Semiconductor Oxides Mediated Photocatalytic Removal of Chemical and Bacterial Pollutants from Wastewater

School of Environmental Studies, Cochin University of Science and Technology

Catalysis by some metal oxides modified with phosphate ions

Surface acidity of phosphate modified La2O3,CeO2 and SnO2 has been estimated by titrimetric Method using Hammett Indicators.Mixed Oxides of tin and lanthanum have also been prepared and subjected to phosphate modification.Surface characterizartion of the samples has been carried out using XRD, surface area,thermal analysis and IR spectroscopy. Phosphate content in the samples has been chemically estimated. The catalytic activity for benzylation and esterification reaction has also been investigated.

Surface properties and catalytic activity of phosphate modified zirconia

Preparation and physico-chemical characterization or phosphate modified zirconia systems and their application to Friedel-Crafts benzylation and benzoylation of toluene have been reported. The influence of transition metals on the surface properties and catalytic activity has also been discussed.

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Electrical conductivity, dielectric constant and phase transitions in pure and doped diammonium hydrogen phosphate

DC and AC electrical conductivity measurements in single crystals of diammonium hydrogen phosphate along the c axis show anomalous variations at 174, 246 and 416 K. The low-frequency dielectric constant also exhibits peaks exactly at these temperatures with a thermal hysteresis of 13 degrees C for the peak at 416 K. These specific features of the electrical properties are in agreement with earlier NMR second-moment data and can be identified with three distinct phase transitions that occur in the crystal. The electrical conductivity values have been found to increase linearly with impurity concentration in specimens doped with a specific amount of SO42- ions. The mechanisms of the phase transition and of the electrical conduction process are discussed in detail.

High‐temperature phase transitions in pure and deuterated ammonium dihydrogen phosphate: Conductivity and dielectric measurements

Results of axiswise measurements of the electrical conductivity (dc and ac) and dielectric constant of NH4H2PO4 confirm the occurrence of the recently suggested high‐temperature phase transition in this crystal (at 133 °C). The corresponding transition in ND4D2PO4 observed here for the first time takes place at 141.5 °C. The mechanism involved in these transitions and those associated with the electrical conduction and dielectric anomalies are explained on the basis of the motional effects of the ammonium ions in these crystals. Conductivity values for deuterated crystals give direct evidence for the predominance of protonic conduction throughout the entire range of temperatures studied (30–260 °C).

Colour Removal From Dye-House Efiluents Using Zero-Valent iron and Fenton Oxidation

This thesis Entitled Colour removal from dye house effluents using zero valent iron and fenton oxidation.Findings reported on kinetic profile during oxidation of dyes with Fenton’s reagent are in good agreement with observations of earlier workers on other organic substrates. This work goes a step further. Critical concentration of the dye at which the reaction mechanism undergoes transition has been identified.The oxidation of Reactive Yellow showed that the initial rates for decolorization increased linearly with an increase in hydrogen peroxide concentration over the range studied. Fenton oxidation of all dyes except Methylene Blue showed that the initial rates increased linearly with an in the ferrous sulphate concentration. This increase was observed only up to an optimum concentration beyond which further increase resulted in a decrease in the initial rates. Variation of initial rates with Ferrous sulphate concentration resulted in a linear plot passing through the origin indicating that the reaction is first order with respect to ferrous sulphate.

Application of chitosan and PASS for the removal of turbidity and colour from water

The most common and conventional method for removing turbidity from water is by coagulating with alum or iron salts, and settling the precipitate in suitably designed clarifiers followed by filtration. But the sludge produced is bulky, difficult to dewater and accumulates in the dumping grounds causing environmental problems. Synthetic polymers such as polyacrylamide and polyethyleneoxide have been investigated for their ability to remove turbidity. They overcome many of the disadvantages of conventional methods, but are cost—effective only when rapid flocculation and reduction in sludge volume are demanded. Considering the aforementioned situation, it was felt that more easily available and eco-friendly materials must be developed for removing turbidity from water. The results of our studies in this direction are presented in this thesis. The thesis comprises of nine chapters, with a common bibliography at the end. Chapter 1 gives an introduction to the nature of turbidity and colour usually present in water. Chapter 2 discusses the nature and availability of the principal material used in these studies, namely chitosan. Chapters 3 to 8, which deal with the actual experimental work, are further subdivided into (a) introduction, (b) materials and methods, (c) results and discussion and (d) conclusions. Chapter 9 summarises the entire work so as to put the results and conclusions into proper perspective.

High-momentum proton removal from 16 O and the (e,e'p) cross section

The cross section for the removal of high-momentum protons from 16O is calculated for high missing energies. The admixture of high-momentum nucleons in the 16O ground state is obtained by calculating the single-hole spectral function directly in the finite nucleus with the inclusion of short-range and tensor correlations induced by a realistic meson-exchange interaction. The presence of high-momentum nucleons in the transition to final states in 15N at 60¿100 MeV missing energy is converted to the coincidence cross section for the (e,e¿p) reaction by including the coupling to the electromagnetic probe and the final state interactions of the outgoing proton in the same way as in the standard analysis of the experimental data. Detectable cross sections for the removal of a single proton at these high missing energies are obtained which are considerably larger at higher missing momentum than the corresponding cross sections for the p-wave quasihole transitions. Cross sections for these quasihole transitions are compared with the most recent experimental data available.

