Continental surface water and energy budgets in the XX and XXI centuries

Tese de doutoramento, Ciências Geofísicas e da Geoinformação (Meteorologia), Universidade de Lisboa, Faculdade de Ciências, 2015

Syngas production by water electrolysis: preliminary tests on methane production

Master Thesis to obtain the Master degree in Chemical Engineering - Branch Chemical Processes

Biochemistry of grape berries: post-genomics approaches to uncover the effects of water deficits on ripening

Dissertation presented to obtain the Ph.D degree in Biochemistry, Plant Physiology

Microcystin-LR detection in water by the Fabry–Pérot interferometer using an optical fibre coated with a sol–gel imprinted sensing membrane

Cyanobacteria deteriorate the water quality and are responsible for emerging outbreaks and epidemics causing harmful diseases in Humans and animals because of their toxins. Microcystin-LR (MCT) is one of the most relevant cyanotoxin, being the most widely studied hepatotoxin. For safety purposes, the World Health Organization recommends a maximum value of 1 μg L−1 of MCT in drinking water. Therefore, there is a great demand for remote and real-time sensing techniques to detect and quantify MCT. In this work a Fabry–Pérot sensing probe based on an optical fibre tip coated with a MCT selective thin film is presented. The membranes were developed by imprinting MCT in a sol–gel matrix that was applied over the tip of the fibre by dip coating. The imprinting effect was obtained by curing the sol–gel membrane, prepared with (3-aminopropyl) trimethoxysilane (APTMS), diphenyl-dimethoxysilane (DPDMS), tetraethoxysilane (TEOS), in the presence of MCT. The imprinting effect was tested by preparing a similar membrane without template. In general, the fibre Fabry–Pérot with a Molecular Imprinted Polymer (MIP) sensor showed low thermal effect, thus avoiding the need of temperature control in field applications. It presented a linear response to MCT concentration within 0.3–1.4 μg L−1 with a sensitivity of −12.4 ± 0.7 nm L μg−1. The corresponding Non-Imprinted Polymer (NIP) displayed linear behaviour for the same MCT concentration range, but with much less sensitivity, of −5.9 ± 0.2 nm L μg−1. The method shows excellent selectivity for MCT against other species co-existing with the analyte in environmental waters. It was successfully applied to the determination of MCT in contaminated samples. The main advantages of the proposed optical sensor include high sensitivity and specificity, low-cost, robustness, easy preparation and preservation.

A spatial modelling framework for assessing climate change impacts on freshwater ecosystems: Response of brown trout (Salmo trutta L.) biomass to warming water temperature

Mountain regions worldwide are particularly sensitive to on-going climate change. Specifically in the Alps in Switzerland, the temperature has increased twice as fast than in the rest of the Northern hemisphere. Water temperature closely follows the annual air temperature cycle, severely impacting streams and freshwater ecosystems. In the last 20 years, brown trout (Salmo trutta L) catch has declined by approximately 40-50% in many rivers in Switzerland. Increasing water temperature has been suggested as one of the most likely cause of this decline. Temperature has a direct effect on trout population dynamics through developmental and disease control but can also indirectly impact dynamics via food-web interactions such as resource availability. We developed a spatially explicit modelling framework that allows spatial and temporal projections of trout biomass using the Aare river catchment as a model system, in order to assess the spatial and seasonal patterns of trout biomass variation. Given that biomass has a seasonal variation depending on trout life history stage, we developed seasonal biomass variation models for three periods of the year (Autumn-Winter, Spring and Summer). Because stream water temperature is a critical parameter for brown trout development, we first calibrated a model to predict water temperature as a function of air temperature to be able to further apply climate change scenarios. We then built a model of trout biomass variation by linking water temperature to trout biomass measurements collected by electro-fishing in 21 stations from 2009 to 2011. The different modelling components of our framework had overall a good predictive ability and we could show a seasonal effect of water temperature affecting trout biomass variation. Our statistical framework uses a minimum set of input variables that make it easily transferable to other study areas or fish species but could be improved by including effects of the biotic environment and the evolution of demographical parameters over time. However, our framework still remains informative to spatially highlight where potential changes of water temperature could affect trout biomass. (C) 2015 Elsevier B.V. All rights reserved.-

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Water and electrolyte content and distribution in tissues of thermally-acclimated rainbow trout, Salmo gairdneri

