Dissertations / Theses on the topic 'Mass flow analysis (MFA)'

The stochastic continuum approach, as an alternative to the discrete fracture-network approach, is applied to hydraulic conductivity data from fractured crystalline rock at Fanay-Augeres, France. Small-scale measurements are transformed into binary indicator values. Viewing the transformed data as defined over a continuum, the statistical correlation structure of the stochastic process is determined. Estimates of hydraulic conductivity and its probability field are obtained using ordinary and median indicator kriging. Indicator kriging results are input into sequential conditional indicator simulation, generating equally likely sets of hydraulic conductivities. An adjoint-state, finite element inverse model is used to derive the effective hydraulic conductivity of an equivalent homogeneous porous medium. Stochastic realizations of hydraulic conductivities are input into a flow model to study their effect on the variability of resulting hydraulic heads and flow rates. Results show that flow in the fractured medium can be analyzed without any reference to geometric fracture data.

Negli ultimi tre decenni la domanda globale di cibo, in particolare di proteine animali (carne, latte, uova), è aumentata in base alla crescita della popolazione che dovrebbe arrivare a 9 miliardi di persone entro il 2050. Questi alimenti rappresentano infatti un'importante fonte di energia, proteine di alta qualità, micronutrienti e vitamine. Pertanto, questo miglioramento potrebbe contribuire all'aumento della durata della vita e della domanda di cibo. Ciò ha costretto il settore agricolo ad un'ulteriore intensificazione che ha interessato anche la coltivazione di colture per l'alimentazione animale. Le produzioni agricole e zootecniche hanno un impatto ambientale rilevante, e questo argomento è oggetto di critiche e di indagini scientifiche anche per definire più accuratamente il loro contributo e le relative potenziali strategie di mitigazione, considerando anche che la fase agricola è il principale contributore dell'impatto ambientale della catena di produzione alimentare. Si riconosce infatti che il settore agricolo contribuisce direttamente al 21% delle emissioni totali di gas serra di origine antropica a livello mondiale e consiste per lo più di metano seguito da protossido di azoto e anidride carbonica. Queste emissioni sono per lo più associate alla produzione zootecnica, in particolare all'allevamento di ruminanti che contribuisce con le emissioni dirette di metano dovute alla fermentazione dei ruminanti e alla fermentazione del letame; la restante parte è composta da emissioni indirette dovute alla deforestazione, all'uso di energia e alla produzione di mangimi. Lo scopo di questa tesi è stato la valutazione dell'impronta ambientale nel settore zootecnico a diversi livelli di scala tematica. La filiera italiana della carne, gli allevamenti lattiero-caseari, un caseificio per la produzione di Grana Padano DOP e i singoli animali sono stati studiati per quantificare l'impronta ambientale. Nel primo lavoro è stata valutata la filiera italiana della carne con un approccio di analisi dei flussi di massa e di valutazione del ciclo di vita. In primo luogo, la quantificazione della carne è stata effettuata dalla macellazione al consumo domestico, partendo dal peso della carcassa fino alla carne realmente consumata. A questo livello si è tenuto conto della carne di bovini, suini, ovini e caprini, equidi e conigli. Durante la catena sono state quantificate anche le perdite di carne e i rifiuti. In particolare, i sottoprodotti di origine animale (SOA) sono stati quantificati per singole specie e classificati in base al rischio a livello sanitario secondo il regolamento (CE) 1069/2009. Secondo la categoria (Cat 1, Cat 2 o Cat 3), supponendo che tutti i SOA fossero destinati al processo di rendering, l'uso e lo smaltimento dei prodotti dopo rendering è stato identificato. L'analisi dei flussi di massa ha confermato come l'Italia sia un importatore netto di carne bovina e suina, mentre è autosufficiente per quanto la carne avicola. L'analisi dei flussi di massa rivela che nel 2013 sono stati consumati in Italia 2,86 Mt di carne. Questo valore equivale a 131 g/giorno/pro-capite e a 47,91 kg/anno/pro-capite di carne consumata. In percentuale la quantità totale di carne consumata è rappresentata dal 46% da carne suina, dal 28% di carne avicola, dal 23% di carne bovina e dal 3% di altre carni (coniglio, equini, ovini e caprini). Questo approccio ha permesso di quantificare anche sottoprodotti di origine animale (SOA) prodotti durante la fase di macellazione e gli scarti alimentari a livello di vendita al dettaglio e fase di consumo. La fase di macellazione è risultata essere la principale fonte di rifiuti, producendo il 48% di rifiuti originati nella filiera della carne. I risultati hanno evidenziato come i SOA siano già quasi completamente riutilizzati, compatibilmente con il loro rischio a livello sanitario, dimostrando la circolarità del sistema e permettendo di quantificare anche i prodotti evitati grazie al loro riutilizzo e le relative emissioni di gas serra evitate. Per quanto riguarda gli altri rifiuti alimentari, i risultati della presente valutazione possono essere considerati solo una stima per la mancanza di specifici coefficienti nazionali. Dopo la fase di quantificazione, è stato applicato l'approccio del Life Cycle Assessment (LCA) per valutare l'impronta ambientale, considerando anche il prodotto evitato grazie al riutilizzo dei sottoprodotti del rendering. I risultati dell'LCA rivelano che il consumo giornaliero di carne pro-capite emette 4,0 kg di CO2eq, con un contributo della care bovina pari al 30%, della carne suina pari al 9.6% e della carne avicola pari all’8%. Le emissioni relative ai SOA sono risultate essere pari al 60% di quelle totali e il loro riutilizzo ha permesso una riduzione di queste del 10%. Il secondo ed il terzo lavoro sono stati invece relativi al potenziale di riscaldamento globale (GWP) di latte bovino e Grana Padano DOP. Complessivamente sono stati valutate ventisette aziende zootecniche con bovine da latte, con latte destinato al formaggio Grana Padano DOP, e un caseificio, situato nella provincia di Piacenza. I dati primari sono stati raccolti utilizzando un questionario appositamente redatto. Questo ha incluso per le aziende agricole la richiesta di dati relativi alla composizione della mandria, la gestione dell'alimentazione, la produzione di latte e performance riproduttive, piani colturali e l'utilizzo delle risorse energetiche e dei materiali di lettime, mentre per il caseificio sono stati richiesti dati relativi all'utilizzo delle risorse energetiche e gli input richiesti dal processo di caseificazione. Nel secondo lavoro sono state valutate 10 aziende lattiere per valutare l'impronta di carbonio del latte (CF) e individuare le principali fonti di emissioni. Lo studio ha utilizzato un approccio dalla culla alla tomba considerando come unità funzionale un 1 kg di latte corretto per contenuto di grasso e proteine (FPCM). Il valore medio di CF di 1 kg di FPCM è risultato essere pari a 1,33 kg di CO2eq/kg FPCM con però un ampio range di variazione, da 1,02 a 1,62 kg di CO2eq/kg FPCM. Le emissioni dovute alle fermentazioni enteriche e alle fermentazioni da reflui rappresentano il 52% del totale, mentre le emissioni relative agli alimenti acquistati il 36%. L'autoproduzione e il consumo energetico rappresentano invece rispettivamente il 6% e il 6%. Nel terzo lavoro invece è stata presa in considerazione la produzione di Grana Padano DOP. In questo caso è stato utilizzato un approccio dalla culla al cancello del caseificio considerando come unità funzionali 1 kg di FPCM e 1 kg di Grana Padano DOP stagionato 9 mesi. Il latte destinato alla produzione del formaggio ha mostrato un valore medio di CF pari a 1,38 kg CO2eq/kg FPCM, con un valore minimo di 1,02 e uno massimo di 1,94 kg CO2eq/kg FPCM. Il valore medio di CF di 1 kg di formaggio Grana Padano DOP è stato invece pari a 9,99 kg di CO2eq, con un contributo della fase agricola pari al 94%. I risultati di questi lavori si sono mostrati in accordo con studi simili riportati in bibliografia e hanno inoltre permesso di evidenziare come gli allevamenti da latte mostrassero un maggior livello di sostenibilità ambientale ma con possibilità di miglioramento principalmente attraverso il miglioramento della gestione delle mandrie (prestazioni produttive e riproduttive). Il quarto lavoro ha riguardato invece lo sviluppo di proxy in grado di prevedere le emissioni di metano da singole bovine da latte. Questo focus è un punto caldo di ricerca, soprattutto perché di fondamentale importanza per individuare strategie di mitigazione efficaci per la riduzione delle emissioni di metano dovute a fermentazioni ruminali, gas ad effetto serra riconosciuto avere il maggior contributo sul totale delle emissioni. Le emissioni di metano dipendono principalmente dal quantitativo di concentrato assunto e dalla composizione generale della dieta, ma tuttavia nelle aziende agricole commerciali risulta difficile quantificare con precisione l’ingestione di alimenti. Lo studio ha quindi mirato a verificare la possibilità di utilizzare la tecnologia del vicino infrarosso (NIRS) utilizzando lo spettro di campioni di feci (NIRSf) e/o in combinazione con altri parametri fenotipici disponibili a livello aziendale per prevedere la produzione di metano (MP, g/giorno) dalle singole vacche da latte in lattazione. Il NIRSf da solo ha permesso una stima abbastanza buona della produzione di metano e le stime sono state migliorate in misura simile quando sono stati considerati il peso vivo o la produzione di latte tal quale o la produzione di latte corretta per il contenuto energetico, mentre la combinazione del NIRSf con più di un altro parametro ha migliorato le stime solo in misura molto limitata. Il metano può essere previsto utilizzando modelli che considerano l’ingestione di sostanza sezza, il peso vivo o la produzione di latte ma il limite principale è rappresentato dalla disponibilità dei dati a livello aziendale. La tecnica del vicino infrarosso applicata ai campioni fecali, in particolare se combinata con altri parametri fenotipici, può rappresentare una valida alternativa per misurazioni su larga scala in allevamenti da latte commerciali, quando l’ingestione di sostanza secca di solito non è disponibile, per la selezione genetica di vacche da latte a bassa emissione.
In the last three decades global demand of food, in particular animal proteins (meat, milk, and eggs), has increased according to the population growth, that is expected to go up to 9 billion by the 2050. These, in fact, represent an important source of energy, high-quality protein, micronutrients and vitamins. Therefore, this improvement could contribute to the lifespan increase and food demand. The latter forced the agricultural sector to a further intensification that affected also the cultivation of crops for animal feeding. Agricultural and livestock productions have a relevant environmental impact, and this topic is object of criticism and scientific investigation also to more accurately define its contribution and potential mitigation strategies, considering also that agricultural stage is the main contributor to the environmental impact of the food production chain. It is recognized, in fact, that agricultural sector directly contribute to the 21% of total global anthropogenic greenhouse gas emissions, mostly consisting of methane followed by nitrous oxide and carbon dioxide. These emissions are mainly associated with the livestock production, in particular with ruminants breeding that contributes directly to methane emissions due to ruminal and manure fermentation; the remaining part is composed by indirect emissions from deforestation, energy use and animal feed production. The scope of this thesis was the evaluation of environmental footprint in the livestock sector at different subject scale level. Italian meat supply chain, dairy farms, Grana Padano PDO cheese factory and single animals was investigated in order to quantify environmental footprint. In the first work, the Italian meat supply chain has been evaluated whit a mass flow analysis (MFA) approach and life cycle assessment (LCA) approach. Firstly, the quantification of meat had been made from slaughter to household consumption, starting form carcass weight to real meat consumed. At these levels, meat form cattle, pig, sheep and goat, equidae, and rabbit was taken in account. During the chain also meat losses and waste were quantified. In particular animal by-products (ABPs) were quantified for single species and categorized into heath level risk according to the Regulation (EC) 1069/2009. According to the category (Cat 1, Cat 2 or Cat3), assuming that all ABPs were destinated to rendering process, use and disposal of rendered products was identified. The MFA confirmed how Italy is a net importer of cattle and pork meat while it is self-sustaining for poultry meat. Mass flow analysis revealed that in 2013, 2.86 Mt of meat were consumed in Italy. It is equivalent to 131 g/day/pro-capita and to 47.91 kg/year/pro-capita of meat consumed. In percentage the total amount of consumed meat is represented by 46% of pig, 28% of poultry and 23% of cattle and 3% of other meat (rabbit, equidae, and sheep and goat). This approach quantified the ABPs produced at slaughtering level and food wastes at retail and consumer levels. Slaughter phase was the main source of waste, producing 0.80 Mt of ABPs, 48% of the total amount of waste originated in the meat supply chain. Results highlighted how the ABPs are already almost completely reused, compatibly with their health level risk, demonstrating the circularity of the system through the quantification of the avoided products and relative GHGs emissions. Concerning other food wastes, the results of the present evaluation could be considered only an estimate due to the lack of specific national coefficients. After quantification LCA was applied in order to evaluate environmental footprint, considering also avoided product due to the re-use of rendered ABPs. LCA results reveal that daily meat consumption pro-capita emits 4.0 kg CO2eq represented by 30% of cattle meat, 9.6% of pig meat and 8% of poultry meat. Emissions allocated to ABPs are the 60% and their re-use decrease the emissions about 10%. Second and third works focused the milk and PDO Grana Padano global warming potential (GWP). Overall, twenty-seven dairy farms, producing milk destinated to Grana Padano PDO cheese and one cheese factory, situated in the Piacenza province were evaluated. Primary data were collected by using a specific survey. This included for the farms the request of data regarding herd composition, feeding management, milk production, herd management and performace, crops cultivation and resource use, whereas for the cheese factory, the survey included energy resource use and input requested by cheese making process. In the second work, 10 dairy farms were evaluated in order to assess the milk Carbon Footprint (CF) and the main source of emissions. The system boundary was a cradle-to-farm-gate and functional unit is 1 kg of FPCM (Fat and Protein corrected milk). The CF of 1 kg of FPCM resulted equal to 1.33 kg CO2eq/kg FPCM with a wide range of variation from 1.02 to 1.62 kg CO2eq/kg FPCM. Emissions due to enteric fermentation and manure fermentation represented the 52% of the total, while acquired feed the 36%. Self-production and energetic consumption represented 6% and 6% respectively. In the third, Grana Padano PDO production was considered. The milk destinated to cheese processing showed an average value of CF equal to 1.38 kg CO2eq/kg FPCM, with a minimum value of 1.02 and a maximum one of 1.94 kg CO2eq/kg FPCM. Instead, the CF average value of 1 kg of PDO Grana Padano cheese was equal to 9.99 kg CO2eq, showing an agricultural stage contribution of 94%. Results of these works were in accord with similar studies reported in literature and had pointed out how dairy farms showed a greater level of environmental sustainability but with possibilities for improvement, mainly through herd management enhancement (productive and reproductive performances). Fourth work was about the development of proxies able to predict the methane emissions from individual cows. This focus is a hot research point in order to improve the mitigation strategies to reduce methane emissions because of the main GHG contributor. Methane emission is mainly driven by feed intake and diet composition, but it is difficult to measure intake in commercial farms. The study aimed to verify the possibility of using NIRS of faeces (NIRSf) alone and in combination with other phenotypic parameters available at a farm level to predict methane production (MP, g/d) from individual lactating dairy cows. NIRSf alone allowed a fairly good estimation of methane yield and the estimations were improved to a similar degree when BW, MY or ECM were considered, whereas combining NIRSf with more than one other parameters improved the estimations with a very little extent only. Methane can be predicted using models that consider the DMI, BW or MY but the main limitation is represented by the data availability. Near Infrared technique applied to faecal samples, in particular when combined with other phenotypic parameters, can represent a valid alternative for large-scale measurements in commercial dairy farms for genetic selection of low emitters dairy cows, when DMI measurement is usually not available.

