Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.

A simple approach for the estimation of food consumption from growth rates at different environmental conditions and its application to juvenile cod (Gadus morhua L.) of a fjordic sea loch on the west coast of Scotland

Abstract Growth and condition of fish are functions of available food and environmental conditions. This led to the idea of using fish as a “consumption sensor” for the measurement of food intake over a defined period of time. A bio-physical model for the estimation of food consumption was developed based on the von Bertalanffy model. Whereas some of the input variables of the model, the initial and final lengths and masses of a fish and the temperature within the time period considered can easily be measured, internal characteristics of the species have to be determined indirectly. Three internal parameters are used in the model: the maintenance consumption at 0°C, the temperature dependence of this consumption and the food efficiency, the percentage of the ingested food utilized. Estimates of the parameters for a given species can be determined by feeding experiments. Here, data from published feeding experiments on juvenile cod, Gadus morhua L., were used to validate the model. The average of the relative error for the food intake predicted by the model for individual fish was about 24 %, indicating that fish used the food with different efficiencies. However, grouping the fish according to size classes and temperature lowered the relative error of the predicted food intake for the group to typically 5 %. For a group containing all fish of the feeding experiment the relative prediction error was about 2 %. Zusammenfassung Wachstum und Kondition der Fische sind von der verfügbaren Nahrung und von Umweltbedingungen abhängig. Dies führte zur Idee, Fisch als „Konsum-Sensor“ für die Messung der Nahrungsaufnahme über einen definierten Zeitraum zu verwenden. Auf Grundlage des von Bertalanffy-Modells wurde ein bio-physikalisches Modell zur Schätzung der Futteraufnahme entwickelt. Während einige der Eingangsgrößen des Modells leicht gemessen werden können (Anfangs- und Endlänge und -körpermasse der Fische und die Temperatur innerhalb des betrachteten Zeitraum), können interne Parameter der betrachteten Art nur indirekt bestimmt werden. Drei interne Parameter werden in dem Modell verwendet: Die Erhaltungskonsumtion bei 0° C, die Temperaturabhängigkeit dieser Rate und der Wirkungsgrad der Nahrung (der Anteil der Nahrung ,der aufgenommen und verwendet und nicht ungenutzt wieder ausgeschieden wird). Die Modellparameter für eine bestimmte Art können durch Fütterungsversuche bestimmt werden. Um das Modell zu validieren wurden Daten aus veröffentlichten Fütterungsversuchen mit juvenilen Kabeljau (Gadus morhua L.) verwendet. Modell und Wirklichkeit weichen in der Regel voneinander ab. Der durchschnittliche relative Fehler der durch das Modell vorhergesagten Nahrungsaufnahme betrug für Einzelfische etwa 24%, was darauf hinweist, dass einzelne Fisch die Nahrung mit unterschiedlichen Wirkungsgraden verwerten. Allerdings senkte die Gruppierung der Fische nach Größenklassen und Temperatur den relativen Vorhersagefehler für die Nahrungsaufnahme der Gruppe auf etwa 5%. Für alle Fische im Fütterungsversuch ist der relative Vorhersagefehler etwa 2%.

Environmental variables and fisheries diversity of the Naaf River Estuary, Bangladesh

The Naaf River estuary is one of the large estuaries in the Bangladesh coastal region not to have been affected by extensive human disturbance. This research provides information about the fisheries diversity status by Estuarine Set Bag Net (ESBN) sampling relation to physicochemical variables in both spatio-temporal scales. About 25 km of the lower estuary was divided into six zones for sample collection by considering the accessibility and availability of the ESBN operation, fish landing centers and location of the fishing villages. In total 48 samples have been analyzed which were taken throughout March to October 2006. To quantify the species diversity, all fisheries data were analyzed by using EstimateS and EcoSim software which accounts the different diversity indices viz., species richness, Shannon–Wiener diversity Index, Dominance and Evenness index. The research results demonstrate that the Naaf River estuary is a habitat of 161 (species richness, Sobs=161, Choa 1=162±2.34, ACE=161.73) different species which belong to 98 fin fishes, 23 shrimps and prawns,13 crabs, 11 molluscs, 3 echinoderms, 4 other crustaceans;while 9 remain unidentified. Results on the aquatic environment,mainly salinity and turbidity were found to have a major influence on their occurrence and distribution. All the findings indicated that the Naaf River estuary is a highly productive system and provides a favourable environment for large variety of estuarine species assemblages.

