmuir adsorption isotherms have been plotted to study the maximum adsorption isotherms have been plotted to study the maximum adsorption capacities for metal ions under different conditions. The older indicates that the adsorption is predominantly by silica surface than that by alumina or iron oxide surfaces. This thesis demonstrates that incorporation of gypsum along with lime in the optimal proportions not only reduces the lime leachability but also greatly enhances the strength and CBR values, reduces the compressibility and minimizes the leaching of trace elements present in them enhancing the potential of fly ashes for many applications. Detailed conclusions are presented in chapter 10. The study greatly helps in promoting the use of fly ashes for many geotechnical and geo-environmental applications.

京都大学 / 0048 / 新制・論文博士 / 博士(地球環境学) / 乙第12827号 / 論地環博第7号 / 新制||地環||24(附属図書館) / 31314 / (主査)教授 勝見 武, 教授 三村 衛, 准教授 乾 徹 / 学位規則第4条第2項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

High density polyethylene (HDPE) geomembranes are normally used as part of a composite liner for waste containment facilities such as municipal solid waste (MSW) landfills and heap leach pads. Field conditions, which include physical stresses on the geomembrane, elevated operating temperatures, and contact with leachate constituents, have the potential to affect the service life of the HDPE geomembranes. This thesis examined the long-term performance of different HDPE geomembranes based on both conventional laboratory accelerated immersion tests and simulated landfill liner tests. A 1.5mm HDPE geomembrane was immersed in different synthetic leachates at different temperatures in order to evaluate the effects of leachate chemical constituents on the depletion of antioxidants. The results showed that a basic leachate with trace metals, surfactant, and a reducing agent was the most appropriate for evaluating the potential degradation of HDPE geomembranes. A similar immersion test was performed to evaluate the effects of thickness on the ageing of HDPE geomembranes. Three commercially available HDPE geomembranes having nominal thicknesses of 1.5, 2.0, and 2.5mm were immersed in a synthetic leachate at four different temperatures in this experiment. The results showed that a thicker geomembrane may have a longer service life if other things are similar. The depletion of antioxidants from a 1.5mm thick HDPE geomembrane was examined by conducting accelerated ageing tests at 55, 70, and 85oC under simulated landfill liner conditions. The results showed that the antioxidant depletion rate was consistently lower for the simulated landfill liner tests compared to the leachate immersion tests. The effectiveness of the aged HDPE geomembrane on the migration of volatile organic compounds (VOCs) was examined by conducting diffusion and partitioning tests using both unaged and aged HDPE geomembranes. The results showed that the ageing of HDPE geomembranes did not increase diffusive migration of organic contaminants, provided that the geomembrane remained intact. A new method was developed to estimate the service life of the HDPE geomembrane based on the landfill liner temperature history. The service lives of the HDPE geomembranes were calculated to be between 20 and 4700 years, depending on the geomembrane type, exposure conditions, and the time-temperature history examined. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2009-01-30 09:30:49.135