The aim of this thesis is to discuss and analyse the influenceof data uncertainties with regard to the reliability of materialflow analysis (MFA) studies. MFA, as a part of environmentalsystems analysis, is a method belonging to the research field ofindustrial ecology and more specifically industrial metabolism.As such, the method strives at giving a holistic view of thecomplex world we live in, in order to reduce negativeenvironmental impact. Among other things, MFA studies have beenproposed to be useful for priority setting and following up inmunicipalities.

Serving as a starting point is a local case study of flows ofnitrogen in a Swedish municipality, Västerås. The casestudy has been performed using the ComBoxmodel. The years studiedare 1995 and 1998. The main sectors in society emitting nitrogento water were identified as the agricultural and householdsectors. The dominating sectors emitting nitrogen to air wereidentified as the agricultural, transport and infrastructuresectors.

As a basis for discussing data uncertainties qualitatively andquantitatively a literature survey was performed. 50 articles andbooks were identified as in some way or another dealing with datauncertainties in MFA. The literature survey showed that theuncertainties for results from a MFA study might vary between±30 % and a factor 10 depending on what kind of parameter isinvestigated. Only one method was found that dealt with datauncertainties in MFA in a complete way; a model developed byHedbrant and Sörme (HS model).

When applying the HS model to the case study of nitrogen flowsin Västerås, it was found that when uncertaintyintervals were calculated the possible conclusions changed. Ofthe two pair of flows compared in relation to priority setting,none of the earlier conclusions remained. Of the three flowsanalysed in relation to following up, only the flow from onepoint source supported the same conclusion when uncertainty wasconsidered.

In all, it is concluded that data uncertainties in MFAanalysis are an important aspect and that further research isneeded in order to improve input data quality estimations andframeworks for determining, calculating and presenting data, datauncertainties and results from MFA studies. However, theunderlying reality remains, e.g. that management of materialflows are important for understanding and reducing the negativeenvironmental impact. Thus, MFA is one useful tool in thiswork.

Keywords:data uncertainties, sensitivity analysis,Material flow analysis, MFA, method to determine datauncertainties, case study, ComBox model, nitrogenflows.

A great deal of work has been conducted on in-tube condensation in horizontal and vertical smooth tubes. The available literature points to mechanisms governing two-phase condensation heat transfer coefficients and pressure drops, which are directly linked to the local flow pattern for both horizontal and inclined configurations. However, the work has been limited to flow pattern observations, heat transfer, pressure drops and void fractions for both horizontal and inclined tubes at high mass fluxes. No work has been conducted on the analysis of the observed flow patterns and the effect of temperature difference between the average wall temperature and average saturation temperature for different inclination angles at mass fluxes of 100 kg/m2.s and below. The purpose of this study is to carry out a qualitative analysis of flow patterns, and show the effect of temperature difference on the heat transfer coefficient for inclination angles from +90° (upward flow) to -90° (downward flow) at mass fluxes below 100 kg/m2.s. An experimental set-up provided the measurements for the two-phase condensation of R-143a in a smooth tube with an inside diameter of 8.38 mm and a length of 1.5 m. The mass fluxes were 25 kg/m2.s to 100 kg/m2.s, the saturation temperature was 40 °C and the mean qualities were 0.1 to 0.9. A high-speed camera was used to visually analyse and determine the flow patterns for both the inlet and the outlet of the test section. Through the results, eight flow patterns were observed: stratified-wavy, stratified, wavy, wavy-churn, intermittent, churn, annular and wavy-annular. The maximum heat transfer was observed for downward flow between inclination angles of -15° and -30°. The Thome-Hajal flow pattern map correctly predicted horizontal flow patterns, but failed to predict most of the inclined flow patterns. Various flow pattern transitions were identified and proposed for all the investigated inclination angles in this study. Finally, the heat transfer coefficient was found to be dependent on quality, mass flux, temperature difference and inclination angle.
Dissertation (MSc)--University of Pretoria, 2016.
Mechanical and Aeronautical Engineering
MSc
Unrestricted

The applicability of the technique of inductively coupled plasma mass spectrometry to the analysis of geological samples was investigated using a variety of sample introduction techniques including: solution nebulisation; slurry nebulisation; flow injection; electrothermal vaporisation; and laser ablation, Solution sample introduction is limited by the amount of time required to prepare the sample, and the relative intolerance of the technique to high concentrations of sample matrix. The maximum level of dissolved solids for a refractory matrix such as a digested igneous rock was found to be 0.2% w/v. Good accuracy and precision are achievable. Acceptable results can be obtained using slurry nebulisation. However, standardisation is a problem due to the difference in response for aqueous and slurried analytes. Calibration against aqueous standards and the use of an internal standard is therefore precluded. In addition, the preparation of stable slurries is a highly skilled and time consuming task. Flow injection analysis offers the most benefit to the geochemical analyst. Flow injection was found to increase sample throughput and, more important, to improve matrix tolerance by a factor of l0x, thus allowing the direct determination of the platinum group elements and gold in geological samples without pretreatment. Small samples, such as fluid inclusion leachates can also be analysed without dilution and the matrix effects experienced when analysing samples containing high salt concentrations can be reduced by careful control of dispersion. The potential for increased detection limits by electrothermal vaporisation was not proved for geological materials due to the same matrix tolerance problems which limit detection limits in solution work. Laser ablation sampling allows direct analysis of the solid but quantitation requires matrix matched standards or independent variable internal standardisation, limiting the applicability of the technique for bulk screening. The use of laser ablation to analyse trace element concentrations in individual mineral grains has been investigated and partition coefficients for trace elements, including the rare earths in a large zoned pyroxene crystal, were determined.

This thesis reports the development and characterisation of the fast flow argon flow discharge source, coupled to quadrupole mass spectrometry, as a novel detector for gas chromatography. Also described are fundamental studies of the chemical and electrical properties of the flowing plasma, which further support the excited state model proposed in previous publications from this laboratory. The fast flow glow discharge source has been used for the GC-MS analysis of simple mixtures of halocarbons and organotin compounds. Detection limits in the low and sub-picogram range were obtained and the technique is shown to be a robust, simple and low cost alternative to existing plasma sources for elemental speciation. The voltage applied to the ion sampling cone has been used to easily control the degree of fragmentation of organic samples. When a small (< 10 V) positive bias was applied, molecular mass spectra were obtained with detection limits < 1 pg. When a negative bias was applied, the sample fragmented and dispersed the charge, which lowered the sensitivity. A progression to more fragmented ions was observed as the voltage was increased. This was similar to the type of information obtained from tandem mass spectrometry but only a single quadrupole was used in this work. The effect of the ion exit voltage on the organic ion intensities has been shown to be consistent with a secondary discharge of argon Rydberg (highly excited) states close to the sampling cone. When a negative bias is applied, the sample is fragmented in collisions with electrons accelerated in the field. When a positive bias is applied, positive ions are repelled but neutral molecular Rydberg species can pass through the exit aperture to the mass spectrometer, where they are then ionised. Therefore, the molecular mass spectra obtained may be considered as a form of Rydberg state mass spectrometry.

