Polycyclic aromatic hydrocarbons and toxic trace metals in seawater and sediments from the west coast of India and their bioaccumulation in some selected species of fishes

Polycyclic Aromatic Hydrocarbons and other toxic compounds from industrial effluents are noted for their high potency for skin, lung, bladder and gastrointestinal cancers. Increased industrialization, and population growth led to greater production of wastes, Pesticides and PAHs have received attention due to their carcinogenic effects. The main objectives of the study were; to collect base line data on the concentration of PAHs in seawater and sediment from the west coast of India, the concentration of PAHs in certain species of fishes, the comparative levels of PAHs in fish, the influence of sediment characteristics on the concentration of PAH in sediment, changes in PAH concentration in water, sediment and fish, to provide a base line concentration of trace metals in water, sediment and fish, the seasonal changes in content of selected trace metals in water, sediment and fish from the west coast of India. The present study revealed that a predominance of silt and clay at all stations in the off Cochin area. The study has provided comprehensive information available to date for PAHs in seawater, sediment and fishes from the west cost of India especially from the Quilon to Mangalore region.

Distribution of Polycyclic Aromatic Hydrocarbons in the Cochin Estuary and Backwaters

Department of Chemical Oceanography,Cochin University of Science and Technology

Studies on the effect of Polycyclic Aromatic Hydrocarbons in the life and activity of Perna spp

In the present study an endeavour has been made to analyse the acute toxicity of WAFs of Bombay High crude and Light Diesel oil on commercially important bivalve species Perna viridis and Perna indica by static bioassay methods. The toxic effects of chemicals in the WAF on the organisms ; their tissues and eventually on rate functions have been elucidated. Marine oil pollution not only affects productivity and quality of marine organisms but also eventually affects the health of human population due to a possible health risk by way of consumption of oil contaminated seafood

Biodegradation Of Phenol Using Spent Substrate Of Pleurotus Sp.

Phenol is an aromatic hydrocarbon which exists as a colorless or white solid in its pure state. Over the past several decades, there is growing concern about wide spread contamination of surface and ground water by phenol, due to rapid development of chemical and petrochemical industries. Phenol affects aquatic life even at relatively low concentration (5-25mg/L). Treatment for removal of phenol includes chemical as well as biological processes. Studies show that ligninases such as Lignin Peroxidase and Laccase, produced by Pleurotus sp., can degrade phenol. Spent substrate of Pleurotus mushrooms consists of ligninases. Present work was to investigate the potential of spent substrate of edible mushroom P. ostreatus for biodegradation of phenol. P. ostreatus was cultivated on paddy straw. After harvest, spent substrate was utilized for phenol degradation. According to the enzyme profile of two ligninases present in the spent substrate of P. ostreatus, maximum specific activity for Laccase was observed in 35 day old spent substrate and LiP activity was maximum in 56 day old spent substrate, which together contributed significantly for removal of phenol. Spent substrate of 35th and 56th day were each incubated with phenol sample (1:1w/v) for one day, which resulted in degradation of phenol by 48% and 45% respectively. From these results it appears that, spent substrate of P. ostreatus can be used effectively to remove phenol from industrial effluents

Investigations on the Effects of Petroleum Hydrocarbons on the Marine Bivalves Perna viridis (Linnaeus) and Sunetta scripta (Linne')

The thesis deals with different aspects connected with the distribution and toxicity of PHC in crude oils in the aquatic environment and marine molluscs. Information has been gathered and presented on the present status of research in the field based on a thorough review of recent literature. It is seen from the literature that the resident time of PHC becomes lesser and lesser when crude oil is discharged in large quantities into the coastal waters where excess oxygenation light penetration, temperature availability and strong tidal currents persist. This results in the reduction of the onslaught of oil pollution. This probably shows that taxic insult of crude oil in tropical shores will be relatively lesser than that occurring in temperate and boreal waters. However, there is no record of major episodal oil pollution comparable in quantum and extent to that of Torrey Canyon or Amoco Cadiz which prevents a more reliable analysis on the issue. Considerable controversy exists on the method of estimation of PHC in seawater. However, Ultra-violet fluorescence spectroscopy has been widely recommended as an analytical tool for the determination of total hydrocarbons. Similarly representation of values as chrysene equivalents has been recognised as the most reliable method of Quantum representation.

INVESTIGATIONS ON THE STRESS EFFECTS OF PETROLEUM HYDROCARBONS ON METAPENAEUS DOBSON (MIERS)

The present investigation has addressed the effects of PHC contaminated culture medium on the morphology, physiology and behaviour of shrimps. The shrimp Metapenaeus dobsoni is an important member of the crustacean animal community abounding the oil contaminated benthic regions of Cochin backwater system. Since it is known that true pollutants can disrupt the sustainability of ecosystems by its effect on species, populations and communities,a representative species was used for the study. The results discussed in this work is bound to help in understanding the ecotoxicant resistance that the animal may display under toxic conditions compared to dynamic steady-state systems in nature.

Biodegradation of phenolic compounds in different ecosystems in Cochin

The purpose of this study is to determine the ability of specifically adapted bacteria to degrade phenol and to quantify the rate of biodegradation at. Different concentrations by mixed as well as individual isolates. Regular quantitative analysis of phenolics and aerobic phenololytic heterotrophs from five different ecosystems were done during 1990-1991, and the ability of microorganisms isolated from those areas, to utilize phenol, o-cresol and orcinol was also studied. In addition, data on environmental parameters like temperature, dissolved oxygen, salinity, pH, organic carbon and nutrients were also collected during the period of study The present study is one of its first kind in natural aquatic environment and has aimed to bring out some idea about the potential phenol biodegrades in such environments where the phenol concentration is beyond permitted level.