The primary objective of this investigation was that of providing a comprehensive tissue-by-tissue assessment of water-electrolyte status in thermally-acclimated rainbow trout, Salmo gairdneri. To this end levels of water and the major ions, sodium, chloride and potassium were evaluated in the plasma, at three skeletal muscle sites, and in cardiac muscle, liver, spleen, gut and brain of animals acclimated to 2°, 10° and 18°C. The occurrence of possible seasonal variations in water-electrolyte balance was evaluated by sampling sununer and late fall-early winter populations of trout. On the basis of values for water and electrolyte content, estimates of extracellular and cellular phase volumes, cellular electrolyte concentrations and Nernst equilibrium potentials were made. Since accurate assessment of the extracellular phase volume is critical in the estimation of cellular electrolyte concentrations and parameters based on assumed cellular ion levels, [14 C]-polyethylene glycol-4000, which is assumed to be confined to the extracellular space, was employed to provide comparisons with various ion-defined spaces (H20~~s, H20~~/K and H20~~s). Subsequently, the ion-defined space yielding the most realistic estimate of extracellular phase volume for each tissue was used in cellular electrolyte calculations. Water and electrolyte content and distribution varied with temperature. Tissues, such as liver, spleen and brain appeared to be the most thermosensitive, whereas skeletal and cardiac muscle and gut tissue were less influenced. 'Summer' series trout appeared to be more capable of maintaining their water- electrolyte balance than the ~fall-winter' series animals. i The data are discussed in terms of their possible effect on maintenance of appropriate cellular metabolic and electrophysiological functions.

The Alberta Dilemma: Optimal Sharing of a Water Resource by an Agricultural and an Oil Sector

The purpose of this paper is to characterize the optimal time paths of production and water usage by an agricultural and an oil sector that have to share a limited water resource. We show that for any given water stock, if the oil stock is sufficiently large, it will become optimal to have a phase during which the agricultural sector is inactive. This may mean having an initial phase during which the two sectors are active, then a phase during which the water is reserved for the oil sector and the agricultural sector is inactive, followed by a phase during which both sectors are active again. The agricultural sector will always be active in the end as the oil stock is depleted and the demand for water from the oil sector decreases. In the case where agriculture is not constrained by the given natural inflow of water once there is no more oil, we show that oil extraction will always end with a phase during which oil production follows a pure Hotelling path, with the implicit price of oil net of extraction cost growing at the rate of interest. If the natural inflow of water does constitute a constraint for agriculture, then oil production never follows a pure Hotelling path, because its full marginal cost must always reflect not only the imputed rent on the finite oil stock, but also the positive opportunity cost of water.

Studies on the Deep - Water Crab Charybdis (Goniohellenus ) Smithii Macleay From the Seas Around India

The present study deals with a general introduction which outlines the objective of the study providing an exhaustive review of works on crabs with particular reference to deep-sea forms. In the first section, Taxonomy and Geographical disribution of the crab are dealt with. The species is described in detail based on several male and female specimens obtained from the pelagic and bottom collections, and its identity in Indian waters is established. It is also distinguished from a closely allied species so far not reported from Indian waters. The second section comprises the biology of the species and it is dealt with under four subheading, namely Habit and Habitats, Reproduction, Food and feeding and Proximate composition. The different habitats occupied by juveniles, subadults and adults of the species have been described and discussed in the light of available information on differential distribution of other related species. The reproductive biology is described in various details touching on gross anatomy and histology of the reproductive systems, spermatogenesis, oogenesis, size at maturity, ovarian maturation process, fecundity, egg carriage and breeding. The food and feeding habits of the species have been studied with reference to the different life stages such as juveniles, subadults and adults during the different phases of life based on stomach content analysis. The percentage of meat recovery and protein, carbohydrate and lipid content of meat have been described in the section dealing with proximate composition. In section three the distribution and abundance of the crab for the entire Indian EEZ and some contiguous ares have been described and illustrated in detail separately for pelagic and benthic realms. The size frequency disrtibution, sex ratios, length weight relationship and relative abundance of breeding population in the experimental catches have been dealt with in detail and discussed.

Geochemistry of transition, non-transition and rare-earth elements in the surficial sediments of continental shelf of Kerala and an annex to the Cochin estuarine system

