This diploma thesis focuses on interactions of chosen pharmaceuticals with soil and study their mobility. First part is devoted to the characteristics of the most common pharmaceuticals that appear in the environment, specifically antibacterial chemoterapeutics and analgetics. Subsequently, the occurrence of the pharmaceuticals in environment, their sources and effects are described. Further, the work focuses on soil components and soil organic matter. In conclusion of the theoretical part is the description of used analytical method for processing of the results and also the current state of the problematics. In the practical part of the thesis the experiments were made and analyzed and further served for better understanding of adsorption and interactions of chosen pharmaceuticals with soil and humin acids as the main reactive part of the soil.

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New explosive compounds that are less sensitive to shock and high temperatures are being tested on military ranges as replacements for 2, 4, 6-trinitrotoluene (TNT) and hexahydro-1, 3, 5-trinitro-1, 3, 5-triazine (RDX). One of the two compounds being tested is 2, 4-dinitroanisole (DNAN), which has good detonation characteristics and is one of the main ingredients in a suite of explosive formulations being tested. Data on the fate and transport of DNAN is needed to determine its potential to reach groundwater and be transported off base, a result which could create future contamination problems on military training ranges and trigger regulatory action. In this study, I measured how DNAN in solution interacts with different types of soils from across the United States. I conducted kinetic and equilibrium batch soil adsorption experiments, saturated column experiments with DNAN and dissolution and transport studies of insensitive munitions (IMX-101, IMX -104), which include DNAN, 3-nitro-1,2,4-triazol-5-one (NTO), nitroguanidine (NQ) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), under steady state and transient conditions. In the rate studies, change in DNAN concentration with time was evaluated using the first order kinetic equation. Solution mass-loss rate coefficients ranged between 0.0002 h-1 and 0.0068 h-1. DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3 L kg-1, and Freundlich coefficients between 1.3 and 34 mg1-n Ln kg-1. Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil. In saturated miscible-displacement experiments, it was shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-amino-4-nitroanisole (2-ANAN) and 4-amino-2-nitroanisole (4-ANAN). Dissolution miscible-displacement experiments demonstrated that insensitive munition compounds dissolved in order of aqueous solubility as indicated by earlier lab and outdoor dissolution studies. The sorption of NTO and NQ was low, while RDX, HMX, and DNAN all adsorbed to the soils. DNAN transformed in soils with formation of amino-reduction products, 2- ANAN and 4-ANAN. Adsorption parameters determined by HYDRUS-1D generally agreed with batch and column study adsorption coefficients for pure NTO and DNAN. The magnitudes of retardation and transformation observed in these studies result in significant attenuation potential for DNAN in soils, which would reduce risk of groundwater contamination.

The overall objective of this study was to evaluate the performance of selected furrow irrigation models for field conditions in south-east Australia. The other important aspects which were examined during this study include: developing a methodology for estimating of infiltrating characteristics, assessing the applicability of the Manning and other similar equations for flows in furrow irrigation, investigating the variation of shape factor during irrigation developing methodology for estimation of recession time and exploring the sensitivity of the models to the input parameters. Field experiments were conducted at Walla Park in northern N.S.W. and on two selected paddocks at the University Farm, Richmond, in western Sydney,Australia, over a period of three years. The validity of the assumption that the shape factor of advancing water front during furrow irrigation varies between 0.7 and 0.8 was investigated using field data collected from irrigation events monitored in the study. It was found that the average values of the shape factor varied from 0.96 to 1.80 at Walla Park site, from 0.56 to 0.80 at Field Services unit paddock site and from 0.78 to 0.84 at Horticulture Farm paddock site. The value of shape factor was affected by uniformity of furrow cross section along the length, the value and uniformity of furrow slope, furrow length and infiltration characteristics of soil. This means it is difficult to recommend a typical value for the shape factor for a given field situation.The performance of the models for prediction of advance and recession characteristics and runoff were evaluated using different indices of performance. In general, it was found that the Walker-HD and ZI model was the most satisfactory for the field conditions encountered in this study. This finding can provide a basis for initiating work on developing design criteria and management strategies for furrow irrigation in south-east Australia. / Doctor of Philosophy (PhD)

