Dispersal and metacommunity dynamics in a soft-sediment benthic system : how well is the seafloor connected?

Connectivity depends on rates of dispersal between communities. For marine soft-sediment communities continued small-scale dispersal as post-larvae and as adults can be equally important in maintaining community composition, as initial recruitment of substrate by pelagic larvae. In this thesis post-larval dispersal strategies of benthic invertebrates, as well as mechanisms by which communities are connected were investigated. Such knowledge on dispersal is scarce, due to the difficulties in actually measuring dispersal directly in nature, and dispersal has not previously been quantified in the Baltic Sea. Different trap-types were used underwater to capture dispersing invertebrates at different sites, while in parallel measuring waves and currents. Local community composition was found to change predictably under varying rates of dispersal and physical connectivity (waves and currents). This response was, however, dependent on dispersal-related traits of taxa. Actively dispersing taxa will be relatively better at maintaining their position, as they are not as dependent on hydrodynamic conditions for dispersal and will be less prone to be passively transported by currents. Taxa also dispersed in relative proportions that were distinctly different from resident community composition and a significant proportion (40 %) of taxa were found to lack a planktonic larval life-stage. Community assembly was re-started in a large-scale manipulative field experiment over one year across several sites, which revealed how patterns of community composition (α-, β- and λ-diversity) change depending on rates of dispersal. Results also demonstrated that in response to small-scale disturbance, initial recruitment was by nearby-dominant species after which other species arrived from successively further away. At later assembly time, the number of coexisting species increased beyond what was expected purely by local niche requirements (species sorting), transferring regional differences in community composition (β-diversity) to the local scale (α-diversity, mass effect). Findings of this thesis complement more theoretical studies in metacommunity ecology by demonstrating that understanding how and when individuals disperse relative to underlying environmental heterogeneity is key to interpreting how patterns of diversity change across different spatial scales. Such information from nature is critical when predicting responses to, for example, different types of disturbances or management actions in conservation.

"It's Barack Obama Who's Soft" Political Bias on BBC, CNN, and Fox News: A Critical Discourse Analysis of News Websites

Tutkielmassa analysoidaan kolmen internetsivuston uutisartikkeleita kielitieteen näkökulmasta. Tavoitteena on selvittää esiintyykö internetsivustojen BBC, CNN ja Fox News uutisoinnissa politiikkaan liittyviä ennakkoasenteita tai puolueellisuuksia ja miten ne käytännössä näkyvät uutisartikkeleiden kielessä. Kriittiseen diskurssianalyysiin pohjautuen tutkielma esittelee jokaisen uutissivuston taustaan (esimerkiksi rakenteeseen ja rahoitukseen) liittyviä seikkoja sekä mediadiskurssiin ja politiikkaan liittyvät taustatiedot, jolla taataan Norman Fairclough'n kolmivaiheisen menetelmän mahdollisimman perusteellinen toteuttaminen. Uutissivustoja analysoidaan kriittiselle diskurssianalyysille sopivan funktionaalisen kieliopin ja muiden lingvististen välineiden avulla. Koko aineiston (404 artikkelia) otsikot analysoidaan ensin, minkä jälkeen analysoidaan yhdeksän kokonaista artikkelia kolmeen eri aihealueeseen liittyen niin, että jokaiselta internetsivustolta analysoidaan yksi artikkeli jokaista aihetta kohden. Analyysikeinoina käytetään ensisijaisesti systeemis-funktionaalisen kieliopin tekstuaalisen metafunktion välineitä (thematic structure). Myös ideationaalisen metafunktion välineitä (transitivity), referenssiketjuja (referential identity chains) ja leksikaalista analyysia käytetään hyväksi. Lähtökohtaisesti tavoitteena on analysoida uutissivustoja vertailevasti, jolloin analyysin tulokset ovat paremmin havainnoitavissa ja perusteltavissa. Hypoteesi aikaisempien tutkimusten ja yleisen mielikuvan perusteella on, että CNN uutisoi demokraattipuolueelle ja Fox News taas republikaanipuolueelle edulliseen sävyyn. Tutkimustulokset vaihtelivat hypoteesia tukevista ja sen vastaisista tuloksista niihin, jotka eivät olleet tarpeeksi tuettuja kumpaankaan suuntaan. Vahvimmat tulokset ovat kuitenkin hypoteesia tukevia, joten tässä tutkielmassa todetaan, ettei uutisointi ole puolueetonta ainakaan näiden kolmen internetsivuston kohdalla. Lisäksi muutaman aihealueen kohdalla uutisointi on niin toistuvaa tietystä näkökulmasta, että luonnollistumisteorian mukaista aatteiden luonnollistumista saattaa tapahtua. Tutkielmassa käytettyjen menetelmien menestyksen perusteella suositellaan, että tekstuaalisen metafunktion analyysivälineitä käytetään enemmän. Lisäksi suositellaan meta-analyysin harkitsemista, jotta voitaisiin selvittää, mitkä analyysimetodit parhaiten sopivat minkäkinlaisen aineiston analysointiin.

