Chemical Evaluation of Selected Organics and Trace Metals in the Mangrove Macroflora Of Cochin

Mangroves are considered to play a significant role in global carbon cycling. Themangrove forests would fix CO2 by photosynthesis into mangrove lumber and thus decrease the possibility of a catastrophic series of events - global warming by atmospheric CO2, melting of the polar ice caps, and inundation of the great coastal cities of the world. The leaf litter and roots are the main contributors to mangrove sediments, though algal production and allochthonous detritus can also be trapped (Kristensen et al, 2008) by mangroves due to their high organic matter content and reducing nature are excellent metal retainers. Environmental pollution due to metals is of major concern. This is due to the basic fact that metals are not biodegradable or perishable the way most organic pollutants are. While most organic toxicants can be destroyed by combustion and converted into compounds such as C0, C02, SOX, NOX, metals can't be destroyed. At the most the valance and physical form of metals may change. Concentration of metals present naturally in air, water and soil is very low. Metals released into the environment through anthropogenic activities such as burning of fossils fuels, discharge of industrial effluents, mining, dumping of sewage etc leads to the development of higher than tolerable or toxic levels of metals in the environment leading to metal pollution. Of course, a large number of heavy metals such as Fe, Mn, Cu, Ni, Zn, Co, Cr, Mo, and V are essential to plants and animals and deficiency of these metals may lead to diseases, but at higher levels, it would lead to metal toxicity. Almost all industrial processes and urban activities involve release of at least trace quantities of half a dozen metals in different forms. Heavy metal pollution in the environment can remain dormant for a long time and surface with a vengeance. Once an area gets toxified with metals, it is almost impossible to detoxify it. The symptoms of metal toxicity are often quite similar to the symptoms of other common diseases such as respiratory problems, digestive disorders, skin diseases, hypertension, diabetes, jaundice etc making it all the more difficult to diagnose metal poisoning. For example the Minamata disease caused by mercury pollution in addition to affecting the nervous system can disturb liver function and cause diabetes and hypertension. The damage caused by heavy metals does not end up with the affected person. The harmful effects can be transferred to the person's progenies. Ironically heavy metal pollution is a direct offshoot of our increasing ability to mass produce metals and use them in all spheres of existence. Along with conventional physico- chemical methods, biosystem approachment is also being constantly used for combating metal pollution

Assessment of trophic change and its probable impact on tropical estuarine environment (the Kodungallur-Azhikode estuary, India)

The cumulative effects of global change, including climate change, increased population density and domestic waste disposal, effluent discharges from industrial processes, agriculture and aquaculture will likely continue and increases the process of eutrophication in estuarine environments. Eutrophication is one of the leading causes of degraded water quality, water column hypoxia/anoxia, harmful algal bloom (HAB) and loss of habitat and species diversity in the estuarine environment. The present study attempts to characterize the trophic condition of coastal estuary using a simple tool; trophic index (TRIX) based on a linear combination of the log of four state variables with supplementary index Efficiency Coefficient (Eff. Coeff.) as a discriminating tool. Numerically, the index TRIX is scaled from 0 to10, covering a wide range of trophic conditions from oligotrophic to eutrophic. Study area Kodungallur-Azhikode Estuary (KAE) was comparatively shallow in nature with average depth of 3.6±0.2 m. Dissolve oxygen regime in the water column was ranged from 4.7±1.3 mgL−1 in Station I to 5.9±1.4 mgL−1 in Station IV. The average nitrate-nitrogen (NO3-N) of KAE water was 470 mg m−3; values ranged from Av. 364.4 mg m−3 at Station II to Av. 626.6 mg m−3at Station VII. The mean ammonium-nitrogen (NH4 +-N) varied from 54.1 mg m−3 at Station VII to 101 mg m−3 at Station III. The average Chl-a for the seven stations of KAE was 6.42±3.91 mg m−3. Comparisons over different spatial and temporal scales in the KAE and study observed that, estuary experiencing high productivity by the influence of high degree of eutrophication; an annual average of 6.91 TRIX was noticed in the KAE and seasonal highest was observed during pre monsoon period (7.15) and lowest during post monsoon period (6.51). In the spatial scale station V showed high value 7.37 and comparatively low values in the station VI (6.93) and station VII (6.96) and which indicates eutrophication was predominant in land cover area with comparatively high water residence time. Eff. Coeff. values in the KAE ranges from −2.74 during monsoon period to the lowest of −1.98 in pre monsoon period. Present study revealed that trophic state of the estuary under severe stress and the restriction of autochthonous and allochthonous nutrient loading should be keystone in mitigate from eutrophication process

ANALYSIS, MODIFICATION, AND EVALUATION OF THE COLD FLOW PROPERTIES OF VEGETABLE OILS AS BASE OIL FOR INDUSTRIAL LUBRICANTS

