Cardiovascular effects of short term exposure to electric and magnetic fields of electricity power transmission

In the electrical industry the 50 Hz electric and magnetic fields are often higher than in the average working environment. The electric and magnetic fields can be studied by measuring or by calculatingthe fields in the environment. For example, the electric field under a 400 kV power line is 1 to 10 kV/m, and the magnetic flux density is 1 to 15 µT. Electricand magnetic fields of a power line induce a weak electric field and electric currents in the exposed body. The average current density in a human being standing under a 400 kV line is 1 to 2 mA/m2. The aim of this study is to find out thepossible effects of short term exposure to electric and magnetic fields of electricity power transmission on workers' health, in particular the cardiovascular effects. The study consists of two parts; Experiment I: influence on extrasystoles, and Experiment II: influence on heart rate. In Experiment I two groups, 26 voluntary men (Group 1) and 27 transmission-line workers (Group 2), were measured. Their electrocardiogram (ECG) was recorded with an ambulatory recorder both in and outside the field. In Group 1 the fields were 1.7 to 4.9 kV/m and 1.1 to 7.1 pT; in Group 2 they were 0.1 to 10.2 kV/m and 1.0 to 15.4 pT. In the ECG analysis the only significant observation was a decrease in the heart rate after field exposure (Group 1). The drop cannot be explained with the first measuring method. Therefore Experiment II was carried out. In Experiment II two groups were used; Group 1 (26 male volunteers) were measured in real field exposure, Group 2 (15 male volunteers) in "sham" fields. The subjects of Group 1 spent 1 h outside the field, then 1 h in the field under a 400 kV transmission line, and then again 1 h outside the field. Under the 400 kV linethe field strength varied from 3.5 to 4.3 kV/m, and from 1.4 to 6.6 pT. Group 2spent the entire test period (3 h) in a 33 kV outdoor testing station in a "sham" field. ECG, blood pressure, and electroencephalogram (EEG) were measured by ambulatory methods. Before and after the field exposure, the subjects performed some cardiovascular autonomic function tests. The analysis of the results (Experiments I and II) showed that extrasystoles or arrythmias were as frequent in the field (below 4 kV/m and 4 pT) as outside it. In Experiment II there was no decrease detected in the heart rate, and the systolic and diastolic blood pressure stayed nearly the same. No health effects were found in this study.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Combination of catalyst development and chemical reaction engineering : a key aspect to improve the hydrogen peroxide direct synthesis

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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).

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Dynamical and Chemical Structure of Galactic Halos

This doctoral dissertation presents studies of the formation and evolution of galaxies, through observations and simulations of galactic halos. The halo is the component of galaxies which hosts some of the oldest objects we know of in the cosmos; it is where clues to the history of galaxies are found, for example, by how the chemical structure is related to the dynamics of objects in the halo. The dynamical and chemical structure of halos, both in the Milky Way’s own halo, and in two elliptical galaxies, is the underlying theme in the research. I focus on the density falloff and chemistry of the two external halos, and on the dynamics, density falloff, and chemistry of the Milky Way halo. I first study galactic halos via computer simulations, to test the long- term stability of an anomalous feature recently found in kinematics of the Milky Way’s metal-poor stellar halo. I find that the feature is transient, making its origin unclear. I use a second set of simulations to test if an initially strong relation between the dynamics and chemistry of halo glob-ular clusters in a Milky Way-type galaxy is affected by a merging satellite galaxy, and find that the relation remains strong despite a merger in which the satellite is a third of the mass of the host galaxy. From simulations, I move to observing halos in nearby galaxies, a challenging procedure as most of the light from galaxies comes from the disk and bulge components as opposed to the halo. I use Hubble Space Tele scope observations of the halo of the galaxy M87 and, comparing to similar observations of NGC 5128, find that the chemical structure of the inner halo is similar for both of these giant elliptical galaxies. I use Very Large Telescope observations of the outer halo of NGC 5128 (Centaurus A) and, because of the difficultly in resolving dim extragalac- tic stellar halo populations, I introduce a new technique to subtract the contaminating background galaxies. A transition from a metal-rich stellar halo to a metal-poor has previously been discovered in two different types of galaxies, the disk galaxy M31 and the classic elliptical NGC 3379. Unexpectedly, I discover in this third type of galaxy, the merger remnant NGC 5128, that the density of metal-rich and metal-poor halo stars falls at the same rate within the galactocentric radii of 8 − 65 kpc, the limit of our observations. This thesis presents new results which open opportunities for future investigations.

