Seasonal dry deposition and canopy leaching of base cations in a subtropical evergreen mixed forest, China

Abstract

Crystallization of selected anions and cations from mine waters

The aim of this Master’s thesis was to review some methods that are already being utilized in a field of mine water purification and to find and study possible new methods and chemicals for mine water purification by precipitation. The target was also to list the optimal process conditions for these precipitating chemicals. Separation methods were reviewed for several anions and cations, but being a real topical issue, sulphate removal was selected to be in the main focus. Sulphate salts e.g. Na2SO4 are relatively soluble in water, which makes the separation processes difficult. Eutectic freeze crystallization was studied more closely in laboratory tests for sodium sulphate removal. Gravimetric solubility tests were made for three cases of mixed electrolyte solutions: Na2SO4 – NaOH, BaSO4 – NaOH and Na3PO4 – NaOH. The aim of these experiments was to study the effect of NaOH addition on solubility of the studied salt. These phenomena were however noticed to be difficult to see in the used laboratory tests. Thus mathematical modelling was utilized to contribute the laboratory experiments and to bring additional information of the influence of NaOH presence on solubility of selected electrolytes, Na2SO4 and Na3PO4. The results from mathematical modelling of activity coefficients suggest Na2SO4 and Na3PO4 to be precipitated rather with presence and with higher concentrations of NaOH, since the raise of NaOH concentration decreases the solubility of these electrolytes in water.

Epäpuhtauksien vaikutus monokaliumfosfaattikiteen kasvuun

Työssä on tutkittu epäpuhtauksien vaikutusta kastelulannoitesuolojen monokaliumfosfaatin, kaliumnitraatin ja ureafosfaatin kiteytyksessä. Kirjallisuusosassa on käsitelty kastelulannoiteprosessit ja epäpuhtauksien vaikutus kastelulannoitteiden valmistuksessa. Kiteytys ja kiteenkasvu on esitetty perusyhtälöin, joissa on otettu epäpuhtauksien vaikutus huomioon. Tarkemmin on perehdytty monokaliumfosfaatin kiteytykseen ja kolmenarvoisten kationeiden, Al3+, Fe3+ ja Cr3+, vaikutukseen kiteiden kasvuun. Kolmenarvoiset metalli-ionit adsorboituvat kiteen pintaan haitaten kiteenkasvua, mikä vaikuttaa erityisesti kiteen prismapinnan kasvuun. Lisäksi on esitelty muita kiteenkasvuun vaikuttavia olosuhteita. Lopuksi on käsitelty kompleksinmuodostajia metalli-ionien haitallisten vaikutusten ehkäisijöinä. Kokeellisessa osassa suoritettiin liukoisuuskokeita monokaliumfosfaatin liukoisuuden selvittämiseksi eri pH-olosuhteissa. Suoritetuissa yksikidekokeissa tutkittiin pH:n ja kolmenarvoisten kationeiden; Al3+, Fe3+ ja Cr3+, vaikutus monokaliumfosfaattikiteen pituus- ja leveyskasvuun ja kidemuotoon eri ylikylläisyyksillä. Lisäksi tutkittiin voidaanko lämpötilaa ja pH muuttamalla tai pyrofosfaattia lisäämällä poistaa raudan kasvua inhiboima vaikutus. Kiteytyslämpötilaa nostamalla voidaan poistaa raudan haitallinen vaikutus kiteen kasvuun.