The metals present in the surface sediments have high demand on a global perspective, and the main reservoir of these elements is believed to be the ocean floor. A lot of studies on metals are going on throughout the world for its quantification and exploitation. Even though, some preliminary attempts have been made in selected areas for the quantitative study of metals in the western continental shelf of India, no comprehensive work has been reported so far. The importance of this study also lies on the fact that there has not been a proper evaluation of the impact of the Great Tsunami of 2004 on the coastal areas of the south India. In View of this, an attempt has been made to address the seasonal distribution, behavior and mechanisms which control the deposition of metals in the sediments of the western continental shelf and Cochin Estuary, an annex to this coastal marine region.Surface sediment samples were collected seasonally from two subenvironemnts of southwest coast of India, (continental shelf of Kerala and Cochin estuarine system), to estimate the seasonal distribution and geochemical behavior of non-transition, transition, rare-earth elements, Th and U. Bottom water samples were also taken from each station, and analysed for temperature, salinity and dissolved oxygen, hence the response of redox sensitive elements to oxygen minimum zone can be addressed. In addition, other sedimentary parameters such as sand, silt, clay fractions, CaCO3 and organic carbon content were also estimated to evaluate the control factors on level of metals present in the sediment. The study used different environmental data analysis techniques to evaluate the distribution and behavior of elements during different seasons. This includes environmental parameters such as elemental normalisation, enrichment factor, element excess, cerium and europium anomalies and authigenic uranium.

Seasonal and interannual variability of sea level and associated surface meteorological parameters at Cochin

This thesis entitled seasonal and interannual variability of sea level and associated surface meteorological parameters at cochin.The interesting aspect of studying sea level variability on different time scales can be attributed to the diversity of its applications.Study of tides could perhaps be the oldest branch of physical oceanography.The thesis is presented in seven chapters. The first chapter gives, apart from a general introduction, a survey of literature on sea level variability on different time scales - tidal, seasonal and interannual (geological scales excluded), with particular emphasis on the work carried out in the Indian waters. The second chapter is devoted to the study of observed tides at Cochin on seasonal and interannual time scales using hourly water level data for the period 1988-1993. The third chapter describes the long-term climatology of some important surface oceanographic and meteorological parameters (at Cochin) which are supposed to affect the sea level. The fourth chapter addresses the problem of seasonal forecasting of the meteorological and oceanographic parameters at Cochin using autoregressive, sinusoidal and exponentially weighted moving average techniques and testing their accuracy with the observed data for the period 1991-1993. The fifth chapter describes the seasonal cycles of sea level and the driving forces at 16 stations along the Indian subcontinent. It also addresses the observed interannual variability of sea level at 15 stations using available multi-annual data sets. The sixth chapter deals with the problem of coastal trapped waves between Cochin and Beypore off the Kerala coast using sea level and atmospheric pressure data sets for the year 1977. The seventh and the last chapter contains the summary and conclusions and future outlook based on this study.

Development of Zero Water Exchange Shrimp Culture System Integrated With Bioremediation of Detritus and Ammonia- Nitrogen

Aquaculture is one of the fastest growing food sectors in the world. Amongst the various branches of aquaculture, shrimp culture has expanded rapidly across the globe because of its faster growth rate, short culture period, high export value and demand in the International market. Indian shrimp farming has experienced phenomenal development over the decades due to its excellent commercial viability. Farmers have adopted a number of innovative technologies to improve the production and to maximize the returns per unit area. The culture methods adopted can be classified in to extensive, modified extensive and semi intensive based on the management strategies adopted in terms of pond size, stocking density, feeding and environmental control. In all these systems water exchanges through the natural tidal effects, or pump fed either from creek or from estuaries is a common practice. In all the cases, the systems are prone to epizootics due to the pathogen introduction through the incoming water, either brought by vectors, reservoir hosts, infected tissue debris and free pathogens themselves. In this scenario, measures to prevent the introduction of pathogen have become a necessity to protect the crop from the onslaught of diseases as well as to prevent the discharge of waste water in to the culture environment.The present thesis deals with Standardization of bioremediation technology for zero water exchange shrimp culture system

“Urban Water Supply Management: A Study Of Centralised And Community Based Systems In Calicut City

Studies in urban water supply system are few in the state of Kerala. It is a little researched area. In the case of water pricing a number of studies are available. In Kerala state, exception to Jacob John’s study on “Economics of Public Water Supply System”, which is a case study of Trivandrum Water Supply System in 1997, no exhaustive research work has so far come out in this field. loreover no indepth research study has come up, so far, relating to household ater demand analysis and the distribution system of urban piped water supply. he proposed study is first of its kind, which focuses on the distributional and Iailability problems of piped water supply in an urban centre in Kerala state. Hence there is a felt need for enquiring into the sufficiency of )table water supplied to people in urban areas and the efficiency maintained in roviding the scarce resource and preventing its misuse by the consumers. It is in llS backdrop that this study was undertaken and its empirical part was conducted |Calicut city in the state of Kerala. Study is confined to the water supply system ithe city of Calicut