Characterisation of pigment particles by scanning electron microscope and image analysis programs

Coating and filler pigments have strong influence to the properties of the paper. Filler content can be even over 30 % and pigment content in coating is about 85-95 weight percent. The physical and chemical properties of the pigments are different and the knowledge of these properties is important for optimising of optical and printing properties of the paper. The size and shape of pigment particles can be measured by different analysers which can be based on sedimentation, laser diffraction, changes in electric field etc. In this master's thesis was researched particle properties especially by scanning electron microscope (SEM) and image analysis programs. Research included nine pigments with different particle size and shape. Pigments were analysed by two image analysis programs (INCA Feature and Poikki), Coulter LS230 (laser diffraction) and SediGraph 5100 (sedimentation). The results were compared to perceive the effect of particle shape to the performance of the analysers. Only image analysis programs gave parameters of the particle shape. One part of research was also the sample preparation for SEM. Individual particles should be separated and distinct in ideal sample. Analysing methods gave different results but results from image analysis programs corresponded even to sedimentation or to laser diffraction depending on the particle shape. Detailed analysis of the particle shape required high magnification in SEM, but measured parameters described very well the shape of the particles. Large particles (ecd~1 µm) could be used also in 3D-modelling which enabled the measurement of the thickness of the particles. Scanning electron microscope and image analysis programs were effective and multifunctional tools for particle analyses. Development and experience will devise the usability of analysing method in routine use.

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.

Analysis and modelling of chemical looping combustion process with and without oxygen uncoupling

Effective control and limiting of carbon dioxide (CO₂) emissions in energy production are major challenges of science today. Current research activities include the development of new low-cost carbon capture technologies, and among the proposed concepts, chemical combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) have attracted significant attention allowing intrinsic separation of pure CO₂ from a hydrocarbon fuel combustion process with a comparatively small energy penalty. Both CLC and CLOU utilize the well-established fluidized bed technology, but several technical challenges need to be overcome in order to commercialize the processes. Therefore, development of proper modelling and simulation tools is essential for the design, optimization, and scale-up of chemical looping-based combustion systems. The main objective of this work was to analyze the technological feasibility of CLC and CLOU processes at different scales using a computational modelling approach. A onedimensional fluidized bed model frame was constructed and applied for simulations of CLC and CLOU systems consisting of interconnected fluidized bed reactors. The model is based on the conservation of mass and energy, and semi-empirical correlations are used to describe the hydrodynamics, chemical reactions, and transfer of heat in the reactors. Another objective was to evaluate the viability of chemical looping-based energy production, and a flow sheet model representing a CLC-integrated steam power plant was developed. The 1D model frame was succesfully validated based on the operation of a 150 kWth laboratory-sized CLC unit fed by methane. By following certain scale-up criteria, a conceptual design for a CLC reactor system at a pre-commercial scale of 100 MWth was created, after which the validated model was used to predict the performance of the system. As a result, further understanding of the parameters affecting the operation of a large-scale CLC process was acquired, which will be useful for the practical design work in the future. The integration of the reactor system and steam turbine cycle for power production was studied resulting in a suggested plant layout including a CLC boiler system, a simple heat recovery setup, and an integrated steam cycle with a three pressure level steam turbine. Possible operational regions of a CLOU reactor system fed by bituminous coal were determined via mass, energy, and exergy balance analysis. Finally, the 1D fluidized bed model was modified suitable for CLOU, and the performance of a hypothetical 500 MWth CLOU fuel reactor was evaluated by extensive case simulations.