The investigations presented in the thesis are theoretical studies of magnetohydrodynamic flows, heat and mass transfer in Newtonian/non-Newtonian cooling liquids, due to horizontal/vertical stretching sheet. The theoretical studies include the effect of magnetic field, uniform and non-uniform heat source/sink (flow and temperature dependent heat source/sink) effects. The considered problems include flow of viscous fluids in the presence of applied magnetic field and electric field with first order chemical reactions. The viscous incompressible Newtonian fluid flow in porous medium with Darcy-Forchheimmer model, electrically conducting fluid and nanofluid is studied. We introduce innovative techniques for finding solutions of highly nonlinear coupled boundary value problems such as Runge-Kutta method, Perturbation method and Differential Transform Method (DTM).   Chapter 1-2 gives a brief introduction. Chapter 3 focuses on Lie group analysis of MHD flow and heat transfer over a stretching sheet. The effects of viscous dissipation, uniform heat source/sink and MHD on heat transfer are addressed. In Chapter 4-6 we examined the laminar flow, thermocapillary flow of a nanoliquid thin film over an unsteady stretching sheet in presence of MHD and thermal Radiation in different situations. An effective medium theory (EMT) based model is used for the thermal conductivity of the nanoliquid.  Metal and metal oxide nanoparticles are considered in carboxymethyl cellulose (CMC) - water base liquid. In Chapter 7-9 we analyzed, heat and mass transfer in MHD, mixed convection, viscoelastic fluid flow, non-Darcian flow due to stretching sheet in presence of viscous dissipation, non-uniform heat source/sink and porous media have been investigated in different situations.  MHD and viscous dissipation have a significant influence on controlling of the dynamics.    In Chapter 10 the linear stability of Maxwell fluid-nanofluid flow in a saturated porous layer is examined theoretically when the walls of the porous layers are subjected to time-periodic temperature modulations. A modified Darcy-Maxwell model is used to describe the fluid motion, and the nanofluid model used includes the effects of the Brownian motion. The thermal conductivity and viscosity are considered to be dependent on the nanoparticle volume fraction. In Chapter 11 we studied MHD flow in a vertical double passage channel taking into account the presence of the first order chemical reactions. The governing equations are solved by using a regular perturbation technique valid for small values of the Brinkman number and a DTM valid for all values of the Brinkman number.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2011.
Nanofluid, which was first discovered by the Argonne laboratory, is a nanotechnology- based heat transfer fluid. This fluid consists of particles which are suspended inside conventional heat transfer liquid or base fluid. The purpose of this suspension is for enhancing thermal conductivity and convective heat transfer performance of this base fluid. The name nanofluid came about as a result of the nanometer- sized particles of typical length scales 1-100nm which are stably suspended inside of the base fluids. These nanoparticles are of both physical and chemical classes and are also produced by either the physical process or the chemical process. Nanofluid has been discovered to be the best option towards accomplishing the enhancement of heat transfer through fluids in different unlimited conditions as well as reduction in the thermal resistance by heat transfer liquids. Various manufacturing industries and engineering processes such as transportation, electronics, food, medical, textile, oil and gas, chemical, drinks e.t.c, now aim at the use of this heat transfer enhancement fluid. Advantages such organisations can obtain from this fluid includes, reduced capital cost, reduction in size of heat transfer system and improvement of energy efficiencies. This research has been able to solve numerically, using Maple 12 which uses a fourth- fifth order Runge -kutta- Fehlberg algorithm alongside shooting method, a set of nonlinear coupled differential equations together with their boundary conditions, thereby modelling the heat and mass transfer characteristics of the boundary layer flow of the nanofluids. Important properties of these nanofluids which were considered are viscosity, thermal conductivity, density, specific heat and heat transfer coefficients and microstructures (particle shape, volume concentration, particle size, distribution of particle, component properties and matrixparticle interface). Basic fluid dynamics equations such as the continuity equation, linear momentum equation, energy equation and chemical species concentration equations have also been employed.

2016 - 2017
Flow-like mass movements are catastrophic events occurring all over the world and may result in a great number of casualties and widespread damages. The analysis of the time-space evolution of the kinematic quantities is a useful tool to understand the propagation stage of these phenomena as well as for control works design. The thesis deals with study of flow regime of Newtonian and non-Newtonian fluids and provides a contribution to this topic through the use of numerical procedures based on FV (finite volume) scheme and SPH (smoothed particle hydrodynamics) method. The FV model, developed by Rendina et al., 2017, is a single phase equivalent model, while the Geoflow-SPH, developed by Pastor et al.2009, considers the propagating mass with an average behavior of solid skeleton and pore water pressure. The flow kinematics are analyzed through the Froude number, widely used in hydraulic engineering, discriminates two different kinematical features i.e. subcritical (slow) or supercritical (rapid) flows. The analysis concern a 1D/2D dam break of Newtonian (water flow) and non-Newtonian flows (in particular based on a viscoplastic and frictional laws). The numerical results highlighted flows are supercritical even in areas far from trigger zones and Froude numbers of viscoplastic flows are higher than frictional flows. Later, the Froude number is used as a quantitative descriptor of the control works response and, more generally, as an useful tool to estimate the efficiency of existing storage basins. The first case study regards Cancia, in the Dolomite Alps, where two storage basins dramatically failed on 2009 due to a short-time sequence of rainfall-induced debris flows and flash floods. The kinematic analysis highlighted that debris flow can be associated to a subcritical flow while flash flood is similar to a supercritical flow and for latter lower is the potential efficacy of control works. The second case study regards Sarno, in the Campania region, where one of the most complex systems of passive control works was built after the 1998 events. The performance of the protection system is analyzed referring to Froude number again which highlighted the importance of planning the emergency/ordinary maintenance of control works. Finally, a new type of passive control work is described, i.e. the permeable rack that has the function of decrease the pore water pressures at the base and inside the propagating mass, thus causing the landslide body to brake and stop. The rack performance is tested as adaptation structure in existing protection systems also.[edited by Author]
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Kayaking is a watersport activity that involves paddling performed within leisure purposes. Although kayaking provides pleasure to the practitioners, there are some adverse environmental issues concerning the site used to perform kayaking due to the equipment. This paper identifies and analyzes the lifecycle stages in which negative environmental impacts are generated. Melker of Sweden is an outdoor company specialized in delivering high-quality kayaks. This study aims to present an overview of the current environmental performance of Melker of Sweden’s kayaks. For this purpose, two environmental assessment tools are applied: material flow analysis and life cycle assessment. The Material Flow Analysis (MFA) results show that the transport of material to the manufacturing unit generates a considerable amount of emissions. Additionally, hull manufacturing and assembling accessories were found to be the least resource-efficient operation among all. The Life Cycle Assessment (LCA) results identify the transport of material and the manufacturing phase as the primary sources responsible for environmental impacts. On the one hand, the use of epoxy resin and gel coat is the root cause of high contribution of the manufacturing phase. On the other hand, the use of flax fiber found to be the least contributing material to adverse environmental impacts. This report also presents a list of recommendations regarding the import of material, the efficacy of the manufacturing operations, the type of raw material, and waste treatment alternatives.
Fysisk aktivitet kan innefatta olika fritidsaktiviteter, däribland friluftsliv. Kajakpaddling är en sådan friluftslivaktivitet, alltefter utövares syfte. I denna rapport är kajakpaddling en fritidsaktivitet där där utövarens naturupplevelse främjas. Oaktat fördelarna vid utövandet av denna aktivitet kan ej förbises faktum att det också kan medföras vissa negativa konsekvenser. Denna masteruppsats har som mål att identifiera och analysera den miljöpåverkan och dennes efterspel som orsakats av en kajaks tillverkning. Melker of Sweden är ett utomhusföretag specialiserat på att leverera kajaker av hög kvalitet. I linje med företagets vision syftar denna studie till att undersöka den nuvarande miljöprestandan samt kvantifiera den potentiella miljöpåverkan från en kajaks livscykel. För detta ändamål tillämpas det två miljöbedömningsverktyg, nämligen en materialflödesanalys och livscykelanalys. Materialflödesanalysen visar att mängden av utsläpp som genereras från transporten av material till tillverkningsenheten är enorm. Utöver detta var den hulltillverkning samt den montering av tillbehörsverksamheter bland de minst resurseffektiva tillverkningssteg. Livscykelanalysen identifierar import av material och tillverkningsfas som de viktigaste källorna till miljöpåverkan. Å ena sidan är användningen av epoxiharts och gelbeläggning i tillverkningen grundorsaken till huvudbidraget. Å andra sidan är användningen av linfiber det minst bidragande material då det gäller negativa miljöeffekter. I denna studie ges rekommendationer rörande import av vissa material och materialval, sätt att öka tillverkningseffektiviteten, typ av råmaterial samt avfallsbehandlingsalternativ.

The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the taste of olive oil, while antioxidants afford some protection from harmful reactions involving radical species inside the body by scavenging radicals when olive oil is ingested. The VOCs of olive oil are used by sensory panel judges to classify oils by their degree of suitability for human consumption. The major parameters used for this evaluation are the strengths of any defects and the degree of fruitiness. A defect is an indication of an undesired process which has occurred in the oil, while fruitiness is a fragile attribute which denotes a good quality oil and is easily masked by defects. SIFT MS was used to measure the strengths of the olive oil defects rancid, winey, musty, fusty and muddy. Great potential was demonstrated for all defects except musty and the concentrations of VOCs in olive oil head space were correlated with the peroxide value, a measure of the degree of oil oxidation. A study aimed at correlating the strength of the fruitiness attribute as determined by a sensory panel with the concentrations of VOCs in olive oil head space was unsuccessful. The SIFT MS Total Oxyradical Scavenging Capacity (TOSC) assay was used to measure olive oil antioxidants. This assay measures all antioxidants in oil, not only those removed by extraction with a solvent, as it is conducted in an emulsion. SIFT MS TOSC assay results were found to correlate well with those of the widely used Folin Ciocalteu assay and the total concentration of phenolic compounds present in olive oil. Discrepancies between the two assays were most likely due to hydrophobic antioxidants which are measured by the SIFT MS TOSC assay but not the other tests.