A Soft Contact Collision Method For Real-Time Simulation of Triangularized Geometries in Multibody Dynamics

When modeling machines in their natural working environment collisions become a very important feature in terms of simulation accuracy. By expanding the simulation to include the operation environment, the need for a general collision model that is able to handle a wide variety of cases has become central in the development of simulation environments. With the addition of the operating environment the challenges for the collision modeling method also change. More simultaneous contacts with more objects occur in more complicated situations. This means that the real-time requirement becomes more difficult to meet. Common problems in current collision modeling methods include for example dependency on the geometry shape or mesh density, calculation need increasing exponentially in respect to the number of contacts, the lack of a proper friction model and failures due to certain configurations like closed kinematic loops. All these problems mean that the current modeling methods will fail in certain situations. A method that would not fail in any situation is not very realistic but improvements can be made over the current methods.

Biodegradable packaging materials in 2013 and their feasibility in chocolate industry

The development of biopolymers has been rapid in recent years and the range of available bioplastics is increasing continuously, driven by a growing demand for sustainable solutions. There are several key drivers behind this growth. The oil reservoirs are decreasing which is causing a price increase for the traditional plastic materials and therefore the gap to bioplastics’ price is getting smaller. In addition, other environmental topics, such as waste disposal and green production, have become more and more important factors for institutes, companies and consumers. Legislation and directives have to be taken into account as well in decision making concerning different packaging materials. The new environmental law with waste disposal responsibility will also have an effect on the packaging business. Therefore a need has risen to study closer the current offering closer of bio-based materials that could be used in chocolate packaging. In this Master’s Thesis the bioplastics’, and especially biodegradable materials’ technical properties and their development, availability, possible existing products in the markets, waste disposal possibilities and consumers attitude towards environmental friendly packaging is studied. This is a case study where the offering of biodegradable materials was investigated during March 2013 for Fazer Confectionary.

Electric field control of magnetism in hydrid ferromagnetic / ferroelectric materials

Väisälän palkinnon 2012 saaja.

The role of potassium in the corrosion of superheater materials in boilers firing biomass

Inhibition of global warming has become one of the major goals for the coming decades. A key strategy is to replace fossil fuels with more sustainable fuels, which has generated growing interest in the use of waste-derived fuels and of biomass fuels. However, from the chemical point of view, biomass is an inhomogeneous fuel, usually with a high concentration of water and considerable amounts of potassium and chlorine, all of which are known to affect the durability of superheater tubes. To slow down or reduce corrosion, power plants using biomass as fuel have been forced to operate at lower steam temperatures as compared to fossil fuel power plants. This reduces power production efficiency: every 10°C rise in the steam temperature results in an approximate increase of 2% in power production efficiency. More efficient ways to prevent corrosion are needed so that power plants using biomass and waste-derived fuels can operate at higher steam temperatures. The aim of this work was to shed more light on the alkali-induced corrosion of superheater steels at elevated temperatures, focusing on potassium chloride, the alkali salt most frequently encountered in biomass combustion, and on potassium carbonate, another potassium salt occasionally found in fly ash. The mechanisms of the reactions between various corrosive compounds and steels were investigated. Based on the results, the potassium-induced accelerated oxidation of chromia protected steels appears to occur in two consecutive stages. In the first, the protective chromium oxide layer is destroyed through a reaction with potassium leading to the formation of intermediates such as potassium chromate (K2CrO4) and depleting the chromium in the protective oxide layer. As the chromium is depleted, chromium from the bulk steel diffuses into the oxide layer to replenish it. In this stage, the ability of the material to withstand corrosion depends on the chromium content (which affects how long it takes the chromium in the oxide layer to be depleted) and on external factors such as temperature (which affects how fast the chromium diffuses into the protective oxide from the bulk steel). For accelerated oxidation to continue, the presence of chloride appears to be essential.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Negative refractive index materials and propagation