Water quality status and Primary productivity of Valanthakad Backwater in Kerala

The water quality and primary productivity of Valanthakad backwater (9° 55 10. 24 N latitude and 76° 20 01. 23 E longitude) was monitored from June to November 2007. Significant spatial and temporal variations in temperature, transparency, salinity, pH, dissolved oxygen, sulphides, carbon dioxide, alkalinity, biochemical oxygen demand, phosphatephosphorus, nitrate-nitrogen, nitrite-nitrogen as well as primary productivity could be observed from the study. Transparency was low (53.75 cm to 159 cm) during the active monsoon months when the intensity of solar radiation was minimum, which together with the run off from the land resulted in turbid waters in the study sites. The salinity in both the stations was low (0.10 ‰ to 4.69 ‰) except in August and November 2007. The presence of total sulphide (0.08 mg/ l to 1.84 mg/ l) and higher carbon dioxide (3 mg/ l to 17 mg/ l) could be due to hospital discharges and decaying slaughter house wastes in Station 1 and also from the mangrove vegetation in Station 2. Nitrate-nitrogen and phosphate-phosphorus depicted higher values and pronounced variations in the monsoon season. Maximum net primary production was seen in November (0.87 gC/ m3/ day) and was reported nil in September. The chlorophyll pigments showed higher values in July, August and November with a negative correlation with phosphate-phosphorus and nitrite-nitrogen. The study indicated that the water quality and productivity of Valanthakad backwater is impacted and is the first report from the region

Modelling and simulation of a photovoltaic fuel cell hybrid system

A stand-alone power system is an autonomous system that supplies electricity to the user load without being connected to the electric grid. This kind of decentralized system is frequently located in remote and inaccessible areas. It is essential for about one third of the world population which are living in developed or isolated regions and have no access to an electricity utility grid. The most people live in remote and rural areas, with low population density, lacking even the basic infrastructure. The utility grid extension to these locations is not a cost effective option and sometimes technically not feasible. The purpose of this thesis is the modelling and simulation of a stand-alone hybrid power system, referred to as “hydrogen Photovoltaic-Fuel Cell (PVFC) hybrid system”. It couples a photovoltaic generator (PV), an alkaline water electrolyser, a storage gas tank, a proton exchange membrane fuel cell (PEMFC), and power conditioning units (PCU) to give different system topologies. The system is intended to be an environmentally friendly solution since it tries maximising the use of a renewable energy source. Electricity is produced by a PV generator to meet the requirements of a user load. Whenever there is enough solar radiation, the user load can be powered totally by the PV electricity. During periods of low solar radiation, auxiliary electricity is required. An alkaline high pressure water electrolyser is powered by the excess energy from the PV generator to produce hydrogen and oxygen at a pressure of maximum 30bar. Gases are stored without compression for short- (hourly or daily) and long- (seasonal) term. A proton exchange membrane (PEM) fuel cell is used to keep the system’s reliability at the same level as for the conventional system while decreasing the environmental impact of the whole system. The PEM fuel cell consumes gases which are produced by an electrolyser to meet the user load demand when the PV generator energy is deficient, so that it works as an auxiliary generator. Power conditioning units are appropriate for the conversion and dispatch the energy between the components of the system. No batteries are used in this system since they represent the weakest when used in PV systems due to their need for sophisticated control and their short lifetime. The model library, ISET Alternative Power Library (ISET-APL), is designed by the Institute of Solar Energy supply Technology (ISET) and used for the simulation of the hybrid system. The physical, analytical and/or empirical equations of each component are programmed and implemented separately in this library for the simulation software program Simplorer by C++ language. The model parameters are derived from manufacturer’s performance data sheets or measurements obtained from literature. The identification and validation of the major hydrogen PVFC hybrid system component models are evaluated according to the measured data of the components, from the manufacturer’s data sheet or from actual system operation. Then, the overall system is simulated, at intervals of one hour each, by using solar radiation as the primary energy input and hydrogen as energy storage for one year operation. A comparison between different topologies, such as DC or AC coupled systems, is carried out on the basis of energy point of view at two locations with different geographical latitudes, in Kassel/Germany (Europe) and in Cairo/Egypt (North Africa). The main conclusion in this work is that the simulation method of the system study under different conditions could successfully be used to give good visualization and comparison between those topologies for the overall performance of the system. The operational performance of the system is not only depending on component efficiency but also on system design and consumption behaviour. The worst case of this system is the low efficiency of the storage subsystem made of the electrolyser, the gas storage tank, and the fuel cell as it is around 25-34% at Cairo and 29-37% at Kassel. Therefore, the research for this system should be concentrated in the subsystem components development especially the fuel cell.