The work presented in this thesis was initiated in order to develop a non-invasive real-time gas phase analytical technique, based on selected ion flow tube mass spectrometry (SIFT-MS), for monitoring the progression of human cell cultures and the detection of microbial contamination in such cultures by monitoring and quantifying the emitted volatile compounds. Fundamental SIFT experiments were performed to characterise the reactions of the SIFT-MS precursor ions (H3O+, NO+ and O2 +●) with several volatile compounds of potential value to biological research; a necessity for their quantification. The work has resulted in new methods for the quantification acetaldehyde and CO2 in gaseous samples. The compounds present in the headspace of sealed cultures of six human cell types were analysed by SIFT-MS, the key finding being their consumption of the toxic volatile compound acetaldehyde from the media. Further experiments involved the addition of the enzyme aldehyde dehydrogenase inhibitors diethylaminobenzaldehyde and disulfiram to cultures of hepG2 (hepatocellular carcinoma) cells, when it was observed that consumption of acetaldehyde from the cultures/headspace was reduced, and in some cases, acetaldehyde was even produced due to the actions of the cellular alcohol dehydrogenase enzyme. Furthermore, the solvent dimethylsulphoxide was reduced to imethylsulphide by the cells, which is known to occur via the enzyme methionine sulphoxide reductase. This process was retarded by the ALDH inhibitors. The use of SIFT-MS for the detection of microbial infection in mammalian cell cultures was also explored. The volatile compounds emitted by E. coli (strain JM109), into the gas phase above two different culture media, were analysed using SIFT-MS. Further, the progression of a culture of this bacterium was monitored continuously over a 4-hour period. The findings of this research were then applied to the study of human cell cultures intentionally infected by E. coli bacterium, including cultures contained in a 1L bioreactor.

SIFT-MS is a relatively new trace gas analysis technique that has wide application. One particular attribute of the instrument is the ability to detect and quantify volatile organic compounds to the parts per trillion in real-time without the need for sample preparation. However the issue of maintaining accuracy at these low concentrations required attention as it was evident large or polar analytes were being lost by adsorption to the SIFT instrument’s inlet system. The purpose of this research was to evaluate the performance of a passivated inlet in lowering any adsorption in the inlet system compared to the current unpassivated inlet of the SIFT instrument. Volatile concentrations of vanillin (C₈H₈O₃ 152.15 g/mol), ammonia (NH₃ 17.03 g/mol), and hydrogen sulfide (H₂S 34.08 g/mol) were measured. The results determined the passivated inlet provided a significantly better inlet response to these compounds. Consequently improved passivated inlets were installed on current models of SIFT-MS VOICE200®, and also the research laboratory VOICE100™ instrument. Having established a more reliable sampling system for very low concentrations of analyte, attention was paid to SIFT-MS flavour analysis of two foods, cheese and chocolate. The volatile matrix of these foods is highly complex and the compounds of interest are typically difficult to measure. The key aroma compounds for analysis were based on reported literature and earlier SIFT-MS studies which provided a useful framework for the current food flavour research. A significant finding from the SIFT-MS examination of Parmesan cheese is that differences in the relative concentration of some characteristic aroma compounds were a consequence of the milk type used in manufacture. Endogenous enzymes responsible for a multitude of reactions are mostly if not completely inactivated by the pasteurization temperature. A similar analysis approach was attempted for chocolate analysis. Here flavour differences were not as clearly recognised as for the cheese samples. In chocolate there are a greater number of parameters that are involved in its manufacture. Nevertheless, some recognisable differences in chocolate could be attributed to cocoa bean type and flavour additions by the manufacturer.

An investigation of binary fluid heat and mass transfer in ammonia-water absorption was conducted. Experiments were conducted on a horizontal-tube falling-film absorber consisting of four columns of six 9.5 mm (3/8 in) nominal OD, 0.292 m (11.5 in) long tubes, installed in an absorption heat pump. Measurements were recorded at both system and local levels within the absorber for a wide range of operating conditions (nominally, desorber solution outlet concentrations of 5 - 40% for three nominal absorber pressures of 150, 345 and 500 kPa, for solution flow rates of 0.019 - 0.034 kg/s.). Local measurements were supplemented by high-speed, high-resolution visualization of the flow over the tube banks. Using the measurements and observations from videos, heat and mass transfer rates, heat and vapor mass transfer coefficients for each test condition were determined at the component and local levels. For the range of experiments conducted, the overall film heat transfer coefficient varied from 923 to 2857 W/m²-K while the vapor and liquid mass transfer coefficients varied from 0.0026 to 0.25 m/s and from 5.51×10^-6 to 3.31×10^-5 m/s, respectively. Local measurements and insights from the video frames were used to obtain the contributions of falling-film and droplet modes to the total absorption rates. The local heat transfer coefficients varied from 78 to 6116 W/m²-K, while the local vapor and liquid mass transfer coefficients varied from -0.04 to 2.8 m/s and from -3.59×10^-5 (indicating local desorption in some cases) to 8.96×10^-5 m/s, respectively. The heat transfer coefficient was found to increase with solution Reynolds number, while the mass transfer coefficient was found to be primarily determined by the vapor and solution properties. Based on the observed trends, correlations were developed to predict heat and mass transfer coefficients valid for the range of experimental conditions tested. These correlations can be used to design horizontal tube falling-film absorbers for ammonia-water absorption systems.

The main objective of this study is to explore the complex fluid flow phenomena that result in the generation of a high frequency noise in counterbalance valves through an experimental and numerical investigation of the flow. Once the influence of the different components involved in noise generation is established, a secondary objective is the introduction of design modifications that eliminate the undesired effect without altering the operation envelope or the performance of the valve. A hydraulic test bench was used to carry out an experimental investigation of the noise generation process. A computer based data acquisition system was used to record pressure fluctuations, flowrates and hydraulic oil temperatures in a production valve under a variety of operational conditions. Extensive experimental measurements and numerical modeling lead to the hypothesis that noise generation is the result of an acoustic resonance triggered by shear layer instability at the valve inlet. The pressure gradients developed when the shear layer entrains the stagnant fluid in the valve main cavity cause the layer to become unstable and oscillate. The oscillation frequency will depend on a great number of factors such as valve geometry, pressure and velocity gradients and the density and viscosity of the fluid. It is postulated that the observed noise is generated when this frequency matches one of the resonant frequencies of the valve cavity. The proposed mechanism is theoretically poorly understood and well beyond simplified analysis, its accurate numerical simulation is computational very intensive requiring sophisticated CFD codes. The numerical investigation was carried out using STAR–CCM+, a commercially available CFD code featuring 3-D capabilities and sophisticated turbulence modeling. Streamline, pressure, velocity-vector and velocity-scalar plots were obtained for several valve configurations using steady and unsteady state flow simulations. An experimental and numerical analysis of an alternative valve geometry was carried out. Experimental results demonstrated a greatly reduced instability range. The numerical analysis of the unsteady behavior of the shear-layer streamlines for both valves yielded results that were compatible with the experimental work. The results of this investigation promise a great positive impact on the design of this type of hydraulic valves.

The Vehicle Routing Problem (VRP) has been studied for many decades . The majority of these works focus on the static and deterministic cases of vehicle routing in which all information is known at the time of the planning of the routes. A Green Vehicle Routing Problem (G-VRP) is formulated and solution for these techniques are developed to aid organizations with alternative fuel-powered vehicle fleets in overcoming difficulties that exist as a result of limited number of vehicle driving range in conjunction with limited refueling infrastructure. The G-VRP is formulated as a mixed integer linear program.During the past decade the number of published papers dealing with dynamic transportation models has been growing. The dynamic vehicle routing problem is only a subset of these models. In most real-life applications though, stochastic and/or dynamic information occurs parallel to the routes being carried out. In Real-life examples of stochastic and/or dynamic routing problems they commonly include the distribution of oil to private households, the pick-up of courier mail packages and the dispatching of busses for the transportation of elderly and handicapped people. In these examples the customer profiles (i.e. the time to begin service, the geographic location, the actual demand etc.) may not be known at the time of the planning or even when service has begun for the advance request customers. Two distinct features make the planning of high quality routes in this environment much more difficult than in its deterministic counterpart; firstly, the constant change, secondly, the time horizon. Here in our thesis we have implemented the part of model which is a Ph.D. thesis of Dossier de candidature pour le prix de lameilleure these en transport et logistique by Yun He and analyse the Electric Vehicle Routing Problem considering the Energy consumption which is solved by using Python and the Mathematical tool Gurobi to solve the integer programming model.

Non-targeted metabolite profiling by liquid chromatography-mass spectrometry (LC-MS) was used to determine the metabolite responses of Arabidopsis roots to auxin or ethylene. Crosstalk between these hormones regulates many important physiological processes in plants, including the initiation of lateral root formation and the response to gravity. These occur in part through alterations in the levels of flavonoids, specialized plant metabolites that have been shown to act as negative regulators of auxin transport. However, much remains to be learned about auxin and ethylene responses at the level of the metabolome. LC-MS analysis showed that a number of ions changed in response to both hormones in seedling roots. Although classes of specialized metabolites such as flavonols and glucosinolates change in abundance in response to both auxin and ethylene, there was little overlap with regard to the specific metabolites affected. These data will be integrated with information from transcriptomic and proteomic experiments to develop framework models that connect phytohormones and specialized metabolism with specific physiological processes. Previous studies by imaging techniques have shown that flavonols increase in response to both auxin and ethylene in the root elongation zone, but LC-MS showed that flavonols decreased in abundance in response to these hormones. Therefore a method was developed for targeted metabolite profiling of flavonols in individual root tips by flow injection electrospray mass spectrometry. This method uncovered spatial differences in metabolic profiles that were masked in analyses of whole roots or seedlings, and verified that flavonols increase in response to these hormones in root tips.
Master of Science

Human food consumption has changed from the late 19th century to the turn of the millennium, and so has the need for resources to sustain this consumption. For the city of Linköping, situated in southeastern Sweden, the environmental imprint of an average inhabitant’s food consumption is studied from the year 1870 to the year 2000. The average consumer is the driving factor in this study, since changes in food consumption have a direct influence on the environmental imprint. This thesis analyses the environmental imprint of human food consumption from a historical perspective, by applying two different methods. An analysis of the average Swedish food consumption creates the basis for a material flow analysis of nitrogen and phosphorus, as well as a study of the spatial imprint. Emissions of nitrogen and phosphorus into the hydrosphere have decreased over this period for the system of food consumption and production for an average consumer, while the input via chemical fertilizer has increased significantly. The efficiency of this system could be increased if for instance more phosphorus in human excreta would be reused within the system instead of large deposition and losses into the hydrosphere. The spatial imprint of human food consumption shows, given the changing local preconditions, that less space would be needed for regional production of the consumed food. However, the share of today’s import and thus globally produced food doubles this spatial imprint. The results of this study show not only a strong influence of the consumption of meat and other animal products on the environmental imprint, but also great potential in the regional production of food. In the context of an increasing urban population, and thus additional billions of people who will live at an increasing distance from the agricultural production land, concern for the direct effects of our human food consumption can be of decisive importance for future sustainable food supply.

This thesis contributes to the understanding of glacier response to climate change by ice dynamical studies on Storglaciären, Sweden, and Bonnevie-Svendsenbreen, Kibergbreen and Plogbreen in Dronning Maud Land, Antarctica. Ice surface velocities, ice geometry and temperature information is fed through a force budget model to calculate ice mass outflux of these glacial systems via three-dimensional stress distributions for a flux-gate.

Field data were collected through repeated DGPS and GPR observations on Storglaciären between July 2000 to September 2001 and on Kibergbreen and Plobreen during the SWEDARP 2002/03 expedition to Antarctica. The work was strongly supported by remotely-sensed information.