Negative refractive index materials and propagation of electromagnetic waves in them started to draw attention of scientists not so long ago. This review highlights historically important and recent papers on practical and theoretical aspects related to these issues. Namely, basic properties and peculiarities of such materials related to both their design and wave propagation in them, experimental verification of predictions theoretically made for them, possible practical applications and prospects in this area are considered.

Industrial-Scale hydrothermal carbonization of waste sludge materials for fuel production

Hydrothermal carbonization (HTC) is a thermochemical process used in the production of charred matter similar in composition to coal. It involves the use of wet, carbohydrate feedstock, a relatively low temperature environment (180 °C-350 °C) and high autogenous pressure (up to 2,4 MPa) in a closed system. Various applications of the solid char product exist, opening the way for a range of biomass feedstock materials to be exploited that have so far proven to be troublesome due to high water content or other factors. Sludge materials are investigated as candidates for industrial-scale HTC treatment in fuel production. In general, HTC treatment of pulp and paper industry sludge (PPS) and anaerobically digested municipal sewage sludge (ADS) using existing technology is competitive with traditional treatment options, which range in price from EUR 30-80 per ton of wet sludge. PPS and ADS can be treated by HTC for less than EUR 13 and 33, respectively. Opportunities and challenges related to HTC exist, as this relatively new technology moves from laboratory and pilot-scale production to an industrial scale. Feedstock materials, end-products, process conditions and local markets ultimately determine the feasibility of a given HTC operation. However, there is potential for sludge materials to be converted to sustainable bio-coal fuel in a Finnish context.

Kaksi tietä huipulle. Media ja puoluejohtajuus Suomessa naisten noususta populismin aaltoon