Caracterização ambiental da bacia hidrogáfica do Rio São Domingos a partir da análise geoquímica e isotópica Pb/Pb

A bacia hidrográfica do rio São Domingos constitui uma das sub-bacias do rio Muriaé pertencente ao sistema Paraíba do Sul e, tem seus limites coincidentes com os limites do município de São José de Ubá, sendo este o segundo maior produtor de tomate do estado do Rio de Janeiro, com sua principal fonte econômica baseada na agropecuária. Este tipo de atividade resulta em utilização de produtos químicos nas lavouras e juntamente a ocupação inadequada resulta em modificação das paisagens e da mata nativa, resultando em diversos tipos de impactos no ambiente. Neste estudo foram abordados os impactos relacionados a concentração de metais e sua proveniência através das assinaturas isotópicas Pb/Pb, utilizando para tal o procedimento analítico de lixiviação dos sedimentos de corrente e abertura total de rochas para a obtenção de razões isotópicas e concentrações de metais por ICP-MS. Os resultados mostraram que as contribuições nos sedimentos de corrente se dão a partir de cinco fontes compreendidos no intervalo de assinatura isotópica 206Pb/207Pb 1,1229 e 1,1949, representadas em intervalos bem definidos. Por correlação com as respectivas concentrações se observa que, preferencialmente, existe maior influência das rochas do embasamento, seguido de atividade antrópicas como a urbanização e disposição de lixo doméstico. As maiores concentrações estão associadas ao cobre, chumbo, estrôncio, níquel e zinco. Contudo todas as concentrações de metais obtidas se encontram abaixo da legislação vigente. Desta forma a contaminação antrópica é limitada a regiões de maior densidade populacional e as influências naturais predominam na área da bacia.

Sensitivity of sturgeons to environmental hypoxia: a review of physiological and ecological evidence

In this essay, three lines of evidence are developed that sturgeons in the Chesapeake Bay and elsewhere are unusually sensitive to hypoxic conditions: 1. In comparison to other fishes,sturgeons have a limited behavioral and physiological capacity to respond to hypoxia. Basal metabolism, growth, feeding rate, and survival are sensitive to changes in oxygen level, which may indicate a relatively poor ability of sturgeons to oxyregulate. 2. During summertime, temperatures >20°C amplify the effect of hypoxia on sturgeons and other fishes due to a temperature oxygen "squeeze" (Coutant 1987). In bottom waters, this interaction results in substantial reduction of habitat; in dry years, sturgeon nursery habitats in the Chesapeake Bay may be particularly reduced or even eliminated. 3. While evidence for population level effects due to hypoxia is circumstantial, there are corresponding trends between the absence of Atlantic sturgeon reproduction in estuaries like the Chesapeake Bay where summertime hypoxia predominates on a system-wide scale. Also, the recent and dramatic recovery of shortnose sturgeon in the Hudson River (4-bid increase in abundance from 1980 to1995) may have been stimulated by improvement of a large portion of the nursery habitat that was restored from hypoxia to normoxia during the period 1973-1978.

Tecnologia mais limpa aplicada ao tratamento de água em sistemas de resfriamento abertos com recirculação

Os estudos destinados à aplicação de uma tecnologia mais limpa ao tratamento de águas em sistemas de resfriamento abertos com recirculação resultaram no desenvolvimento de uma filosofia de tratamento baseada na busca de uma operação com ciclo de concentração ideal. Assim, por meio do controle do balanço material no sistema de resfriamento, seria alcançado um nível de concentração em que a água de circulação apresentaria, naturalmente e ao mesmo tempo, baixa tendência à corrosão do ferro e baixa tendência à formação de incrustação de carbonato de cálcio. O tratamento com inibidores de corrosão e de formação de depósitos seria apenas complementar e, conseqüentemente, reduzido o emprego de produtos químicos para o condicionamento da água. O presente trabalho procura demonstrar que o critério de tratamento baseado apenas no índice de estabilidade não leva em conta o fato de que as espécies solúveis em água não se concentram de uma mesma forma, principalmente como decorrência de reações de conversão envolvendo o íon bicarbonato e de precipitação do íon cálcio. Como suporte desse trabalho, foram realizados ensaios de campo em um sistema de resfriamento aberto com recirculação em operação normal, porém sem tratamento químico da água. Foi possível, desse modo, observar a variação da concentração de cada espécie crítica presente na água com a vazão de descarga efetuada. Os resultados obtidos e o estudo realizado mostram que a metodologia tradicional pode apresentar desvios da realidade que podem comprometer a qualidade do tratamento, obrigando o emprego de maiores concentrações de produtos químicos para condicionamento da água, contrariando, assim, o próprio propósito original de execução de um tratamento dentro dos princípios de uma produção mais limpa. Este trabalho procura, ainda, salientar a importância qualitativa e quantitativa das espécies presentes, na água de reposição, na qualidade do tratamento, alertando que o emprego de reúso de água, como reposição de um sistema de resfriamento, deve ser criteriosamente analisado, pois uma água de má qualidade pode tornar o tratamento interno impraticável, exigindo a execução de um tratamento prévio muitas vezes inviável do ponto de vista econômico e causador de impacto ambiental