Fly ash and blast furnace slag are the two major industrial solid by-products generated in most countries including India. Although their utilization rate has increased in the recent years, still huge quantities of these material remain unused and are stored or disposed of consuming large land area involving huge costs apart from causing environmental problems. Environmentally safe disposal of Fly ash is much more troublesome because of its ever increasing quantity and its nature compared to blast furnace slag. Bulk utilization of these materials which is essentially possible in civil engineering in general and more particular in geotechnical engineering can provide a relief to environmental problems apart from having economic benefit. One of the important aspects of these waste materials is that they improve physical and mechanical properties with time and can be enhanced to a significant level by activating with chemical additives like lime and cement. Class-C Fly ashes which have sufficient lime are well utilized but class-F Fly ashes account for a considerable portion that is disposed of due to their low chemical reactivity. Blast furnace slag in granulated form is used as a replacement for sand to conserve the fast declining natural source. The granulated blast furnace slag (GBS) is further ground to enhance its pozzolanic nature. If GBS is activated by chemical means rather than grinding, it can provide a good economical option and enhance its utilization potential as well. GGBS is latent hydraulic cement and is mostly utilized in cement and concrete industries. Most uses of these materials are due to their pozzolanic reactivity. Though Fly ash and GGBS are pozzolanic materials, there is a considerable difference in their chemical composition. For optimal pozzolanic reactivity, sufficient lime and silica should be available in desired proportions. Generally, Fly ash has higher silica (SiO2) content whereas GGBS is rich in lime (CaO) content. Combining these two industrial wastes in the right proportion may be more beneficial compared to using them individually. The main objective of the thesis has been to evaluate the suitability of the class-F Fly ash/GGBS mixtures with as high Fly ash contents for Geotechnical and Geo-environmental applications. For this purpose, sufficient amount of class-F Fly ash and GGBS were collected and their mixtures were tested in the laboratory for analyzing their mechanical behavior. The experimental program included the evaluation of mechanical properties such as compaction, strength, compressibility of the Fly ash/GGBS mixtures at different proportions with GGBS content varying from 10 to 40 percent. An external agent such as chemical additives like lime or cement is required to accelerate the hydration and pozzolanic reactions in both these materials. Hence, addition of varying percentages of lime is also considered. However, these studies are not extended to chemically activate GBS and only GGBS is used in the present study. Unconfined compressive strength tests have been carried out on various Fly ash/ GGBS mixtures at different proportions at different curing periods. The test results demonstrated rise in strength with increase in GGBS content and with 30 and 40 percent of GGBS addition, the mixture showed higher strength than either of the components i.e. Fly ash or GGBS after sufficient curing periods. Addition of small amount of lime increased the strength tremendously which indicated the occurrence of stronger cementitious reactions in the Fly ash/GGBS mixtures than in samples containing only Fly ash. Improvement of the strength of the Fly ash/GGBS mixtures was explained through micro-structural and mineralogical studies. The microstructure and mineralogical studies of the original and the stabilized samples were investigated by scanning electron microscopy (SEM) and X-Ray diffraction techniques respectively. These studies together showed the formation of cementitious compounds such as C-S-H, responsible for imparting strength to the pozzolanic materials, is better in the mixture containing 30 and 40 percent of GGBS content than in individual components. Resilient and permanent deformation behavior on an optimized mix sample of Fly ash and GGBS cured for 7 day curing period has been studied. The Resilient Modulus (Mr) is a measure of subgrade material stiffness and is actually an estimate of its modulus of elasticity (E). The permanent deformation behavior is also important in predicting the performance of the pavements particularly in thin pavements encountered mainly in rural and low volume roads. The higher resilient modulus values indicated its suitability for use as subgrade or sub-base materials in pavement construction. Permanent axial strain was found to increase with the number of load cycles and accumulation of plastic strain in the sample reduced with the increase in confining pressure. Consolidation tests were carried on Fly ash/GGBS mixtures using conventional oedometer to assess their volume stability. However, such materials develop increased strength with time and conventional rate of 24 hour as duration of load increment which requires considerable time to complete the test is not suitable to assess their volume change behavior in initial stages. An attempt was thus made to reduce the duration of load increment so as to reflect the true compressibility characteristics of the material as close as possible. By comparing the compressibility behavior of Fly ash and GGBS between conventional 24 hour and 30 minutes duration of load increment, it was found that 30 minutes was sufficient to assess the compressibility characteristics due to the higher rate of consolidation. The results indicated the compressibility of the Fly ash/GGBS mixtures slightly decreases initially but increase with increase in GGBS content. Addition of lime did not have any significant effect on the compressibility characteristics since the pozzolanic reaction, which is a time dependent process and as such could not influence due to very low duration of loading. Results were also represented in terms of constrained modulus which is a most commonly used parameter for the determination of settlement under one dimensional compression tests. It was found that tangent constrained modulus showed higher values only at higher amounts of GGBS. It was also concluded that settlement analysis can also be done by taking into account the constrained modulus. The low values of compression and recompression indices suggested that settlements on the embankments and fills (and the structures built upon these) will be immediate and minimal when these mixtures are used. In addition to geotechnical applications of Fly ash/GGBS mixture, their use for the removal of heavy metals for contaminated soils was also explored. Batch equilibrium tests at different pH and time intervals were conducted with Fly ash and Fly ash/GGBS mixture at a proportion of 70:30 by weight as adsorbents to adsorb lead ions. It was found that though uptake of lead by Fly ash itself was high, it increased further in the presence of GGBS. Also, the removal of lead ions increased with increase in pH of the solution but decreases at very high pH. The retention of lead ions by sorbents at higher pH was due to its precipitation as hydroxide. Results of the adsorption kinetics showed that the reaction involving removal of lead by both the adsorbents follow second-order kinetics. One of the major problems which geotechnical engineers often face is construction of foundations on expansive soils. Though stabilization of expansive soils with lime or cement is well established, the use of by-product materials such as Fly ash and blast furnace slag to achieve economy and reduce the disposal problem needs to be explored. To stabilize the soil, binder comprising of Fly ash and GGBS in the ratio of 70:30 was used. Different percentages of binder with respect to the soil were incorporated to the expansive soil and changes in the physical and engineering properties of the soil were examined. Small addition of lime was also considered to enhance the pozzolanic reactions by increasing the pH. It was found that liquid limit, plasticity index, swell potential and swell pressure of the expansive soil decreased considerably while the strength increased with the addition of binder. The effect was more pronounced with the addition of lime. Swell potential and swell pressure reduced significantly in the presence of lime. Based on the results, it can be concluded that the expansive soils can be successfully stabilized with the Fly ash-GGBS based binder with small addition of lime. This is also more advantageous in terms of lime requirement which is typically high when Fly ash, class-F in particular, is used alone to stabilize expansive soils. Based on the studies carried out in the present work, it is established that combination of Fly ash and GGBS can be advantageous as compared to using them separately for various geotechnical applications such as for construction of embankments/fills, stabilization of expansive soils etc. with very small amount of lime. Further, these mixtures have better potential for geo-environmental applications such as decontamination of soil. However, it is still a challenge to activate GBS without grinding.