The results from Storglaciären show a strength in the force budget model to discern both spatial and temporal variability in ice dynamical patterns. It highlights the influence of seasonality and bedrock topography upon glacier flow. A modeling experiment on Bonnevie-Svendsenbreen suggested that ice temperature increases substantially under conditions of high stress (≥0.4 MPa) due to strain-heating. This provides a positive feedback loop, increasing ice deformation, as long as it overcomes the advection of cool ice from the surface. These results explain, to some extent, the mechanism behind fast flowing ice streams. Mass flux caclulations from Bonnevie-Svendsenbreen suggest that the outflux given from force budget calculations can be used as a gauge for influx assuming steady state conditions. Plogbreen receives an influx of 0.48±0.1 km³ a^-1 and expedites a discharge volume of 0.55±0.05 km³ a^-1. This indicative negative mass balance is explained by a falling trend in upstream accumulation and the recent rise in global sea level, as it is likely to induce glacier acceleration due to a reduction in resistive forces at the site of the gate. This result is comparable with other Antarctic studies reporting negative mass balances, e.g. from WAIS, as caused by changes in the global atmospheric circulation pattern.

Estudos relacionados ao consumo de recursos e à emissão de resíduos na escala territorial local se originaram nas pioneiras pesquisas associadas ao conceito de metabolismo urbano. Nos últimos 15 anos, observa-se um crescimento do número de estudos aplicados a cidades, municípios ou regiões metropolitanas. A Análise dos Fluxos de Materiais - AFM (Material Flow Analysis) vem se consolidando como a abordagem metodológica predominante para esse tipo de investigação, a qual objetiva prover informações sobre fluxos de materiais e de energia, usualmente em unidades de massa, entrando e deixando uma sociedade. No entanto, todos os casos estudados na literatura prévia correspondem a capitais nacionais ou a municípios com centralidade econômica e de gestão do território na região as quais pertencem. Adicionalmente, não há estudos desenvolvidos no Brasil. Em face dessas lacunas, o objetivo principal deste trabalho é a caracterização dos fluxos de materiais associados ao metabolismo de um município brasileiro de pequeno porte (MBPP). Para tanto se adotou como estudo de caso o município de Feliz-RS. Como objetivos intermediários da pesquisa estabeleceram-se: a) Identificação dos métodos existentes para caracterização de fluxos de materiais na escala local e análise das possibilidades de aplicação no contexto dos MBPP; b) Desenvolvimento de um detalhamento metodológico da AFM, para a caracterização dos fluxos de materiais de MBPP; c) Análise das limitações e oportunidades para uso da AFM, na avaliação de sustentabilidade ambiental de municípios. Como resultados, avalia-se que o detalhamento metodológico desenvolvido é funcional e replicável para municípios brasileiros com o mesmo perfil, além de fornecer informações bastante detalhadas acerca dos fluxos ocorrentes no município adotado como caso. Assim, é possível realizar análises com diferentes níveis de desagregação. Quanto aos fluxos de materiais de Feliz, encontrou-se que o consumo doméstico de materiais per capita (DMC/ per capita) do município é alto, se comparado àqueles já caracterizados na literatura. Essa constatação corrobora com a proposição de que municípios com produção primária e secundária tendem a demandar, proporcionalmente, mais recursos do que aqueles que são consumidores finais. Quanto ao uso da AFM, na avaliação de sustentabilidade ambiental, verifica-se um alto potencial, com vantagens, em relação a outros métodos correntemente adotados. Entretanto, essas oportunidades ainda são pouco exploradas no contexto internacional e ignoradas no Brasil, ao se analisar a literatura existente.
Studies related to resources consumption and wastes emissions in a local territorial scale were originated from pioneering researches related to the urban metabolism concept. Over the past 15 years, there was a growth in the number of such studies applied to cities, municipalities and metropolitan areas. At the same time, Material Flow Analysis - MFA was consolidated as the predominant methodological approach for this type of research. However, it must be pointed out that all studied cases have been related to national capitals or counties, with economics centrality and land management in their own area. Besides, no studies of this nature were found as being developed in Brazil. Thus, the main goal of the research presented in this paper was to characterize material flows associated with the metabolism of a small Brazilian municipality and for this purpose the municipality of Feliz was adopted as a case study. Three intermediate objectives were established: a) To identify existing methods for material flows characterization on the local scale and to analyse the possibilities of applying them in the context of small Brazilian municipalities; b) to develop a MFA methodological detailing for the characterization of material flows of small Brazilian municipalities; c) to analyse constraints and opportunities for the use of MFA in the assessment of municipalities environmental sustainability. As results, it is considered that the methodological detailing developed raises the possibility of replicating the procedures applied in Feliz to other Brazilian municipalities, being this research a first and referential step in this direction. Besides, it provides very detailed information on flows occurring in the municipality adopted as the case study. Thus, it is possible ti further develop of analyses considering different levels of disaggregation. Concerning the material flows associated with the metabolism of Feliz, it was found that the studied municipality presents a DMC per capita comparable or superior to that of larger municipalities already analyzed by previous researches. This finding corroborates the hypothesis that municipalities with primary and secondary production tend to demand proportionately more resources than those who are the final consumers. Regarding the use of the MFA in the assessment of municipalities environmental sustainability, it was verified that it presents a high potential, with advantages over other methods currently adopted. However, when analyzing the existing literature it was noticed that these opportunities are still little explored in the international context and ignored in Brazil.