The Bryan/College Station (B/CS) region has been reported to have elevated concentrations of dissolved organic carbon (DOC) in surface water. Increased DOC concentrations are worrisome as DOC has been shown to be an energy source for the recovery and regrowth of E. coli and many watersheds are impaired by high bacteria levels. To examine the sources and fates of DOC in rural and urban regions to better understand DOC movement though the environment, seven watersheds were studied. To investigate source, streams were analyzed using diffuse reflectance near infrared spectroscopy (DR-NIR) and carbon isotopes. Fate of DOC was determined through monthly streams samples, gathered between March 2011 and February 2012, which were incubated for biodegradable DOC (BDOC). Soil in the region was sampled based on land use categories. Soil was analyzed for DOC and BDOC as well as DOC adsorption, the other major fate of DOC. Above ground vegetation was sampled in conjunction with soil and analyzed for BDOC. Data indicated that fecal matter from cliff swallows provided considerable organic material to streams in the B/CS region as shown through DR-NIR. Carbon isotope values in streams ranged from -23.5 +/- 0.7% to -26.8 +/- 0.5%. Stream spectra may be able to predict carbon isotope values in streams (Adj. R2 = 0.88). Mean annual stream DOC concentrations ranged from 11 +/- 3 mg/L to 31 +/- 12 mg/L, which represents a significant decrease in DOC between 2007 and 2011. Concurrent increases in pH and conductivity were also recorded. The decrease in DOC and the increases in pH and conductivity may be due to impacts of high sodium irrigation tap water. Biodegradable DOC was low in streams, which is likely due to DOC being present in streams in refractory forms that are resistant to microbial breakdown. Soil chemistry, including soil adsorption, was greatly influenced by sodium. The elevated adsorption coefficients and release values seen in highly developed and urban open areas can be attributed to frequent exposure to high sodium irrigation water. The results indicate that sodium is a major driver of DOC in the system. Sound management decisions concerning irrigation water chemistry and urban development might eventually emerge to protect water quality as a result of this research.

The explosive 2,4,6-trinitrotoluene (TNT) is currently a main ingredient in munitions; however the compound has failed to meet the new sensitivity requirements. The replacement compound being tested is 2,4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bio-availability and human exposure potential. The objective of this study was to investigate the environmental fate and transport of DNAN in soil, with specific focus on sorption processes. Batch and column experiments were conducted using soils collected from military installations located across the United States. The soils were characterized for pH, electrical conductivity, specific surface area, cation exchange capacity, and organic carbon content. In the batch rate studies, change in DNAN concentration with time was evaluated using the first order equation, while adsorption isotherms were fitted using linear and Freundlich equations. Solution mass-loss rate coefficients ranged between 0.0002 h(-1) and 0.0068 h(-1). DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3 L g(-1), and Freundlich coefficients between 1.3 and 34 mg(1-n) L-n kg(-1). Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil, indicating that similar to TNT, organic matter and clay minerals may influence adsorption of DNAN. The results of the miscible-displacement column experiments confirmed the impact of sorption on retardation of DNAN during transport. It was also shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-ANAN and 4-ANAN. The magnitudes of retardation and transformation observed in this study result in significant attenuation potential for DNAN, which would be anticipated to contribute to a reduced risk for contamination of ground water from soil residues.

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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.

The present work is a contribution to description and understanding of the distribution and movement of water in swelling soils. In order to investigate the moisture distribution in swelling soils a detailed knowledge of volume change properties, flow characteristics and total potential of water in the soil is essential. Therefore, a possible volume change mechanism is first described by dividing the swelling soils into four categories and volume change of a swelling soil is measured under different overburden pressures. The measured and calculated (from volume change data) overburden potential components are used to check the validity of the derivation of a load factor, ∝. Moisture diffusivity in swelling soil under different overburden pressures is measured using Gardner's (1956) outflow method. Behaviour of equilibrium moisture profiles in swelling soils is theoretically explained, solving the differential equation by considering the physical variation of individual soil properties with moisture content and overburden pressure. Using the measured volume change data and moisture potentials under various overburden pressures, the behaviour of possible moisture profiles are described at equilibrium and under steady vertical flows in swelling soils. It is shown that high overburden pressures lead to soil water behaviour quite different from any previously reported.