Tässä väitöskirjassa tarkastellaan suomalaisen puoluejohtajuuden ja suuren puolueen johtajaksi nousun murroskautta 1980-luvun lopulta 2010-luvulle median ja politiikan vuorovaikutuksen näkökulmasta. Puolueiden johtaminen on myös Suomessa ollut miesten työtä, ja perinteisesti tehtävään on ollut yksi väylä: asettuminen ehdolle puheenjohtajavaalissa ja valituksi tulo puoluekokouksessa. Tarkastelujakson alkupuolella naisia oli Suomessa ensimmäistä kertaa ehdolla suurten puolueiden puheenjohtajavaaleissa. Kauden loppupuolella heitä myös valittiin tuohon tehtävään ja ensimmäiset naiset nousivat pääministeriksi. Tämä historiallinen murros päätti liki satavuotisen perinteen, jossa miehet ovat olleet Suomessa sekä suurten puolueiden että hallitustyön johtajia. Julkisessa keskustelussa kysymys tasa-arvosta jäi toissijaiseksi: naisia alettiin valita puoluejohtajiksi tilanteissa, joissa heidän valintansa nähtiin puolueille edulliseksi. Naisen valinta tulkittiin miehen valintaa merkittävämmäksi symboliseksi viestiksi, johon liitettiin ajatuksia uudistumisesta ja puolueen julkisuuskuvan parantamisesta. Merkille pantavaa on, että naisten ensimmäiset valinnat suurten puolueiden johtajiksi tapahtuivat vaiheessa, jossa puoluejohtajien valta-asema on vahvin kautta suomalaisen poliittisen historian. Tässä valossa näyttää siltä, että valta ei aina pakenekaan naisilta. Vaikka suomalainen yhteiskunta ja suomalaiset naiset ovat monessa mielessä olleet edelläkävijöitä tasa-arvon suhteen, politiikan johtopaikkoja tavoitelleet naiset ovat meilläkin kohdanneet kansainvälisessä tutkimuksessa naisten haasteeksi osoitettuja lasikattoja, pyöröovia ja liukkaita jyrkänteitä. Tutkittavan ajanjakson aikana konkretisoitui myös toinen mahdollinen, joskin poikkeuksellinen reitti suuren puolueen johtajaksi: pienen puolueen nouseminen suurten joukkoon eduskuntavaaleissa. Tämä vaihtoehto toteutui vuonna 2011 perussuomalaisten eduskuntavaalivoiton myötä. Perussuomalaisten nousu eduskunnan pienimmästä puolueesta kolmanneksi suurimmaksi mursi perinteisen kolmen suuren puolueen asetelman. Puolueen menestyksen seuraukset ovat olleet kauaskantoisemmat kuin ehkä ensin ajateltiin: perussuomalaisten vaalivoiton sosiaalidemokraateille, keskustalle, ja kokoomukselle aiheuttama järkytys heijastui myöhemmin myös niiden johtajavaihdoksiin ja -valintoihin. Sekä naisten läpimurrossa että populismin voittokulussa median rooli oli monisyisempi kuin siihen perinteisesti liitetty tiedon välittäjän ja valtaa pitävien toimia kriittisesti seuraavan neljännen valtiomahdin tehtävänkuva. Tutkittavalla jaksolla tiedotusvälineet tekivät onnistuneen intervention politiikan osapuoleksi. Toimittajat ottivat kantaa valintoihin ja ohjeistivat puolueita, ja puolueet taas mukauttivat näkyvyyden maksimoidakseen käytäntöjään median tarpeisiin. 1980-luvun lopulta 2010-luvulle ulottuvalla jaksolla suuren puolueen puoluejohtajaksi valikoitumisen kriteerit muuttuivat, samalla kun median merkitys johtajavalinnoissa ja myös puoluejohtajan käytännön työssä kasvoi. Mediasta tuli aiempaa konkreettisemmin johtajavalintojen ja valtakamppailun areena, ja siihen liittyvät näkökohdat nousivat myös keskeisiksi johtajan taitoja arvioitaessa. Kuka ehdokkaista toisi näkyvyyttä, ”pärjäisi” median paineissa ja vakuuttaisi äänestäjät? Vielä 1980- ja 1990-lukujen taitteessa johtajavalinnat olivat pitkälti puolueorganisaatioiden hallinnoimia prosesseja, joista lehdistö raportoi askeleen jäljessä kulkien. Viimeistään 2000-luvun ensimmäisellä vuosikymmenellä puolueet omaksuivat ajatuksen median hyödyllisyydestä. Tämän strategisen muutoksen myötä puolueet tulivat samalla luovuttaneeksi määriteltyvaltaa oman organisaationsa ulkopuolelle. Kokoomuksen vuoden 2014 johtajavaalissa silmiinpistävää oli pyrkimys sekä hyötyä julkisuudesta että palauttaa valtaa takaisin puolueelle. Politiikan mediajulkisuuden alttius tarttua myyviin poliitikkopersooniin, ilmiöihin, ristiriitoihin ja draamaan sekä vastaavasti populistijohtaja Timo Soinin ja perussuomalaisten kyky tarjota kaikkia näitä auttoivat puolueen suurvoittoon vuoden 2011 eduskuntavaaleissa. Organisaatioltaan pieni ja johtajaansa henkilöityvä puolue sai selvästi poliittista painoarvoaan suuremman julkisuuden, koska kiinnostavuus määritti näkyvyyden ja puolueen nousevasta kannatuksesta tuli yksi vaalien pääaiheista. Median ja politiikan suhteessa tapahtuneet muutokset olivat vauhdittamassa niin naisten nousua suurten puolueiden johtajiksi kuin populistisen johtajuuden läpimurtoa ja perussuomalaisten menestystä. Koska suurten puolueiden johtajista valikoituvat myös pääministerit, näiden muutosten vaikutus ulottuu Suomen poliittisesti vaikutusvaltaisimpaan tehtävään asti.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

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.