Development of Craniofacial Bone Defect Reconstruction Implant Based on Fibre-Reinforced Composite with Photopolymerisable Resin Systems. Experimental studies in vitro and in vivo.

Reconstruction of defects in the craniomaxillofacial (CMF) area has mainly been based on bone grafts or metallic fixing plates and screws. Particularly in the case of large calvarial and/or craniofacial defects caused by trauma, tumours or congenital malformations, there is a need for reliable reconstruction biomaterials, because bone grafts or metallic fixing systems do not completely fulfill the criteria for the best possible reconstruction methods in these complicated cases. In this series of studies, the usability of fibre-reinforced composite (FRC) was studied as a biostable, nonmetallic alternative material for reconstructing artificially created bone defects in frontal and calvarial areas of rabbits. The experimental part of this work describes the different stages of the product development process from the first in vitro tests with resin-impregnated fibrereinforced composites to the in vivo animal studies, in which this FRC was tested as an implant material for reconstructing different size bone defects in rabbit frontal and calvarial areas. In the first in vitro study, the FRC was polymerised in contact with bone or blood in the laboratory. The polymerised FRC samples were then incubated in water, which was analysed for residual monomer content by using high performance liquid chromatography (HPLC). It was found that this in vitro polymerisation in contact with bone and blood did not markedly increase the residual monomer leaching from the FRC. In the second in vitro study, different adhesive systems were tested in fixing the implant to bone surface. This was done to find an alternative implant fixing system to screws and pins. On the basis of this study, it was found that the surface of the calvarial bone needed both mechanical and chemical treatments before the resinimpregnated FRC could be properly fixed onto it. In three animal studies performed with rabbit frontal bone defects and critical size calvarial bone defect models, biological responses to the FRC implants were evaluated. On the basis of theseevaluations, it can be concluded that the FRC, based on E-glass (electrical glass) fibres forming a porous fibre veil enables the ingrowth of connective tissues to the inner structures of the material, as well as the bone formation and mineralization inside the fibre veil. Bone formation could be enhanced by using bioactive glass granules fixed to the FRC implants. FRC-implanted bone defects healed partly; no total healing of defects was achieved. Biological responses during the follow-up time, at a maximum of 12 weeks, to resin-impregnated composite implant seemed to depend on the polymerization time of the resin matrix of the FRC. Both of the studied resin systems used in the FRC were photopolymerised and the heat-induced postpolymerisation was used additionally.