Biochemical Effects of Petroleum Hydrocarbons on the Tropical Teleost Oreochromis mossambicus (Peters)

The present work is a base—|ine attempt to investigate and assess the toxicity of water-accommodated fractions (WAF) of Bombay High crude oil. The experimental animal selected for the present study is a euryhaline teleost, Oreochromis mossambicus (Peters), adapted to fresh water. The fish has been selected on account of its economic valve, abundant availability, experimental feasibility, ease of rearing and maintenance and also because it is one of the commonly cultured species in the South-East Asian countries.

Investigations on the stress effects of petroleum hydrocarbons on Metapenaeus dobsoni (Miers)

The present investigation has addressed the eflects of PHC contaminated culture medium on the morphology, physiology and behaviour of shrimps] The shrimp Metapenaeus dobsoni is an important member of the crustacean animal community abounding the oil contaminated benthic regions of Cochin backwater system. Since it is known that true pollutants can disrupt the sustainability of ecosystems by its eflect on species, populations and communities, a representative species was used for the study. The results discussed in this work is bound to help in understanding the ecotoxicant resistance that the animal may display under toxic conditions compared to aynamic steaay-state systems in nature

“A comparative study of medium and large pore zeolites in alkylation reactions”

Zeolites have established themselves as industrial catalysts for over two decades for a variety of hydrocarbon processing reactions where acidity and shape selectivity are important factors. As solid catalysts, zeolites may be advantageous and superior compared to their homogenous counterparts due to their characteristic properties. It is only in recent years that the utility of zeolites for organic synthesis is recognized for producing specific organic intermediates and fine chemicals in high selectivity. In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of oxylene. . The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/Al ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation/ acylation reactions. The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta ofi'ers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Effect of Amylase Producing Vibrios From the Benthic Environment on the Biodegradation of Low Density Polyethylene-Dextrin Blends

Low-density polyethylene was mixed with dextrin having different particle sizes (100, 200 and 300 mesh). Various compositions were prepared and their mechanical properties were evaluated and thermal studies have been carried out. Biodegradability of these samples has been checked using liquid culture medium containing Vibrios (an amylase producing bacteria), which were isolated from marine benthic environment. Soil burial test was done and reprocessability of these samples was evaluated. The results indicate that the newly prepared blends are reprocessable without sacrificing much of their mechanical properties. The biodegradability tests on these blends indicate that these are partially biodegradable

Bioremediation of Hydrocarbons by Lysinibacillus fusiformis BTTS10

There exists a need for potential microorganism that could facilitate effective bioremediation of crude oil pollutants in the environment. Hence it was desired to isolate a potential bacterium from marine sediment, which often experiences oil pollution and develop a bioprocess for crude oil biodegradation. In the present study the sediment deposits in the beach of Munakkal, Trichur dist, Kerala, collected immediately after the major event Tsunami in 2004 was collected and analyzed by enrichment culture technique towards isolation of potential strains that could degrade crude oil and its fractions. From the results obtained it was found that the sediment deposits harbor several bacteria with potential for degrading hydrocarbons. However, among the strains obtained, isolate no. BTTS 10 showed capabilities for utilizing both alkanes and aromatic hydrocarbons and hence the same was selected for further studies.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Effect of curing temperature , fibre loading and bonding agent on the equilibrium swelling of isora-natural rubbercomposites

Isora fibre-reinforced natural rubber (NR) composites were cured at 80, 100, 120 and 150°C using a low temperature curing accelerator system. Composites were also prepared using a conventional accelerator system and cured at 150°C. The swelling behavior of these composites at varying fibre loadings was studied in toluene and hexane. Results show that the uptake of solvent and volume fraction of rubber due to swelling was lower for the low temperature cured vulcanizates which is an indication of the better fibre/rubber adhesion. The uptake of aromatic solvent was higher than that of aliphatic solvent, for all the composites. As the fibre content increased, the solvent uptake decreased, due to the superior solvent resistance of the fibre and good fibre-rubber interactions. The bonding agent improved the swelling resistance of the composites due to the strong interfacial adhesion. Due to the improved adhesion between the fibre and rubber, the ratio of the change in volume fraction of rubber due to swelling to the volume fraction of rubber in the dry sample (V,) was found to decrease in the presence of bonding agent. At a fixed fibre loading, the alkali treated fibre composite showed a lower percentage swelling than untreated one for both systems showing superior rubber-fibre interactions.

Swelling behaviour of isora/natural rubber composites in oils used in automobiles

Natural rubber/isora fibre composites were cured at various temperatures. The solvent swelling characteristics of natural rubber composites containing both untreated and alkali treated fibres were investigated in aromatic and aliphatic solvents like toluene, and n-hexane. The diffusion experiments were conducted by the sorption gravimetric method. The restrictions on elastomer swelling exerted by isora fibre as well as the anisotropy of swelling of the composite have been confirmed by this study. Composite cured at 100°C shows the lowest percentage swelling. The uptake of aromatic solvent is higher than that of aliphatic solvent for the composites cured at all temperatures. The effect of fibre loading on the swelling behaviour of the composite was also investigated in oils like petrol, diesel, lubricating oil etc. The % swelling index and swelling coefficient of the composite were found to decrease with increase in fibre loading. This is due to the increased hindrance exerted by the fibres at higher fibre loadings and also due to the good fibre-rubber interactions. Maximum uptake of solvent was observed with petrol followed by diesel and then lubricating oil. The presence of bonding agent in the composites restrict the swelling considerably due to the strong interfacial adhesion. At a fixed fibre loading, the alkali treated fibre composite showed lower percentage swelling compared to the untreated one.