Palladium-Catalyzed Decarboxylative and Decarbonylative Transformations in the Synthesis of Fine and Commodity Chemicals

Decarboxylation and decarbonylation are important reactions in synthetic organic chemistry, transforming readily available carboxylic acids and their derivatives into various products through loss of carbon dioxide or carbon monoxide. In the past few decades, palladium-catalyzed decarboxylative and decarbonylative reactions experienced tremendous growth due to the excellent catalytic activity of palladium. Development of new reactions in this category for fine and commodity chemical synthesis continues to draw attention from the chemistry community.

The Stoltz laboratory has established a palladium-catalyzed enantioselective decarboxylative allylic alkylation of β-keto esters for the synthesis of α-quaternary ketones since 2005. Recently, we extended this chemistry to lactams due to the ubiquity and importance of nitrogen-containing heterocycles. A wide variety of α-quaternary and tetrasubstituted α-tertiary lactams were obtained in excellent yields and exceptional enantioselectivities using our palladium-catalyzed decarboxylative allylic alkylation chemistry. Enantioenriched α-quaternary carbonyl compounds are versatile building blocks that can be further elaborated to intercept synthetic intermediates en route to many classical natural products. Thus our chemistry enables catalytic asymmetric formal synthesis of these complex molecules.

In addition to fine chemicals, we became interested in commodity chemical synthesis using renewable feedstocks. In collaboration with the Grubbs group, we developed a palladium-catalyzed decarbonylative dehydration reaction that converts abundant and inexpensive fatty acids into value-added linear alpha olefins. The chemistry proceeds under relatively mild conditions, requires very low catalyst loading, tolerates a variety of functional groups, and is easily performed on a large scale. An additional advantage of this chemistry is that it provides access to expensive odd-numbered alpha olefins.

Finally, combining features of both projects, we applied a small-scale decarbonylative dehydration reaction to the synthesis of α-vinyl carbonyl compounds. Direct α-vinylation is challenging, and asymmetric vinylations are rare. Taking advantage of our decarbonylative dehydration chemistry, we were able to transform enantioenriched δ-oxocarboxylic acids into quaternary α-vinyl carbonyl compounds in good yields with complete retention of stereochemistry. Our explorations culminated in the catalytic enantioselective total synthesis of (–)-aspewentin B, a terpenoid natural product featuring a quaternary α-vinyl ketone. Both decarboxylative and decarbonylative chemistries found application in the late stage of the total synthesis.

Reference-growth rate – a simple and handy parameter summarizing the influence of environmental conditions