Työntömastotrukkien tuotannon optimointi

Tutkimuksessa luodaan Tuko Logistics Oy:n työntömastotrukkien toimintaa opti-moivia toimintaehdotuksia varastonohjausjärjestelmästä saatavan työntömastotruk-kidatan pohjalta. Tutkimus on toteutettu haastattelututkimuksena ja käyttäen apuna tieteellisiä julkaisuja. Tehtävien lomittamistutkimuksen ja loogiseen päättelyn tulok-sena on luotu kaksi toimintaehdotusta: A ja B. Toimintaehdotusten vaikutuksia van-haan järjestelmään verrataan mittareilla, joista osa on tehty jonoteorian jonomallien laskukaavojen pohjalta. Mittareita ovat: tehdyt tehtävät tunnissa, tuottamattoman ajon suhde tuottavaan, normaalitehtäväjonon pituus ja normaalitehtäväjonon koko-naisodotusaika. Toimintaehdotus B osoittautuu tehokkaammaksi ehdotukseksi, mutta Toimintaehdotus A:lla voi varmistaa tehtävien riittämisen työntömastotrukeille. Tut-kimuksessa ehdotetaan myös muita työntömastotrukkien toimintaa optimoivia muu-toksia, jotka voidaan ottaa käyttöön jokaisessa toimintamallissa.

Characterisation of Human Neutral and Lysosomal alpha-Mannosidases

Neutral alpha-mannosidase and lysosomal MAN2B1 alpha-mannosidase belong to glycoside hydrolase family 38, which contains essential enzymes required for the modification and catabolism of asparagine-linked glycans on proteins. MAN2B1 catalyses lysosomal glycan degradation, while neutral α-mannosidase is most likely involved in the catabolism of cytosolic free oligosaccharides. These mannose containing saccharides are generated during glycosylation or released from misfolded glycoproteins, which are detected by quality control in the endoplasmic reticulum. To characterise the biological function of human neutral α-mannosidase, I cloned the alpha-mannosidase cDNA and recombinantly expressed the enzyme. The purified enzyme trimmed the putative natural substrate Man9GlcNAc to Man5GlcNAc, whereas the reducing end GlcNAc2 limited trimming to Man8GlcNAc2. Neutral α-mannosidase showed highest enzyme activity at neutral pH and was activated by the cations Fe₂+, Co2+ and Mn₂+, Cu2+ in turn had a strong inhibitory effect on alpha-mannosidase activity. Analysis of its intracellular localisation revealed that neutral alpha-mannosidase is cytosolic and colocalises with proteasomes. Further work showed that the overexpression of neutral alpha-mannosidase affected the cytosolic free oligosaccharide content and led to enhanced endoplasmic reticulum associated degradation and underglycosylation of secreted proteins. The second part of the study focused on MAN2B1 and the inherited lysosomal storage disorder α-mannosidosis. In this disorder, deficient MAN2B1 activity is associated with mutations in the MAN2B1 gene. The thesis reports the molecular consequences of 35 alpha-mannosidosis associated mutations, including 29 novel missense mutations. According to experimental analyses, the mutations fall into four groups: Mutations, which prevent transport to lysosomes are accompanied with a lack of proteolytic processing of the enzyme (groups 1 and 3). Although the rest of the mutations (groups 2 and 4) allow transport to lysosomes, the mutated proteins are less efficiently processed to their mature form than is wild type MAN2B1. Analysis of the effect of the mutations on the model structure of human lysosomal alpha-mannosidase provides insights on their structural consequences. Mutations, which affect amino acids important for folding (prolines, glycines, cysteines) or domain interface interactions (arginines), arrest the enzyme in the endoplasmic reticulum. Surface mutations and changes, which do not drastically alter residue volume, are tolerated better. Descriptions of the mutations and clinical data are compiled in an α-mannosidosis database, which will be available for the scientific community. This thesis provides a detailed insight into two ubiquitous human alpha-mannosidases. It demonstrates that neutral alpha-mannosidase is involved in the degradation of cytosolic oligosaccharides and suggests that the regulation of this α-mannosidase is important for maintaining the cellular homeostasis of N-glycosylation and glycan degradation. The study on alpha-mannosidosis associated mutations identifies multiple mechanisms for how these mutations are detrimental for MAN2B1 activity. The α-mannosidosis database will benefit both clinicians and scientific research on lysosomal alpha‑mannosidosis.