Urban emissions of antibiotics into the environment have the potential to adversely affect terrestrial and aquatic organisms. Developed standardized test methods allow the quantification of the resulting ecotoxicological risk, which strongly relies on a comprehensive situation analysis by predicting or measuring a representative antibiotic concentration of interest. Predicting the input loads of antibiotics to wastewater treatment plants using secondary input data (e.g. prescriptions) is a reasonable method if no analytical data is available. The absence of such data poses the question of an aquired reasonable sample quantity to capture local seasonal differences in prescriptions as well as flow conditions within the catchment area. Both, the theoretical and measurement based determination of environmental concentrations have been scarcely verified in practice. Hence, high resolution prescription data in combination with an extensive monitoring campaign at the wastewater treatment plant Dresden-Kaditz (WWTP) were used as a basis to evaluate the reliability of predicting and measuring urban antibiotic emissions. As expected, the recovery of antibiotic input loads strongly varies among substances. The group of macrolides as well as sulfamethoxazole and trimethoprim were almost fully recovered whereas nearly all substances of the beta-lactam family exhibit high elimination rates during the wastewater transport in the sewer system. Yet other antibiotics (e.g. fluoroquinolones) show distinct fluctuations through the year, which was not obvious from relatively constant prescriptions. The latter substances are an example that available data are not per se sufficient to predict the actual release into the environment which, in certain cases, emphasizes the necessity of adequate measuring campaings. The extensive data pool of this study was hence used to calculate the necessary number of samples to determine a representative annual mean load to the WWTP. Based on the applied approach, a minimum number of 20 to 40 samples per year is proposed to reasonably estimate a representative annual input load of antibiotics and other micropollutants. Regarding the WWTP, the mass flow analysis revealed that macrolides, clindamycin/ clindamycin-sulfoxide and trimethoprim were mainly released with the effluent, while penicillins, cephalosporins as well as sulfamethoxazole were partly degraded in the studied WWTP. Levofloxacin and ciprofloxacin are the only antibiotics under investigation with a significant mass fraction bound to primary, excess and digested sludge. In this context, the sludge concentrations are considered to be highly inconsistent which leads to questionable results. It remains unclear whether the inconsistencies are due to insufficiencies in sampling and/or analytical determination or if the fluctuations can be considered reasonable for digesters. Subsequently, verified antibiotic loads were evaluated regarding their ecotoxicological effects in the aquatic environment. Two approaches were applied (1) to address the ecological impact on individual trophic levels algae, daphnia and fish, and (2) to assess the possible synergistic potential of antibiotic combinations. Ciprofloxacin, levofloxacin and the group of cephalosporins showed to significantly affect the aquatic environment. They either have the highest impact on (one of) the lowest trophic level(s) or disproportionately increase the ecotoxicological risk due to their synergistic characteristics. In this regard, the deficiencies regarding the input prediction of these antibiotics is of particular concern. The underestimation of such critical mass flow conditions weakens the approach of assessing environmental risks on the basis of secondary data like prescriptions. Hence, efforts must be made to further develop the projection model by improving the quality of secondary data, identifying additional emitters and understanding possible retention and degradation dynamics of antibiotics within the sewer system
In der Humanmedizin eingesetzte Antibiotika werden im menschlichen Körper nicht vollständig metabolisiert und gelangen über die Ausscheidungen in das kommunale Abwasser. In der Kläranlage erfolgt nur eine unvollständige Elimination dieser Stoffe, so dass der Kläranlagenablauf einen Hot Spot für Antibiotikaemissionen in die Umwelt darstellt. Das induzierte ökotoxikologische Risiko kann anhand standardisierter Testverfahren und allgemein anerkannter Bewertungsansätze für Einzelsubstanzen abgeschätzt werden. Erfolgt jedoch die Betrachtung von Antibiotikagemischen, wie es für den gereinigten Ablauf einer Kläranlage sinnvoll ist, sind aufgrund zumeist unspezifischer Wirkmechanismen und dem Mangel an repräsentativen Daten eine Reihe von Vereinfachungen und Annahmen zu treffen. Es besteht in der Folge die Gefahr einer Unterschätzung des durch Substanzgemische hervorgerufenen ökotoxikologischen Risikos. Eine vielversprechende Möglichkeit den Entscheidungsprozess über mögliche Vermeidungs- und Eliminationsmaßnahmen zu unterstützen besteht in der Priorisierung von Antibiotika entsprechend ihres Effektpotentials. Hierbei sind Substanzen zu identifizieren, die den größten Einfluss auf die Nahrungskette im Gewässer bzw. das höchste (negative) Synergiepotential mit anderen Substanzen aufweisen. Die Verringerung dieser Substanzen führt zu einer hohen ökologischen Effektivität und Effizienz der eingesetzten Mittel. Wie im Fall des klassischen Bewertungsansatzes, ist auch für den Priorisierungsansatz eine umfängliche und zuverlässige Situationsanalyse die Grundvoraussetzung für verwertbare Ergebnisse. Die Situationsanalyse beruht auf der analytischen Bestimmung bzw. der Abschätzung von emittierten Antibiotikafrachten zur Berechnung von repräsentativen Umweltkonzentrationen. Analytisch ermittelte Umweltkonzentrationen vieler Antibiotika weisen aufgrund saisonaler Verschreibungsmuster eine hohe zeitliche und räumliche Variabilität auf. Die für eine adäquate Erfassung der Situation notwendigen Messkampagnen sind kostenintensiv, wobei die tatsächlich notwendige Häufigkeit der Probenahme von zumeist nicht hinreichend bekannten substanzspezifischen Informationen, wie der chemischen Stabilität im Rohabwasser und der saisonal beeinflussten Applikation, abhängt. Alternativ können Antibiotikaeinträge in die Kanalisation anhand von Verschreibungsdaten abgeschätzt und mit Hilfe von Stoffflussanalysen (SFA) zur ökotoxikologischen Bewertung herangezogen werden. Eine vom Umfang befriedigende, direkte Gegenüberstellung von prognostizierten und analytisch ermittelten Frachten ist bisher jedoch nicht erfolgt, so dass die Verifizierung dieses Ansatzes noch aussteht. Für den Fall einer bestehenden Verschreibungspflicht für Antibiotika besitzen Verschreibungsdaten eine vergleichsweise hohe zeitliche und räumliche Informationsgüte. In Verbindung mit einer an diese Datenqualität angepassten Messkampagne, ergibt sich die Möglichkeit einer detaillierten SFA mit substanzspezifischer Bewertung der Eignung des Prognoseansatzes. Die am Beispiel der Stadt Dresden durchgeführte Bewertung des Prognoseansatzes fußt auf einer 15-monatigen Messkampagne und den für das Einzugsgebiet der Zentralkläranlage Dresden-Kaditz verfügbaren Verschreibungsdaten der AOK PLUS. Erwartungsgemäß ergibt der Abgleich von erwarteten und analytisch ermittelten Frachten eine starke Variation der für den Zulauf der Kläranlage ermittelten Wiederfindungsdaten verschiedener Substanzen. Die analytisch ermittelten Frachten von Sulfamethoxazol, Trimethoprim sowie der Gruppe der Makrolid-Antibiotika entsprechen nahezu den prognostizierten Mengen. Die Beta-Laktam-Antibiotika unterliegen bereits während des Abwassertransports einer umfänglichen, zumeist biologisch bedingten, Elimination, was zu hohen Unterbefunden im Zulauf der Kläranlage führt. Andere Substanzen hingegen (z.B. Fluorchinolone) weisen messtechnisch eine signifikante Jahresdynamik auf, die aufgrund der weitgehend konstanten Verschreibung in dieser Ausprägung nicht zu erwarten ist. Die Auswertung zuletzt genannter Substanzen zeigt deutlich, dass die Nutzung von Verschreibungsdaten nicht per se ausreicht, um die Emission von Antibiotika (und anderer Pharmazeutika) sowie die sich daraus ergebenden Umweltkonzentrationen mit ausreichender Sicherheit prognostizieren zu können. Für eine nachgelagerte ökotoxikologische Bewertung ist in diesen Fällen die Durchführung von Messungen unumgänglich. Zur effizienten Planung derartiger Kampagnen wurde der umfassende Datenpool dieser Studie hinsichtlich der erforderlichen Probenanzahl zur Bestimmung einer repräsentativen mittleren Jahresfracht ausgewertet. Es ergibt sich ein Minimum von 20 bis 40 homogen über das Jahr verteilten Proben, um die jährlich in die Kläranlage eingetragene Fracht an Antibiotika bzw. anderer Mikroschadstoffe mit ausreichender Sicherheit abschätzen zu können. Im Rahmen der SFA in der Kläranlage Dresden-Kaditz wird deutlich, dass Makrolide, Clindamycin und dessen Humanmetabolit Clindamycin-Sulfoxid sowie Trimethoprim in der nahezu keiner Elimination unterliegen, wohingegen Penizilline, Cefalosporine und auch Sulfamethoxazol teilweise bis vollständig abgebaut werden. Mit Levofloxacin und Ciprofloxacin handelt es sich um die einzigen untersuchten Antibiotika, welche zu einem signifikanten Massenanteil an Primär-, Überschuss- und Faulschlamm gebunden vorgefunden werden. Aufgrund der hohen Relevanz dieses Eliminationspfades für die zuvor genannten Antibiotika bedarf die Beobachtung von z. T. widersprüchlichen Schwankungen einer kritischen Betrachtung der Ergebnisse. Es ist nicht abschließend geklärt, ob die beobachteten Fluktuationen auf eine unzureichende Qualität der Probenahme und/oder der Analytik zurückzuführen sind oder sich die Schwankungen in einem für Faulbehälter tolerierbaren Bereich befinden. Im Anschluss an die verifizierten Antibiotikaemissionen erfolgte die Priorisierung der betrachteten Antibiotika nach ihrem ökotoxikologischen Effektpotential. Zum einen wurde der ökologische Einfluss auf verschiedene, die Nahrungskette bildende trophische Ebenen (Alge, Daphnie, Fisch) untersucht. In Anlehnung an die humanmedizinische Kombinationstherapie erfolgte im zweiten Ansatz die Beurteilung der Antibiotika hinsichtlich ihres möglichen Potentials zur Verstärkung von negativen Effekten durch das gleichzeitige Auftreten mit anderen Substanzen. Für Ciprofloxacin, Levofloxacin und die Gruppen der Makrolide und Cefalosporine konnten signifikante Beeinträchtigungen der aquatischen Umwelt nachgewiesen werden. Diese Stoffe und Stoffgruppen führten im Rahmen der untersuchten Substanzen entweder zur höchsten Schadwirkung gegenüber der niedrigsten trophischen Ebene oder besitzen das höchste Synergiepotential in Kombination mit anderen Substanzen. Die Auswertung der SFA bestätigt die grundsätzliche Eignung der Verschreibungsdaten sowie des entwickelten Prognosemodells zur Vorhersage von Antibiotikaemissionen im urbanen Raum. Die Stoffflussanalyse stellt somit ein strategisches, im Vergleich zur Messung kostengünstiges Instrument zur Identifikation von Hot Spots der Antibiotikaemission dar und erleichtert die Entscheidungsfindung für monetär aufwendige Reduktionsmaßnahmen am Ort der Entstehung oder in der Kläranlage (z.B. 4. Reinigungsstufe). Die Vorgehensweise zur Priorisierung von Substanzen hinsichtlich ihres ökotoxikologischen Effektpotentials eignet sich sehr gut, Antibiotika mit dem höchsten Schadpotential zu identifizieren. Die Verschneidung der Kenntnis dieser Substanzen mit den Ergebnissen der SFA macht deutlich, dass mit Ausnahme der Makrolide, alle ökotoxikologisch priorisierten Antibiotika eine mangelhafte Prognosefähigkeit aufweisen. Die unvollständige Abbildung kritischer Stoffströme, wie z.B. Frachtspitzen, führt insbesondere im Fall der ökotoxikologisch priorisierten Substanzen zu einer Minderung der Aussagekraft des auf Verschreibungsdaten beruhenden Prognoseansatzes. An diesem Punkt ist in zukünftigen Betrachtungen anzusetzen, um die Qualität von Verschreibungsdaten zu verbessern, potentiell nicht erfasste Emittenten in die Betrachtungen einzubeziehen, sowie die Dynamik der Rückhalte- und Eliminationsprozesse in der Kanalisation adäquat beschreiben zu können. Die ergänzende Betrachtung weiterer Anlagentechnologien (z.B. Festbettreaktoren) kann zur Bestätigung der am Beispiel der Kläranlage Dresden-Kaditz gewonnenen Ergebnisse beitragen bzw. Unterschiede bei der Elimination von Antibiotika das Potential, die Problematik der Antibiotika und anderer Mikroschadstoffe bereits während der Planung von Abwasseranlagen berücksichtigen zu können

Thesis (Ph.D.)--Case Western Reserve University, 2004
Title from PDF (viewed on 01 October 2009) Department of Mechanical Engineering Includes abstract Includes bibliographical references Available online via the OhioLINK ETD Center

In this work, we address a variety of problems with applications to `ethanol production from biomass', `agile manufacturing' and `mass customization' domains. Our motivation stems from the potential use of biomass as an alternative to non-renewable fuels, the prevalence of `flexible manufacturing systems', and the popularity of `mass customization' in today's highly competitive markets. Production scheduling and design and optimization of logistics network mark the underlying topics of our work. In particular, we address three problems, Biomass Logistics Problem, Hybrid Flow Shop Scheduling Problem, and Stochastic Demand Assembly Job Scheduling Problem. The Biomass Logistics Problem is a strategic cost analysis for setup and operation of a biomass supply chain network that is aimed at the production of ethanol from switchgrass. We discuss the structural components and operations for such a network. We incorporate real-life GIS data of a geographical region in a model that captures this problem. Consequently, we develop and demonstrate the effectiveness of a `Nested Benders' based algorithm for an efficient solution to this problem. The Hybrid Flow Shop Scheduling Problem concerns with production scheduling of a lot over a two-stage hybrid flow shop configuration of machines, and is often encountered in `flexible manufacturing systems'. We incorporate the use of `lot-streaming' in order to minimize the makespan value. Although a general case of this problem is NP-hard, we develop a pseudo-polynomial time algorithm for a special case of this problem when the sublot sizes are treated to be continuous. The case of discrete sublot sizes is also discussed for which we develop a branch-and-bound-based method and experimentally demonstrate its effectiveness in obtaining a near-optimal solution. The Stochastic Demand Assembly Job Scheduling Problem deals with the scheduling of a set of products in a production setting where manufacturers seek to fulfill multiple objectives such as `economy of scale' together with achieving the flexibility to produce a variety of products for their customers while minimizing delivery lead times. We design a novel methodology that is geared towards these objectives and propose a Lagrangian relaxation-based algorithm for efficient computation.
Doctor of Philosophy
In this work, we organize our research efforts in three broad areas - Biomass Supply Chain, Hybrid Flow Shop, and Assembly Job Shop, which are separate in terms of their application but connected by scheduling and logistics as the underlying functions. For each of them, we formulate the problem statement and identify the challenges and opportunities from the viewpoint of mathematical decision making. We use some of the well known results from the theory of optimization and linear algebra to design effective algorithms in solving these specific problems within a reasonable time limit. Even though the emphasis is on conducting an algorithmic analysis of the proposed solution methods and in solving the problems analytically, we strive to capture all the relevant and practical features of the problems during formulation of each of the problem statement, thereby maintaining their applicability. The Biomass Supply Chain pertains to the production of fuel grade ethanol from naturally occurring biomass in the form of switchgrass. Such a system requires establishment of a supply chain and logistics network that connects the production fields at its source, the intermediate points for temporary storage of the biomass, and bio-energy plant and refinery at its end for conversion of the cellulosic content in the biomass to crude oil and ethanol, respectively. We define the components and operations necessary for functioning of such a supply chain. The Biomass Logistics Problem that we address is a strategic cost analysis for setup and operation of such a biomass supply chain network. We focus our attention to a region in South Central Virginia and use the detailed geographic map data to obtain land use pattern in the region. We conduct survey of existing literature to obtain various transportation related cost factors and costs associated with the use of equipment. Our ultimate aim here is to understand the feasibility of running a biomass supply chain in the region of interest from an economic standpoint. As such, we represent the Biomass Logistics Problem with a cost-based optimization model and solve it in a series of smaller problems. A Hybrid Flow Shop (HFS) is a configuration of machines that is often encountered in the flexible manufacturing systems, wherein a particular station of machines can execute processing of jobs/tasks simultaneously. In our work, we approach a specific type of HFS, with a single machine at the first stage and multiple identical machines at the second stage. A batch or lot of jobs/items is considered for scheduling over such an HFS. Depending upon the area of application, such a batch is either allowed to be split into continuous sections or restricted to be split in discrete sizes only. The objective is to minimize the completion time of the last job on its assigned machine at the second stage. We call this problem, Hybrid Flow Shop Scheduling Problem, which is known to be a hard problem in literature. We aim to derive the results which will reduce the complexity of this problem, and develop both exact as well as heuristic methods in order to obtain near-optimal solution to this problem. An Assembly Job Shop is a variant of the classical Job Shop which considers scheduling a set of assembly operations over a set of assembly machines. Each operation can only be started once all the other operations in its precedence relationship are completed. Assembly Job Shop are at the core of some of the highly competitive manufacturing facilities that are principled on the philosophy of Mass Customization. Assuming an inherent nature of demand uncertainty, this philosophy aims to achieve ‘economy of scale’ together with flexibility to produce a variety of products for the customers while minimizing the delivery lead times simultaneously. We incorporate some of these challenges in a concise framework of production scheduling and call this problem as Stochastic Demand Assembly Job Scheduling Problem. We design a novel methodology that is geared towards achieving the set objectives and propose an effective algorithm for efficient computation.