Measurement Problems and Problem-Solving in Kraft Pulping

Tämän työn tarkoituksena on koota yhteen selluprosessin mittausongelmat ja mahdolliset mittaustekniikat ongelmien ratkaisemiseksi. Pääpaino on online-mittaustekniikoissa. Työ koostuu kolmesta osasta. Ensimmäinen osa on kirjallisuustyö, jossa esitellään nykyaikaisen selluprosessin perusmittaukset ja säätötarpeet. Mukana on koko kuitulinja puunkäsittelystä valkaisuun ja kemikaalikierto: haihduttamo, soodakattila, kaustistamo ja meesauuni. Toisessa osassa mittausongelmat ja mahdolliset mittaustekniikat on koottu yhteen ”tiekartaksi”. Tiedot on koottu vierailemalla kolmella suomalaisella sellutehtaalla ja haastattelemalla laitetekniikka- ja mittaustekniikka-asiantuntijoita. Prosessikemian paremmalle ymmärtämiselle näyttää haastattelun perusteella olevan tarvetta, minkä vuoksi konsentraatiomittaukset on valittu jatkotutkimuskohteeksi. Viimeisessä osassa esitellään mahdollisia mittaustekniikoita konsentraatiomittausten ratkaisemiseksi. Valitut tekniikat ovat lähi-infrapunatekniikka (NIR), fourier-muunnosinfrapunatekniikka (FTIR), online-kapillaarielektroforeesi (CE) ja laserindusoitu plasmaemissiospektroskopia (LIPS). Kaikkia tekniikoita voi käyttää online-kytkettyinä prosessikehitystyökaluina. Kehityskustannukset on arvioitu säätöön kytketylle online-laitteelle. Kehityskustannukset vaihtelevat nollasta miestyövuodesta FTIR-tekniikalle viiteen miestyövuoteen CE-laitteelle; kehityskustannukset riippuvat tekniikan kehitysasteesta ja valmiusasteesta tietyn ongelman ratkaisuun. Työn viimeisessä osassa arvioidaan myös yhden mittausongelman – pesuhäviömittauksen – ratkaisemisen teknis-taloudellista kannattavuutta. Ligniinipitoisuus kuvaisi nykyisiä mittauksia paremmin todellista pesuhäviötä. Nykyään mitataan joko natrium- tai COD-pesuhäviötä. Ligniinipitoisuutta voidaan mitata UV-absorptiotekniikalla. Myös CE-laitetta voitaisiin käyttää pesuhäviön mittauksessa ainakin prosessikehitysvaiheessa. Taloudellinen tarkastelu pohjautuu moniin yksinkertaistuksiin ja se ei sovellu suoraan investointipäätösten tueksi. Parempi mittaus- ja säätöjärjestelmä voisi vakauttaa pesemön ajoa. Investointi ajoa vakauttavaan järjestelmään on kannattavaa, jos todellinen ajotilanne on tarpeeksi kaukana kustannusminimistä tai jos pesurin ajo heilahtelee eli pesuhäviön keskihajonta on suuri. 50 000 € maksavalle mittaus- ja säätöjärjestelmälle saadaan alle 0,5 vuoden takaisinmaksuaika epävakaassa ajossa, jos COD-pesuhäviön vaihteluväli on 5,2 – 11,6 kg/odt asetusarvon ollessa 8,4 kg/odt. Laimennuskerroin vaihtelee tällöin välillä 1,7 – 3,6 m3/odt asetusarvon ollessa 2,5 m3/odt.

Regenerated cellulose ultrafiltration membranes in the treatment of pulp and paper mill process waters

Ultrafiltration (UF) is widely applied in different separation processes in the pulp and paper industry. The growing need to protect the environment, a lack of pure water and an interest in producing high-value chemicals from compounds present in process waters will probably lead to an increase in the use of UF in the pulp and paper industry. The efficiency and cost-effectiveness of a UF process depends on the applied membrane. The membrane should have a high and stable filtration capacity, a particular selectivity and a long operational lifetime. To meet these requirements a membrane should have a low fouling tendency. In addition, it should withstand the prevailing operational and chemical conditions. This thesis evaluates the performance and applicability of the regenerated cellulose (RC) membranes 00030T and C2 in the treatment of pulp and paper mill process waters based on the requirements above. The results demonstrated that both the tested RC membranes fulfilled well the requirement of high filtration capacity. In addition, in the filtration of a paper mill clear filtrate (CF) the RC membranes were not as greatly affected by variations in the CF quality as a polysulphone membrane. Furthermore, due to their extreme hydrophilicity and weak charge the fouling tendency of the membranes can be expected to be low in pulp and paper mill filtration applications. It is, however, known that fouling cannot be totally avoided even when the membrane is chosen very carefully. This study indicated that carbohydrates influenced negatively on permeability and caused fouling in the filtration of groundwood mill circulation water. Thus, a pre-treatment effectively reducing the amount of carbohydrates might help to maintain a stable capacity. However, the results of the thesis also showed that the removal of some of the possible foulants might just increase the harmful effect of others. Multivariate examination was useful in the understanding of the complicated factors causing the unstable capacity. The thesis also revealed that the 00030T and C2 membranes can be used at high pressure (max. tested pressure 12 bar). The C2 membrane, having a sponge-like substructure, was more pressure resistant, and its performance was more stable at high pressure compared to the UCO30T membrane containing macrovoids in its substructure. Both tested membranes can, according to the results, also be used at temperatures as high as 70°C in acidic, neutral and alkaline conditions. However, the use at extreme conditions might cause faster ageing of the membranes compared to ageing in neutral conditions. The thesis proved that both the tested RC membranes are very suitable for pulp and paper mill applications and that the membranes can be utilised in processes operating in challenging conditions. Thus, they could be used in more demanding applications than supposed earlier.