Electrocoagulation in the treatment of industrial waters and wastewaters

Chemical coagulation is commonly used in raw water and wastewater treatment plants for the destabilisation of pollutants so that they can be removed in the subsequent separation processes. The most commonly used coagulation chemicals are aluminium and iron metal salts. Electrocoagulation technology has also been proposed for the treatment of raw waters and wastewaters. With this technology, metal cations are produced on the electrodes via electrolysis and these cations form various hydroxides in the water depending on the water pH. In addition to this main reaction, several side reactions, such as hydrogen bubble formation and the reduction of metals on cathodes, also take place in the cell. In this research, the applications of electrocoagulation were investigated in raw water treatment and wastewater applications. The surface water used in this research contained high concentrations of natural organic matter (NOM). The effect of the main parameters – current density, initial pH, electric charge per volume, temperature and electrolysis cell construction – on NOM removal were investigated. In the wastewater treatment studies, the removal of malodorous sulphides and toxic compounds from the wastewaters and debarking effluents were studied. Also, the main parameters of the treatment, such as initial pH and current density, were investigated. Aluminium electrodes were selected for the raw water treatment, whereas wastewaters and debarking effluent were treated with iron electrodes. According to results of this study, aluminium is more suitable electrode material for electrocoagulation applications because it produces Al(III) species. Metal ions and hydroxides produced by iron electrodes are less effective in the destabilisation of pollutants because iron electrodes produce more soluble and less charged Fe(II) species. However, Fe(II) can be effective in some special applications, such as sulphide removal. The resulting metal concentration is the main parameter affecting destabilisation of pollutants. Current density, treatment time, temperature and electrolysis cell construction affect the dissolution of electrodes and hence also the removal of pollutants. However, it seems that these parameters have minimal significance in the destabilization of the pollutants besides this effect (in the studied range of parameters). Initial pH and final pH have an effect on the dissolution of electrodes, but they also define what aluminium or iron species are formed in the solution and have an effect on the ζ-potential of all charged species in the solution. According to the results of this study, destabilisation mechanisms of pollutants by electrocoagulation and chemical coagulation are similar. Optimum DOC removal and low residual aluminium can be obtained simultaneously with electrocoagulation, which may be a significant benefit of electrocoagulation in surface water treatment compared to chemical coagulation. Surface water treatment with electrocoagulation can produce high quality water, which could be used as potable water or fresh water for industrial applications. In wastewater treatment applications, electrocoagulation can be used to precipitate malodorous sulphides to prevent their release into air. Technology seems to be able to remove some toxic pollutants from wastewater and could be used as pretreatment prior to treatment at a biological wastewater treatment plant. However, a thorough economic and ecological comparison of chemical coagulation and electrocoagulation is recommended, because these methods seem to be similar in pollutant destabilisation mechanisms, metal consumption and removal efficiency in most applications.

Nikkelin, koboltin, lyijyn ja sinkin selektiivinen erottaminen ioninleimaustekniikalla syntetisoiduilla kelatoivilla erotusmateriaaleilla