PFCs are used in a wide variety of industrial and commercial applications for more than 50 years. Among variation of PFCs, Perfluorooctane sulfonate (PFOS) (CF3(CF2)7SO3-) and perfluorooctanoic acid (PFOA) (CF3(CF2)6COO-) are the most dominant PFCs. In May 2009, PFOS, its salts and perfluorooctane sulfonyl fluoride (PFOSF) are designated as new Persistent Organic Compounds (POPs) which are resistant, bio-accumulating, and having potential of causing adverse effects to humans and environment (IISD, 2009). However, products containing PFCs are still being manufactured and used, which could be the main reason why they are still observed in the environment and biota (Berger et al., 2004; Saito et al., 2003; Sinclair et al., 2004). The study is focused on the PFCs contamination in water and industrial wastewater around the Central and Eastern Thailand, where is one of the major industrialized areas in the country. The samplings were conducted in major rivers, Chao Phraya, Bangpakong and Tachin River. PFCs were contaminated in all rivers. The average total PFCs were 15.10 ng/L, 18.29 ng/L and 7.40 ng/L in Chao Phraya, Bangpakong and Tachin River, respectively. PFOS and PFOA were the predominant PFCs in all samples. The total of 118.6 g/d PFOS and 323.6 g/d PFOA were released from the three rivers to the Gulf of Thailand. The survey was also conducted in small rivers, reservoirs, and coastal water around Eastern Thailand, where many industrial zones (IZ) are located. The geometric mean (GM) concentration of each PFC was ranged from 2.3 to 107.7 ng/L in small rivers, 2.2 to 212.2 ng/L in reservoirs, and 0.8 to 41.1 ng/L in coastal water samples. The higher PFCs contaminations were detected in the surface water around the industrial zones, where might be the sources of these compounds. Field surveys were also conducted in ten industrial zones (IZ1 – IZ10) to identify the occurrences of PFCs from in industries. The recovery rates of PFCs in the samples indicated that the matrix interference or enhancement was an important problem in PFCs analysis. The elevated concentrations were detected in electronics, textile, chemicals and glass making industries. Total PFCs concentrations in the influent of WWTP were ranged from 39.6 to 3, 344.1 ng/L. Ten industrial zones released 188.41 g/d of PFCs. All of the treatment processes inside industrial zones were biological processes, which were reported that they were not effective to remove PFCs. The influence of industrial discharges was affected not only the rivers and reservoirs but also in the coastal water. The PFCs in rivers and reservoirs were discharged to the Gulf of Thailand, which is the important food source for Thai people and exports. Due to the problems in industrial wastewater analysis, several optimizing options were applied in PFCs analytical method especially in Solid Phase Extraction (SPE) procedure. The combination of PresepC-Agri and Oasis®HLB was the better option for analyzing PFCs in water samples. The optimum flow rate for loading the samples was 5 mL/min. Methanol (2 mL) plus Acetronitrile (2 mL) was the effective way to elute PFCs from the cartridges. The specific solvent percentages to elute each PFCs were identified for both water and industrial wastewater samples. The matrix removal methods by using Envi-Carb and Ultrafilter were effective for different types of industrial wastewater samples. PFCs were detected in surface waters, which are the sources of tap and drinking water for the people in Central and Eastern Thailand. The surveys were conducted in Bangkok city. Samples were collected from water treatment plants (WTPs), tap water, and drinking water. PFCs were detected in all tap water and drinking water samples. PFOS and PFOA concentrations in raw water of WTP were found 4.29 ng/L and 16.54 ng/L, respectively. The average PFOS and PFOA concentrations in tap water were detected 0.17 and 3.58 ng/L, respectively. The tap water results also showed that PFOS and PFOA concentrations were not similarly detected in all area in the city. PFOA were detected higher in the western area, while PFOS concentration was quite similar in all areas. Overall, it can be concluded that the current treatment processes were not completely remove PFCs. Nevertheless, PFCs in particulate phase were effectively removed by the primary sedimentation and rapid sand filtration. Elevated PFCs were found in the industrial zones (IZ2 and IZ5). To understand the distribution and fate of PFCs during industrial wastewater process, PFCs mass flows were studied. Higher PFCs in adsorbed phase were detected only in activated sludge and some influent samples. In IZ2, PFOA loading in the dissolved phase increased after activated sludge process by 5%. There was no degradation of PFOA inside the polishing pond. The highest loading to the treatment plant was PFOS with the loading of 2, 382 mg/d and 1, 529 mg/d in dissolved and adsorbed phase, respectively. Unlike PFCAs that showed no removal in the treatment process, PFOS were decreased during the treatment processes with 36% in the activated sludge process and 36% in the polishing pond. The predominant in this IZ5 was PFOS. The increasing of PFOS was also found in this treatment plant dissimilar to IZ2. PFOS was increasing by 45% in dissolved phase and 47% in adsorbed phase. All of PFCs in this industrial zone were detected higher in the effluent, indicated that PFCs’ precursors should be the major effects of this contamination.
Kyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第14930号
工博第3157号
新制||工||1473(附属図書館)
27368
UT51-2009-M844
京都大学大学院工学研究科都市環境工学専攻
(主査)教授 田中 宏明, 教授 清水 芳久, 教授 藤井 滋穂
学位規則第4条第1項該当

This thesis demonstrates the use of numerical simulation in predicting the behavior of proteins in a flow environment. A novel convection-diffusion-reaction computational model is first introduced to simulate fibroblast growth factor (FGF-2) binding to its receptor (FGFR) on cell surfaces and regulated by heparan sulfate proteoglycan (HSPG) under flow in a bioreactor. The model includes three parts: (1) the flow of medium using incompressible Navier-Stokes equations; (2) the mass transport of FGF-2 using convection-diffusion equations; and (3) the cell surface binding using chemical kinetics. The model consists of a set of coupled nonlinear partial differential equations (PDEs) for flow and mass transport, and a set of coupled nonlinear ordinary differential equations (ODEs) for binding kinetics. To handle pulsatile flow, several assumptions are made including neglecting the entrance effects and an approximate analytical solution for axial velocity within the fibers is obtained. To solve the time-dependent mass transport PDEs, the second order implicit Euler method by finite volume discretization is used. The binding kinetics ODEs are stiff and solved by an ODE solver (CVODE) using Newton’s backward differencing formula. To obtain a reasonable accuracy of the biochemical reactions on cell surfaces, a uniform mesh is used. This basic model can be used to simulate any growth factor-receptor binding on cell surfaces on the wall of fibers in a bioreactor, simply by replacing binding kinetics ODEs. Circulation is an important delivery method for natural and synthetic molecules, but microenvironment interactions, regulated by endothelial cells and critical to the molecule’s fate, are difficult to interpret using traditional approaches. Growth factor capture under flow is analyzed and predicted using computer modeling mentioned above and a three-dimensional experimental approach that includes pertinent circulation characteristics such as pulsatile flow, competing binding interactions, and limited bioavailability. An understanding of the controlling features of this process is desired. The experimental module consists of a bioreactor with synthetic endotheliallined hollow fibers under flow. The physical design of the system is incorporated into the model parameters. FGF-2 is used for both the experiments and simulations. The computational model is based on the flow and reactions within a single hollow fiber and is scaled linearly by the total number of fibers for comparison with experimental results. The model predicts, and experiments confirm, that removal of heparan sulfate (HS) from the system will result in a dramatic loss of binding by heparin-binding proteins, but not by proteins that do not bind heparin. The model further predicts a significant loss of bound protein at flow rates only slightly higher than average capillary flow rates, corroborated experimentally, suggesting that the probability of capture in a single pass at high flow rates is extremely low. Several other key parameters are investigated with the coupling between receptors and proteoglycans shown to have a critical impact on successful capture. The combined system offers opportunities to examine circulation capture in a straightforward quantitative manner that should prove advantageous for biological or drug delivery investigations. For some complicated binding systems, where there are more growth factors or proteins with competing binding among them moving through hollow fibers of a bioreactor coupled with biochemical reactions on cell surfaces on the wall of fibers, a complex model is deduced from the basic model mentioned above. The fluid flow is also modeled by incompressible Navier-Stokes equations as mentioned in the basic model, the biochemical reactions in the fluid and on the cell surfaces are modeled by two distinctive sets of coupled nonlinear ordinary differential equations, and the mass transports of different growth factors or complexes are modeled separately by different sets of coupled nonlinear partial differential equations. To solve this computationally intensive system, parallel algorithms are devised, in which all the numerical computations are solved in parallel, including the discretization of mass transport equations and the linear system solver Stone’s Implicit Procedure (SIP). A parallel SIP solver is designed, in which pipeline technique is used for LU factorization and an overlapped Jacobi iteration technique is chosen for forward and backward substitutions. For solving binding equations ODEs in the fluid and on cell surfaces, a parallel scheme combined with a sequential CVODE solver is used. The simulation results are obtained to demonstrate the computational efficiency of the algorithms and further experiments need to be conducted to verify the predictions.

A new surface aeration system for water and wastewater treatment has been studied. Its uniqueness lies in its ability to operate in two modes: aeration or simply blending (mixing) by just reversing the direction of rotation. An experimental plant has enabled to focus on mass transfer performance and hydrodynamics. The flow pattern and the velocity field measurements inside the agitated tank were performed by both the Laser Doppler Velocimetry (LDV) and the Particle Image Velocimetry (PIV) techniques for the single phase (Mixing) mode and for the two phases (Aeration) mode. The oxygen mass transfer occurs both in the water bulk and in the spray above water surface and has been independently investigated. Different configurations and operational conditions were tested during the experimental part in order to interpret phenomenon effect of the draft tube and RTP propeller, rotational speed, turbine blades submergence and else on the flow field and the oxygen mass transfer in the agitated system that produced mainly by a cone shape turbine. The experimental part dealing with hydrodynamics and flow field shows that the down-pumping operation mode with the draft tube has the most convenient results in the mixing mode with respect to turbulent flow field and mixing time. Whilst for the up-pumping aeration mode the hydrodynamics experimental results show the whole system configuration is the most convenient with regarded to mean velocities, turbulent flow intensity and mixing time. For the oxygen mass transfer experimental part, it is found that the highest standard liquid bulk aeration efficiency is achieved (SAEb = 2.65 kgO2 kw-1h-1) when the whole system configuration is used. The highest standard aeration efficiency at 20°C for the water spray zone is accomplished ((Esp)20 = 51.3 %) with the whole system configuration. Several correlations models have been derived for the oxygen mass transfer in water bulk and spray zones, power consumption and mixing time, on the basis of experimental results. They can be used as tools to estimate these parameters for geometrical and dynamical similar systems at industrial scales.