Microwave Slot Transmission Line Filled with Ferroelectric and Ferromagnetic Layers

Now when the technology is fast developing it is very important to investigate new hybrid structures. One way is to use ferrite ferroelectric layered structures. Theoretical and experimental investigation of such structures was made. These structures have advantages of both layers and it is possible to tune the behavior of this structure by external electric and magnetic field. But these structures have some disadvantages connected with presence of thick ferroelectric layer. One way to overcome this problem is to use slotline. So this is another new way to create hybrid ferrite ferroelectric structures, but it is needed to create new theory and find experimental proof that the behavior of these structures can be tuned with external magnetic and electric fields.

Treatment of oily wastewater by ultrafiltration: The effect of different operating and solution conditions

In many industries, such as petroleum production, and the petrochemical, metal, food and cosmetics industries, wastewaters containing an emulsion of oil in water are often produced. The emulsions consist of water (up to 90%), oils (mineral, animal, vegetable and synthetic), surfactants and other contaminates. In view of its toxic nature and its deleterious effects on the surrounding environment (soil, water) such wastewater needs to be treated before release into natural water ways. Membrane-based processes have successfully been applied in industrial applications and are considered as possible candidates for the treatment of oily wastewaters. Easy operation, lower cost, and in some cases, the ability to reduce contaminants below existing pollution limits are the main advantages of these systems. The main drawback of membranes is flux decline due tofouling and concentration polarisation. The complexity of oil-containing systems demands complementary studies on issues related to the mitigation of fouling and concentration polarisation in membranebased ultrafiltration. In this thesis the effect of different operating conditions (factors) on ultrafiltration of oily water is studied. Important factors are normally correlated and, therefore, their effect should be studied simultaneously. This work uses a novel approach to study different operating conditions, like pressure, flow velocity, and temperature, and solution properties, like oil concentration (cutting oil, diesel, kerosene), pH, and salt concentration (CaCl2 and NaCl)) in the ultrafiltration of oily water, simultaneously and in a systematic way using an experimental design approach. A hypothesis is developed to describe the interaction between the oil drops, salt and the membrane surface. The optimum conditions for ultrafiltration and the contribution of each factor in the ultrafiltration of oily water are evaluated. It is found that the effect on permeate flux of the various factors studied strongly depended on the type of oil, the type of membrane and the amount of salts. The thesis demonstrates that a system containing oil is very complex, and that fouling and flux decline can be observed even at very low pressures. This means that only the weak form of the critical flux exists for such systems. The cleaning of the fouled membranes and the influence of different parameters (flow velocity, temperature, time, pressure, and chemical concentration (SDS, NaOH)) were evaluated in this study. It was observed that fouling, and consequently cleaning, behaved differently for the studied membranes. Of the membranes studied, the membrane with the lowest propensity for fouling and the most easily cleaned was the regenerated cellulose membrane (C100H). In order to get more information about the interaction between the membrane and the components of the emulsion, a streaming potential study was performed on the membrane. The experiments were carried out at different pH and oil concentration. It was seen that oily water changed the surface charge of the membrane significantly. The surface charge and the streaming potential during different stages of filtration were measured and analysed being a new method for fouling of oil in this thesis. The surface charge varied in different stages of filtration. It was found that the surface charge of a cleaned membrane was not the same as initially; however, the permeability was equal to that of a virgin membrane. The effect of filtration mode was studied by performing the filtration in both cross-flow and deadend mode. The effect of salt on performance was considered in both studies. It was found that salt decreased the permeate flux even at low concentration. To test the effect of hydrophilicity change, the commercial membranes used in this thesis were modified by grafting (PNIPAAm) on their surfaces. A new technique (corona treatment) was used for this modification. The effect of modification on permeate flux and retention was evaluated. The modified membranes changed their pore size around 33oC resulting in different retention and permeability. The obtained results in this thesis can be applied to optimise the operation of a membrane plant under normal or shock conditions or to modify the process such that it becomes more efficient or effective.