Kelatoivat erotusmateriaalit ovat osoittautuneet lupaaviksi haitallisten metallien erottamiseksi vedestä. Puhdistettava vesiliuos sisältää vain harvoin pelkästään erotettavaksi tarkoitettuja metallikationeja, sillä useimmiten mukana on erotusmateriaalien tehokkuutta heikentäviä kationeja. Parantamalla erotusmateriaalin selektiivisyyttä voitaisiin häiritsevien ionien vaikutusta vähentää selvästi. Kandidaatintyön tavoitteena oli tutkia ioninleimaustekniikan avulla syntetisoitujen kelatoivien erotusmateriaalien selektiivisyyttä nikkelille, koboltille, lyijylle ja sinkille. Käyttämällä esimerkiksi nikkelitemplaattia materiaalin synteesivaiheessa materiaalin nikkeliselektiivisyys kasvaa verrattuna perinteiseen synteesitekniikkaan. Tässä työssä tutkittiin erotusmateriaaleja, joissa oli käytetty nikkeli- tai lyijytemplaattia, vertaamalla niitä ilman templaattia syntetisoituihin materiaaleihin. Lisäksi erotustehokkuutta verrattiin kaupalliseen erotusmateriaaliin häiritsevien magnesium- ja kalsiumionien tapauksessa. Lyijyn havaittiin sitoutuvan tehokkaimmin kaikkiin syntetisoituihin materiaaleihin riippumatta nikkelitemplaatin käyttämisestä. Kinetiikkakokeet osoittivat lyijyn sitoutumisnopeudenkin olevan vertailtavista metalleista suurin. Kaikki kokeet suoritettiin huoneenlämpötilassa liuoksen pH-arvon ollessa 7,5. Nikkelitemplaatin käyttö lisäsi materiaalin selektiivisyyttä nikkelille verrattuna templaatittomaan muuten identtiseen materiaaliin. Kuitenkin materiaalien lyijyselektiivisyys oli huomattavasti nikkeliselektiivisyyttä suurempi. Lyijytemplaatin käyttö ei lisännyt lyijyselektiivisyyttä, mutta materiaalin nikkeliselektiivisyys parantui. Materiaaliin sitoutuneet nikkeli-, koboltti- ja sinkkipitoisuudet jäivät huomattavasti vähäisemmiksi verrattuna kaupalliseen materiaaliin. Magnesiumin ja kalsiumin tarttumista syntetisoituihin materiaaleihin tutkittiin myös ja tulosten mukaan IIPD2:een ja IIPD2-Methoxiin sitoutui erittäin vähän magnesiumia ja kalsiumia verrattuna kaupalliseen materiaaliin, jonka kalsiumkapasiteetti oli erityisen suuri. Kyseiset materiaalit soveltuvat tulosten perusteella myös häiritseviä ioneja sisältävien liuosten puhdistamiseen. Näin ollen valittujen kahden materiaalin jatkotutkimuksella olisi mahdollista parantaa nikkelikapasiteettia ja -selektiivisyyttä.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Working fluid selection and design of small-scale waste heat recovery systems based on organic Rankine cycles

Demand for the use of energy systems, entailing high efficiency as well as availability to harness renewable energy sources, is a key issue in order to tackling the threat of global warming and saving natural resources. Organic Rankine cycle (ORC) technology has been identified as one of the most promising technologies in recovering low-grade heat sources and in harnessing renewable energy sources that cannot be efficiently utilized by means of more conventional power systems. The ORC is based on the working principle of Rankine process, but an organic working fluid is adopted in the cycle instead of steam. This thesis presents numerical and experimental results of the study on the design of small-scale ORCs. Two main applications were selected for the thesis: waste heat re- covery from small-scale diesel engines concentrating on the utilization of the exhaust gas heat and waste heat recovery in large industrial-scale engine power plants considering the utilization of both the high and low temperature heat sources. The main objective of this work was to identify suitable working fluid candidates and to study the process and turbine design methods that can be applied when power plants based on the use of non-conventional working fluids are considered. The computational work included the use of thermodynamic analysis methods and turbine design methods that were based on the use of highly accurate fluid properties. In addition, the design and loss mechanisms in supersonic ORC turbines were studied by means of computational fluid dynamics. The results indicated that the design of ORC is highly influenced by the selection of the working fluid and cycle operational conditions. The results for the turbine designs in- dicated that the working fluid selection should not be based only on the thermodynamic analysis, but requires also considerations on the turbine design. The turbines tend to be fast rotating, entailing small blade heights at the turbine rotor inlet and highly supersonic flow in the turbine flow passages, especially when power systems with low power outputs are designed. The results indicated that the ORC is a potential solution in utilizing waste heat streams both at high and low temperatures and both in micro and larger scale appli- cations.