ECG Noise Removal using GA tuned Sign-Data Least Mean Square Algorithm

Adaptive filter is a primary method to filter Electrocardiogram (ECG), because it does not need the signal statistical characteristics. In this paper, an adaptive filtering technique for denoising the ECG based on Genetic Algorithm (GA) tuned Sign-Data Least Mean Square (SD-LMS) algorithm is proposed. This technique minimizes the mean-squared error between the primary input, which is a noisy ECG, and a reference input which can be either noise that is correlated in some way with the noise in the primary input or a signal that is correlated only with ECG in the primary input. Noise is used as the reference signal in this work. The algorithm was applied to the records from the MIT -BIH Arrhythmia database for removing the baseline wander and 60Hz power line interference. The proposed algorithm gave an average signal to noise ratio improvement of 10.75 dB for baseline wander and 24.26 dB for power line interference which is better than the previous reported works

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.

Sono, Photo and Sonophoto Catalytic Removal of Chemical and Bacterial Pollutants from Wastewater

The term ‘water pollution’ broadly refers to the contamination of water and water bodies (e.g. lakes, rivers, oceans, groundwater etc). Water pollution occurs when pollutants are discharged directly or indirectly into water bodies without adequate treatment to remove the harmful contaminants. This affects not only the plants and organisms living in these bodies of water but also the entire natural biological communities and the biodiversity.Advanced Oxidation Processes (AOPs) have been tested as environment-friendly techniques for the treatment of contaminated water, in view of their ability to convert pollutants into harmless end products. These techniques refer to a set of treatment procedures designed to remove organic or inorganic contaminants in wastewater by oxidation. The contaminants are oxidized by different reagents such as air, oxygen, ozone, and hydrogen peroxide which are introduced in precise, preprogrammed dosages, sequences and combinations under appropriate conditions. The procedure when combined with light in presence of catalyst is known as photocatalysis. When ultrasound (US) is used as the energy source, the process is referred as sonication. Sonication in presence of catalyst is referred as sonocatalysis. Of late, combination of light and sound as energy sources has been tested for the decontamination of wastewater in the presence of suitable catalyst. In this case, the process is referred as sonophotocatalysis. These AOPs are specially advantageous in pollution control and waste water treatment because unlike many other technologies, they do not just transfer the pollutant from one phase to another but completely degrade them into innocuous substances such as CO2 and H2O.

Effects of Tithonia diversifolia, farmyard manure and urea, and phosphate fertiliser application methods on maize yields in western Kenya

Maize production in western Kenya is often limited by deficiencies of nitrogen and phosphorus. We assessed the effectiveness of Tithonia diversifolia green manure (tithonia), farmyard manure (FYM) and urea as sources of nitrogen (N) for maize when inorganic phosphorus (P) fertiliser was either broadcast (BR) or spot-placed in the planting hole (SP) for two consecutive seasons; October to December of 1998 and April to August of 1999 at two sites; Nyabeda and Khwisero in western Kenya. A randomised complete block design with four replications was used. Maize yields were higher at Nyabeda and responded to P application better than at Khwisero. At the same N rate, tithonia and FYM were as effective as urea in increasing maize yields at both sites. There were no significant differences in maize yields when phosphate fertiliser was either BR or SP regardless of the N source used in the first season. However, in the second season, the residual yields for the BR treatments were consistently higher than those of the SP. Our results suggest that tithonia and FYM can substitute for urea as N sources and that fertiliser P should be broadcast and incorporated together with the organic materials at the time of planting to save on labour costs.

Biological nutrient removal in SBR technology: from floccular to granular sludge

Biological nutrient removal has been studied and applied for decades in order to remove nitrogen and phosphorus from wastewater. However, more anthropogenic uses and the continued demand for water have forced the facilities to operate at their maximum capacity. Therefore, the goal of this thesis is to obtain more compact systems for nutrient removal from domestic wastewater. In this sense, optimization and long-term stabilization of high volume exchange ratios reactors, treating higher volumes of wastewater, have been investigated. With the same target, aerobic granular sludge was proposed as a reliable alternative to reduce space and increase loading rates in treatment plants. However, the low organic loading rate from low-strength influents (less than 1 Kg COD•m-3d-1) results in slower granular formation and a longer time to reach a steady state. Because of that, different methodologies and operational conditions were investigated in order to enhance granulation and nutrient removal from domestic wastewater.

Operation and control of SBR processes for enhanced biological nutrient removal from wastewater

In the last decades, the awareness of environmental issues has increased in society considerably. There is an increasing need to improve the effluent quality of domestic wastewater treatment processes. This thesis describes the application of the Sequencing Batch Reactor (SBR) technology for Biological Nutrient Removal (BNR) from the wastewater. In particular, the work presented evolves from the nitrogen removal to the biological nutrient removal (i.e. nitrogen plus phosphorous removal) with special attention to the operational strategy design, the identification of possible reactor cycle controls or the influent composition related to the process efficiency. In such sense, also the use of ethanol as an external carbon (when low influent Carbon:Phosphorus (C:P) or Carbon:Nitrogen (C:N) ratios are presented) are studied as an alternative to maintain the BNR efficiency.