Abstract Environmental changes may have an impact on life conditions of the fish, e.g. food supply for the fish. The prevailing environmental conditions apply evenly to all age groups of one stock. Small fish have high growth rates, whereas large fish grow with low rates. But, it can be shown on the basis of the von Bertalanffy-growth model that it is sufficient to know only the growth rate of one single age group to compute the growth rates of all other age groups. The growth rate of a reference fish GRF (e.g. a fish with a body mass of 1 kg) was introduced as a reference growth describing the current food condition of all age groups of the stock. As an example a time series of the reference-growth rate of the northern cod stock (NAFO, 3K) was computed for the time span 1979 to 1999. For the northern cod stock it can be observed that environmental conditions caused growth rates below the long-term mean for seven years in a row. After a prolonged hunger period the fish stock collapsed in 1992 also by the impact of fisheries - and this was probably not a coincidence. Now, with the reference-growth rate GRF a simple and handy parameter was found to summarize the influence of the environmental conditions on growth and other derived models and therefore makes it easier to compute the influence of environmental changes within stock assessment. Zusammenfassung Veränderungen der Umwelt können Auswirkungen auf die Lebensbedingungen der Fische haben, z. B. auf das Nahrungsangebot der Fische. Die vorherrschenden Umgebungsbedingungen wirken gleichmäßig auf alle Altersgruppen eines Bestandes, wobei typischer Weise kleineFische hohe Wachstumsraten haben, während die großen Fische mit niedrigen Raten wachsen. Auf der Grundlage des von Bertalanffy-Wachstumsmodells kann gezeigt werden, dass es ausreicht, nur die Wachstumsrate von einer einzigen Altersgruppe zu kennen, um die Wachstumsraten von allen anderen Altersgruppen berechnen zu können. Die Wachstumsrate eines Referenz-Fisches (z.B. eines Fisches mit einer Körpermasse von 1 kg) wurde als Referenz-Wachstum GRF eingeführt, die den aktuellen Zustand des Nahrungsangebots füralle Altersgruppen des Bestandes beschreibt. Als Beispiel wurde einer Zeitreihe der Referenz-Wachstumsraten des nördlichen Kabeljaubestandes (NAFO, 3K) für die Zeitsraum 1979 bis 1999 berechnet. Für diesen Kabeljaubestand war zu beobachten, dass Umgebungsbedingungen für sieben Jahre in Folge Wachstumsraten unter dem langjährigen Mittelwert verursachten. Nach einer längeren Hungerperiode kollabierte dieser Fischbestand im Jahr 1992 auch durch den Einfluß der Fischerei - und dies war sicher kein Zufall. Jetzt, mit der Referenz-Wachstumsrate GRF, ist ein einfacher und handlicher Parameter gefunden, der es gestattet den Einfluss der Umweltbedingungen auf die Wachstumsbedingungen und andere davon abgeleitete Modelle zusammenzufassen. Dies macht es einfach, den Einfluss von Umweltveränderungen innerhalb der Bestandsabschätzungen zu berechnen.

The design and development of the Windermere Profiler. An instrument for measuring how various environmental parameters vary with depth in lakes, reservoirs and rivers

A review article detailing the background, development and functionality of the Windermere Profiler, a multi parameter environmental monitoring instrument for use in lakes, reservoirs and rivers. The article explains the requirement for regular data collection by the Freshwater Biological Association at Windermere. The article covers the requirements of a profiling instrument, the design considerations, the electronic circuitry, the computer program, the operation of the computer software, the profiler in use and further developments to the design. A number of figures and images accompany the article.

Interpreting the environmental record in the sediments of Blelham Tarn

Two aspects of the environmental record in the sediments of Blelham Tarn have been investigated: (1) the ecological history of the catchment, and lake-catchment relationships, by detailed analysis of the preserved pollen (as an indication of vegetation) and sediment composition with respect to a range of inorganic and organic geochemical variables and (2) a detailed investigation of the manner in which sediment is being formed today, including the way in which microfossils (pollen and diatoms) are being recruited and incorporated into sediments. When the record was examined by biological and geochemical analysis, together with radionuclide dating, of closely spaced samples, it was found that the changes of the last 30 yrs represented only the most recent episode in a long history of modification of the lake by man. To find an approach to this it is necessary to go back for at least 2500 yrs.

The effects of environmental stress on the physiology of growth in rainbow trout, Salmo gairderi Richardson

There is little doubt that both mammalian and teleost growth hormones can accelerate growth and increase food conversion efficiency in all commonly-reared species of salmonid fish. In those vertebrates that have been closely studied (predominantly mammals), the pituitary hormone somatotropin (GH or growth hormone) is a prime determinant of somatic growth. The hormone stimulates protein biosynthesis and tissue growth, enhances lipid utilization and lipid release from the adipose tissues (a protein-sparing effect) and suppresses the peripheral utilization of glucose. The present study is a prerequisite for future work on growth hormone physiology in salmonids and should contribute to our understanding of the mechanisms of growth suppression in stressed fish. Plasma growth hormone (GH) levels were measured in rainbow trout using a radioimmunoassay developed against chinook salmon growth hormone.