A study of the extraction of cobalt II ions from an aqueous growing drop into a continuous medium of di-2-ethylhexylphosphoric acid (D2EHPA) is made. The apparatus for this technique is described and a flow injection analysis method for measuring the cobalt remaining in the aqueous phase has been developed. In this study the feed concentration of cobalt has varied between 8.48 x 10-3 and 16.97 x 10-3 mole 9-1. The D2EHPA held in n-heptane, has been altered between 0.143 and 2.41 mole P. Also, pH has been adjusted between 3.10 and 4.44. The principal temperature applied to this study was 25 ±0.5*C. Acetate buffers have been used, but it is shown by calculation that about 70% of the cobaltous ion is in an uncomplexed form. The kinetics of the extraction have been modelled using a method based upon reaction in an aqueous zone near to the liquid-liquid interface with diffusion of species towards and away from the interface. This model provided a fundamental parameter 01 which incorporates the chemical rate constant kR, the D2EHPA partition coefficient PHR, the acid dissociation constnat KD for D2EHPA and the metal ion diffusivity in the interface diffusion region. The results have been compared with those of other workers who studied the transfer of cobalt into an organic drop from an aqueous continuum. The diffusion controlling film is the aqueous one. The rate constant for, the extraction reaction equation is, from this work, kR - 106.34 M3 kmol-1 sec-1 which can be compared with that found by another worker using the reverse transfer system, i. e. kR - 106.18 m3 kmol-I sec-i. . Finally, the mass transfer coefficients were found to change with varying feed concentrations and pH, this is also in agreement with other workers who have studied different liquid-liquid systems.

This thesis describes a combined 1-D numerical and experimental analysis of a GDI injection system. The aim is to design the GDI injection system to have the minimum injection variability between injectors. This is possible analysing the rail pressure waves that affect the injections. Thanks to a MATLAB numerical code the results coming from a first calibration attempt were compared with experimental data to verify the reliability of the acquired results. They were calculated after specific tests made on the hydraulic test bench developed at Lamborghini. Different configurations were studied changing the system geometry, such as rail diameter, high pressure pipe length and inlet position inside the rail, flow-restrictor diameter at the end of high pressure pipe. Eight different configurations were analysed and the one that showed the lowest CoV of injection was proposed as a final design. Then a 1-D numerical analysis of the GDI injection system was developed on the chosen configuration with the aim of predicting pressure waves propagation phenomena and the injected mass flow rate. The focus of the 1-D analysis is to verify through the comparison between simulated values and experimental ones if the model predicts accurately the physics of the system, in order to use it on a wider range of operating points. The following step consisted in controlling the GDI pump in MIL environment through a cosimulation between high pressure system model built in GT-ISE and control model made with Simulink. The high pressure control model was developed and validated. The aim was to have a closed loop control of the rail pressure using the same ECU control strategy. The main task of the control is to actuate the angle, respect to pump TDC, the MSV valve had to be closed to make the actual pressure follow the target one. The control model and the simulation in MIL environment are very useful since they help on the precalibration of ECU functions, reducing testing activities.

Degradation of water resources has become one of the most pressing global concerns currently facing mankind. Constructed Wetlands (CWs) represent a concept to combat deterioration of water resources by acting as buffers between wastewater and receiving water bodies. Still, constructing wetlands for the sole purpose of wastewater treatment is a challenging task. To contribute to this research area, the fundamental question raised in this doctorate thesis was: how do factors such as vegetation and residing water movements (hydraulics) influence wastewater treatment in CWs? Also, effects of different data analysis methods for results of CW hydraulics and wastewater treatment were investigated. Research was focused on  phosphorus (P), ammonium-nitrogen (NH4+-N) and solids (TSS) in wastewater and o n P in macrophyte biomass. Studies were performed in pilot-scale free water surface (FWS) CW systems in Kenya (Chemelil) and Sweden (Halmstad) and as computer simulations. Results from the Chemelil CWs demonstrated that meeting effluent concentration standards simultaneously for all water quality parameters in one CW was difficult. Vegetation harvest, and thus nutrient uptake by young growing macrophytes, was important for maintaining low effluents of NH4+-N and P, especially during dry seasons. On the other hand, mature and dense vegetation growing for at least 4 months secured meeting TSS standards. Phosphorus in above-ground green biomass accounted for almost 1/3 of the total P mass removal, demonstrating high potential for P removal through macrophyte harvest in CWs. Also, results suggested that harvest should be species-specific to achieve high P removal by macrophytes and overall acceptable wastewater treatment in CWs. Still, different methods to estimate evapotranspiration (ET) from the Chemelil CWs showed that water balance calculations greatly impacted estimations of wastewater treatment results. Hydraulic tracer studies performed in the Chemelil and Halmstad CWs showed that mature and dense emergent vegetation in CWs could reduce effective treatment volumes (e-values), which emphasized the importance of regulating this type of vegetation. Also, it was shown that hydraulic tracer studies with lithium chloride performed in CWs with dense emergent vegetation had problems with low tracer recoveries. This problem could be reduced by promoting the distribution of incoming tracer solution into the CW using a barrier near the CW inlet pipe. Computer simulation results showed that the choice of tracer data analysis method greatly influenced quantifications of CW hydraulics and pollutant removal. The e-value could be 50% higher and the pollutant removal 13% higher depending upon used method. Moreover, unrealistic evalues (above 100%) in published literature could to some extent be explained by tracer data analysis method. Hence, to obtain more reliable hydraulic data and wastewater treatment results from CWs, more attention should be paid to the choice of tracer data analysis method.
Konstruerade våtmarker representerar ett koncept för möjligheten att nå en hållbar vattenresurshantering genom att agera som ”filter” mellan föroreningskälla och viktiga vattenresurser såsom sjöar och hav. Mycket kunskap saknas däremot om hur man konstruerar våtmarker med en optimal och pålitlig vattenreningskapacitet. Den här avhandlingen undersöker därför hur vegetation och vattnets väg genom våtmarken (hydrauliken) påverkar avloppsvattenrening i våtmarker. Dessutom undersöktes hur valet av dataanalysmetod av insamlad data påverkar resultaten. Studier genomfördes i Kenya och Sverige i experimentvåtmarker (ca. 40-60 m2) och inkluderadedatainsamling av vattenkvalité, hydraulik (spårämnesexperiment) samt biomassa och fosfor i biomassan av två olika våtmarksväxter. Dessutom genomfördes datorsimuleringar. Resultaten från Kenya visade att växtskörd och efterföljande näringsupptag av nyskördade växter var viktig för att uppnå låga utgående koncentrationer av fosfor och ammonium i en tropisk våtmark, speciellt under torrsäsongen. Däremot var en välutvecklad och tät vegetation viktig för reningen av partiklar. Fosfor i grön växtbiomassa representerade cirka 1/3 av våtmarkernas totala fosforrening, vilket påvisade potentialen i att genom skörd ta bort fosfor från avloppsvatten m.h.a. konstruerade våtmarker. Resultaten pekade också på att skörden bör vara art-specifik för att uppnå en hög fosforrening och generellt bra vattenreningsresultat. Dock visade olika beräkningsmetoder att vattenbalansen i en tropisk våtmark markant kan påverka vattenreningsresultaten. Resultaten från spårämnesexperimenten demonstrerade att den effektiva våtmarksvolymen för vattenrening blev mindre vid hög täthet av övervattensväxter. Detta pekade på att regelbunden växtskörd var viktig för att uppnå god vattenrening i våtmarker. Experiment med spårämnet litium visade att man kan få felaktiga resultat p.g.a. att en del spårämne fasthålls på botten i våtmarken om denna har mycket övervattensväxter. Därför bör spridningen av spårämnet i sådana våtmarker underlättas m.h.a. en spridningsbarriär nära inloppsröret. Simuleringar visade också att valet av dataanalysmetod av spårämnesdata starkt kan påverka resultaten och därmed också vår tolkning av en våtmarks hydraulik och reningskapacitet. Den effektiva volymen kunde vara 50% högre och reningseffekten 13% högre beroende på vilken metod som användes. Likaså kan valet av dataanalysmetod ha bidragit till överskattade och orealistiska effektiva volymer (över 100%) i artiklar publicerade de senaste 25 åren. Genom att fokusera mer på valet av dataanalysmetod och t.ex. jämföra resultaten från två olika metoder kan man minimera risken för bristfälliga resultat och därmed felaktiga slutsatser om en våtmarks vattenreningskapacitet.

Large and ever-increasing numbers of chemicals, including large quantities of a broad spectrum of organic compounds are used in modern society. More than 30 000 of the more than 100 000 chemical substances registered in the EU are estimated to be daily used, of which many will be discharged into the waste-streams handled by municipal sewage treatment plants (STPs). The main objective of the work underlying this thesis was to improve understanding of the relationships between the characteristics of sewage contaminants and their sewage treatment efficiency. Further objectives were to examine the relationships between socio-economic uses of chemicals and sludge quality, and the effects of regulatory actions on sludge quality. The quality of the sewage sludge and the levels and distribution patterns of the sludge contaminants, both within and between the STPs, seem to remain quite constant over time. The overall findings indicate that the levels of contaminants in sewage sludge seem to be largely independent of the location, size and treatment techniques applied at the STPs, and generally, of the types of human activity connected to them. The total and relative concentrations of the sludge contaminants were found to be fairly constant on a dry weight basis, with some exceptions, indicating that the pollutants originate from broad usage and diffuse dispersion rather than (industrial) point sources. The proportion of cyclic methylsiloxanes recovered in sludge seems to strongly depend on their vapour pressure, which decreases with the number of siloxane units. The higher water solubility and biodegradability of organophosphorus flame retardants and plasticizers than polybrominated diphenyl ethers (PBDEs) were also reflected in lower percentages (relative to their national use) found in sludge. Significant time-trends in levels of a-third of the sludge contaminants included in the annual national measurement program were detected over a period of seven years. The levels of compounds displaying significant time-trends generally decreased following declines in the quantities used nationally. However, a quarter of these compounds showed increasing trends, of which the linear methylsiloxanes followed the same trend as used quantities. The decaBDE was also found to be increasing in sludge, probably as a result of the phase-out of pentaBDE and octaBDE. The results indicate that the STP removal efficiency of anthropogenic substances, in Sweden, is generally good and that STPs, at least those in cold climates, do not efficiently remove certain polar contaminants. A non-targeted screening (by use of environmetrics and GCxGC-TOFMS) was performed and found to fulfil the objective to assess the STP removal efficiency, with emphasis to systematically analyse which compound classes that are not efficiently removed using the current STP technology. Many polar aromatic compounds were identified to be poorly removed. The acquired data on levels, profiles and variations in sludge contaminants (sludge quality) extend both the available information and understanding of the degree and nature of sludge contamination, which should help attempts to track changes in its contaminants and revisions, if necessary, of guideline values. This thesis also contributes to improve the knowledge base for the development of future STP technologies, and that archived sewage sludge can be used in retrospective analysis of new and emerging pollutants.