Hardware Accelarated Visual Tracking Algorithms. A Systematic Literature Review

Many industrial applications need object recognition and tracking capabilities. The algorithms developed for those purposes are computationally expensive. Yet ,real time performance, high accuracy and small power consumption are essential measures of the system. When all these requirements are combined, hardware acceleration of these algorithms becomes a feasible solution. The purpose of this study is to analyze the current state of these hardware acceleration solutions, which algorithms have been implemented in hardware and what modifications have been done in order to adapt these algorithms to hardware.

Defining Contexts in Context-Free Grammars

This thesis introduces an extension of Chomsky’s context-free grammars equipped with operators for referring to left and right contexts of strings.The new model is called grammar with contexts. The semantics of these grammars are given in two equivalent ways — by language equations and by logical deduction, where a grammar is understood as a logic for the recursive definition of syntax. The motivation for grammars with contexts comes from an extensive example that completely defines the syntax and static semantics of a simple typed programming language. Grammars with contexts maintain most important practical properties of context-free grammars, including a variant of the Chomsky normal form. For grammars with one-sided contexts (that is, either left or right), there is a cubic-time tabular parsing algorithm, applicable to an arbitrary grammar. The time complexity of this algorithm can be improved to quadratic,provided that the grammar is unambiguous, that is, it only allows one parsefor every string it defines. A tabular parsing algorithm for grammars withtwo-sided contexts has fourth power time complexity. For these grammarsthere is a recognition algorithm that uses a linear amount of space. For certain subclasses of grammars with contexts there are low-degree polynomial parsing algorithms. One of them is an extension of the classical recursive descent for context-free grammars; the version for grammars with contexts still works in linear time like its prototype. Another algorithm, with time complexity varying from linear to cubic depending on the particular grammar, adapts deterministic LR parsing to the new model. If all context operators in a grammar define regular languages, then such a grammar can be transformed to an equivalent grammar without context operators at all. This allows one to represent the syntax of languages in a more succinct way by utilizing context specifications. Linear grammars with contexts turned out to be non-trivial already over a one-letter alphabet. This fact leads to some undecidability results for this family of grammars

Reseptikeskuksen lääkekohtaisen tiedon laadun kartoitus toiminnallisesta näkökulmasta

Diplomityössä kartoitetaan tiedon laatuun vaikuttavia tekijöitä kirjallisuuden pohjalta sekä tutkitaan empiirisesti sähköisen reseptin tietosisällön laatua toiminnallisuuden näkökulmasta tarkasteltuna. Tutkimuksen tavoitteena on tuottaa esiselvitys Reseptikeskuksen tietosisällön toiminnallisesta laadusta käytettäväksi lähtötietona tiedon laadun arviointiin ja seurantaan. Tutkimuksen empiirinen osuus toteutettiin kvantitatiivisena tutkimuksena analysoimalla Reseptikeskuksen tietosisällöstä poimittua n. 600 potilaan otosta. Tutkitussa tietosisällössä havaittiin joitain poikkeamia tietosisältöä koskeviin määrityksiin verrattuna, mutta merkittäviä eroja terveydenhuollon eri toimijaryhmien apteekeissa, julkisella ja yksityisellä sektorilla kirjaamien reseptien tietosisällön laadussa ei havaittu. Tiedon kontekstisidonnaisuus on keskeinen tekijä tiedon toiminnallisen laadun määrittämisessä, arvioinnissa ja kehittämisessä. Toiminnan kannalta merkityksellinen tieto rakentuu dataan liitettyjen merkitysten, tiedon käyttäjien kokemusten sekä teknisen ja sosiaalisen käyttöympäristön muodostamana kokonaisuutena. Tiedon laadun parantaminen on jatkuva prosessi, jota tulee ylläpitää arvioimalla ja kehittämällä käytettäviä laatumittareita ja analysointimalleja. Reseptikeskuksen tietosisällön laatua voidaan edelleen kehittää ja nyt tehdyn esikartoituksen pohjalta voidaan jatkossa seurata tietosisällön laadun kehittymistä uusien tutkimusten avulla