Poor cold flow properties of vegetable oils are a major problem preventing the usage of many abundantly available vegetable oils as base stocks for industrial lubricants. The major objective of this research is to improve the cold flow properties of vegetable oils by various techniques like additive addition and different chemical modification processes. Conventional procedure for determining pour point is ASTM D97 method. ASTM D97 method is time consuming and reproducibility of pour point temperatures is poor between laboratories. Differential Scanning Calorimetry (DSC) is a fast, accurate and reproducible method to analyze the thermal activities during cooling/heating of oil. In this work coconut oil has been chosen as representative vegetable oil for the analysis and improvement cold flow properties since it is abundantly available in the tropics and has a very high pour point of 24 °C. DSC is used for the analysis of unmodified and modified vegetable oil. The modified oils (with acceptable pour points) were then subjected to different tests for the valuation of important lubricant properties such as viscometric, tribological (friction and wear properties), oxidative and corrosion properties.A commercial polymethacrylate based PPD was added in different percentages and the pour points were determined in each case. Styrenated phenol(SP) was added in different concentration to coconut oil and each solution was subjected to ASTM D97 test and analysis by DSC. Refined coconut oil and other oils like castor oil, sunflower oil and keranja oil were mixed in different proportions and interesterification procedure was carried out. Interesterification of coconut oil with other vegetable oils was not found to be effective in lowering the pour point of coconut oil as the reduction attained was only to the extent of 2 to 3 °C.Chemical modification by acid catalysed condensation reaction with coconut oil castor oil mixture resulted in significant reduction of pour point (from 24 ºC to -3 ºC). Instead of using triacylglycerols, when their fatty acid derivatives (lauric acid- the major fatty acid content of coconut oil and oleic acid- the major fatty acid constituents of monoand poly- unsaturated vegetable oils like olive oil, sunflower oil etc.) were used for the synthesis , the pour point could be brought down to -42 ºC. FTIR and NMR spectroscopy confirmed the ester structure of the product which is fundamental to the biodegradability of vegetable oils. The tribological performance of the synthesised product with a suitable AW/EP additive was comparable to the commercial SAE20W30 oil. The viscometric properties (viscosity and viscosity index) were also (with out additives) comparable to commercial lubricants. The TGA experiment confirmed the better oxidative performance of the product compared to vegetable oils. The sample passed corrosion test as per ASTM D130 method.

Development of Best Practices for Ship Recycling Processes

Ship recycling has been considered as the best means to dispose off an obsolete ship. The current state of art of technology combined with the demands of sustainable developments from the global maritime industrial sector has modified the status of erstwhile ‘ship breaking’ involving ship scrap business to a modern industry undertaking dismantling of ships and recycling/reusing the dismantled products in a supply chain of pre owned product market by following the principles of recycling. Industries will have to formulate a set of best practices and blend them with the engineering activities for producing better quality products, improving the productivity and for achieving improved performances related to sustainable development. Improved performance by industries in a sustainable development perspective is accomplished only by implementing the 4E principles, ie.,. ecofriendliness, engineering efficiency, energy conservation and ergonomics in their core operations. The present study has done a comprehensive investigation into various ship recycling operations for formulating a set of best practices.Being the ultimate life cycle stage of a ship, ship recycling activities incorporate certain commercial procedures well in advance to facilitate the objectives of dismantling and recycling/reusing of various parts of the vessel. Thorough knowledge regarding these background procedures in ship recycling is essential for examining and understanding the industrial business operations associated with it. As a first step, the practices followed in merchant shipping operations regarding the decision on decommissioning have been and made available in the thesis. Brief description about the positioning methods and important preparations for the most feasible ship recycling method ie.,. beach method have been provided as a part of the outline of the background information. Available sources of guidelines, codes and rules & regulations for ship recycling have been compiled and included in the discussion.Very brief summary of practices in major ship recycling destinations has been prepared and listed for providing an overview of the global ship recycling activities. The present status of ship recycling by treating it as a full fledged engineering industry has been brought out to establish the need for looking into the development of the best practices. Major engineering attributes of ship as a unique engineering product and the significant influencing factors on her life cycle stage operations have been studied and added to the information base on ship recycling. Role of ship recycling industry as an important player in global sustainable development efforts has been reviewed by analysing the benefits of ship recycling. A brief synopsis on the state of art of ship recycling in major international ship recycling centres has also been incorporated in the backdrop knowledgebase generation on ship recycling processes.Publications available in this field have been reviewed and classified into five subject categories viz., Infrastructure for recycling yards and methods of dismantling, Rules regarding ship recycling activities, Environmental and safety aspects of ship recycling, Role of naval architects and ship classification societies, Application of information technology and Demand forecasting. The inference from the literature survey have been summarised and recorded. Noticeable observations in the inference include need of creation of a comprehensive knowledgebase on ship recycling and its effective implementation in the industry and the insignificant involvement of naval architects and shipbuilding engineers in ship recycling industry. These two important inferences and the message conveyed by them have been addressed with due importance in the subsequent part of the present study.As a part of the study the importance of demand forecasting in ship recycling has been introduced and presented. A sample input for ship recycling data for implementation of computer based methods of demand forecasting has been presented in this section of the thesis.The interdisciplinary nature of engineering processes involved in ship recycling has been identified as one of the important features of this industry. The present study has identified more than a dozen major stake holders in ship recycling having their own interests and roles. It has also been observed that most of the ship recycling activities is carried out in South East Asian countries where the beach based ship recycling is done in yards without proper infrastructure support. A model of beach based ship recycling has been developed and the roles, responsibilities and the mutual interactions of the elements of the system have been documented as a part of the study Subsequently the need of a generation of a wide knowledgebase on ship recycling activities as pointed out by the literature survey has been addressed. The information base and source of expertise required to build a broad knowledgebase on ship recycling operations have been identified and tabulated. Eleven important ship recycling processes have been identified and a brief sketch of steps involved in these processes have been examined and addressed in detail. Based on these findings, a detailed sequential disassembly process plan of ship recycling has been prepared and charted. After having established the need of best practices in ship recycling initially, the present study here identifies development of a user friendly expert system for ship recycling process as one of the constituents of the proposed best practises. A user friendly expert system has been developed for beach based ship recycling processes and is named as Ship Recycling Recommender (SRR). Two important functions of SRR, first one for the ‘Administrators’, the stake holders at the helm of the ship recycling affairs and second one for the ‘Users’, the stake holders who execute the actual dismantling have been presented by highlighting the steps involved in the execution of the software. The important output generated, ie.,. recommended practices for ship dismantling processes and safe handling information on materials present onboard have been presented with the help of ship recycling reports generated by the expert system. A brief account of necessity of having a ship recycling work content estimation as part of the best practices has been presented in the study. This is supported by a detailed work estimation schedule for the same as one of the appendices.As mentioned earlier, a definite lack of involvement of naval architect has been observed in development of methodologies for improving the status of ship recycling industry. Present study has put forward a holistic approach to review the status of ship recycling not simply as end of life activity of all ‘time expired’ vessels, but as a focal point of integrating all life cycle activities. A new engineering design philosophy targeting sustainable development of marine industrial domain, named design for ship recycling has been identified, formulated and presented. A new model of ship life cycle has been proposed by adding few stages to the traditional life cycle after analysing their critical role in accomplishing clean and safe end of life and partial dismantling of ships. Two applications of design for ship recycling viz, recyclability of ships and her products and allotment of Green Safety Index for ships have been presented as a part of implementation of the philosophy in actual practice.

Legal Control of Industrial Pollution

Industries constitute the main spring of development. Without industrial development no country could reach a stage in which a decent living for its citizens would be achieved. Increasing production to meet the basic needs of society augmented scientific invention and machine oriented industrial order.Environmental pollution ls a burning global issue. It is more serious and dangerous than terrorism. Started with the discovery of fire and development of civilization. Pollution went unnoticed throughout the centuries of human growth until its adverse effects on human environment become explicit.National concern tor environment started in our country only atter the cause of protection of environment received global attention. At present legal control ot industrial pollution is in a scattered framework of piece meal processes with overlapping provisions and authorities.Environmental protection- should be an item not only in the concurrent list of schedule 7 to the Constitution but also in the list of matters entrusted to the panchayati institutions in the Schedule 11. It is heartening to note that so far as municipalities are concerned the Constitution of India lives up to the expectation. In the wake of New Industrial Policy based on liberalisation a long list of small scale industries fall outside the purview of environmental clearance. The Indian concept of environmental im»act assessment introduced under the Environment Act by notification excludes the entire gamut of small scale industries and r.elates only to scheduled industries covered by the notifica~ion. Most of them are subjected to ETA only it the investment goes above ~.50 crores. This provision dilutes the impact assessment considerably A mandatory impact assessment with public partiCipation and with provision for a review by specialized environmental courts will eliminate the possible evils of this judicial passiveness.

Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)

The research work which was carried out to Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)Estuaries are considered as sink or source for terrestrial and various anthropogenically generated materials. These include naturally occurring elements Al, Si, Fe or trace inorganics or industrial pollutants of different types. There have been reports on both positive and negative impacts by the introduction of above materials into the ecosystem.This thesis deals with the trace metal Aluminium (Al) whose average concentration (about 8%) in the earths crust is surpassed only by that of Oxygen and Silicon. There can be no doubt that most of the land derived materials reaches the ocean through rivers via estuaries. An important aspect noticed here is that the concentration of dissolved Al is much lower in sea water than in river water.On critically analysing Cochin estuary, for the entire cycles, covering monsoon, postmonsoon and premonsoon, the following salient features are documented as hereunder. Dissolved Al exhibits high and variable trends in Cochin estuary, the influencing parameters being salinity, SPM, pH and dissolved Si. A general profile showed removal in upper/mid estuary followed by regeneration in the mid/lower estuary and further decrease seawards in the southern/northem arms.Distribution appears to be a function of freshwater input, the monsoon season exhibiting very high concentrations throughout the estuary. As the river discharge decreased with the progress of seasons, dissolved Al concentration also decreased, the metal limiting itself to the upper and mid estuary.

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.