Past, present and future - assessing changes in aquatic environments using subfossil diatoms

The deterioration of surface waters is one of the most important issues in the environmental management of the European Union. Thus, the EU Water Framework Directive 2000/60/EC (WFD) requires “good ecological and chemical status” of surface waters by 2015 allowing only a slight departure from ecological reference conditions characterized by the biological communities typical for the conditions of minimal anthropogenic impact. The WFD requires the determination of ecological reference conditions and the present ecological status of surface waters. To meet this legislative demand, sedimentary diatom assemblages were used in these studies with various methods 1) to assess natural and human activity induced environmental changes, 2) to characterize background conditions 3) to evaluate the present ecological status and 4) to predict the future of the water bodies in the light of palaeolimnological data. As the WFD refers to all surface waters, both coastal and inland sites were included. Two long and two short sediment cores from the Archipelago Sea in the northern Baltic Sea were examined for their siliceous microfossils in order to assess (1) the Holocene palaeoenvironmental history and (2) the recent eutrophication of the area. The diatom record was divided into local diatom assemblage zones (LDAZ, long cores) and diatom assemblage zones (DAZ, short cores). Locally weighted weighted averaging regression and calibration (LWWA) was applied for the quantitative reconstruction of past TN concentrations (short cores). An age model for the long cores was constructed by using independent palaeomagnetic and AMS-14C methods. The short cores were dated using radiometric (210Pb, 226Ra and 137Cs) methods. The long cores date back to the early history of the Archipelago Sea, which was freshwater – no salinity increase referable to the brackish phase of the Yoldia Sea is recognized. The nutrient status of the lacustrine phase was slightly higher in the Archipelago Sea than in the Baltic Proper. Initial brackish-water influence is observed at 8 150 ±80 cal. BP (LDAZ4), but fully brackish conditions were established at 7 700 ±80 cal. BP (LDAZ5). The diatom assemblages indicate increasing salinity, warming climate and possible eutrophic conditions during the lacustrine to brackish-water transition. The decreasing abundance of Pseudosolenia calcar-avis (Schultze) Sundström and the increasing abundance of the ice-cover indicator species Pauliella taeniata (Grunow) Round and Basson indicate decreasing salinity and climatic cooling after ca. 5 000 cal. BP. Signs of eutrophication are visible in the most recent diatom assemblage zones of both short cores. Diatom-inferred total nitrogen (DI-TN) reconstructions partially fail to trace the actual measured total nitrogen concentrations especially from the late 1980s to the mid 1990s. This is most likely due to the dominating diatom species Pauliella taeniata, Thalassiosira levanderi Van Goor and Fragilariopsis cylindrus (Grunow) W. Krieger being more influenced by factors such as the length of the ice-season rather than nutrient concentrations. It is concluded that the diatom assemblages of the study sites are principally governed by climate fluctuations, with a slight influence of eutrophication visible in the most recent sediments. There are indications that global warming, with reduced ice cover, could impact the spring blooming diatom species composition in the Archipelago Sea. In addition, increased sediment accumulation in the early 90s coincides with the short ice-seasons suggesting that warming climate with decreasing ice-cover may increase sedimentation in the study area. The diverse diatom assemblages dominated by benthic species (54 %) in DAZ1 in the Käldö Fjärd core can be taken as background diatom assemblages for the Archipelago Sea. Since then turbidity has increased and the diatom assemblages have been dominated by planktonic diatoms from around the mid 1800s onwards. The reconstructed reference conditions for the total nitrogen concentrations fluctuate around 400 μg l-1. Altogether two short sediment cores and eight short cores for top-bottom analysis were retrieved from Lake Orijärvi and Lake Määrjärvi to assess the impact of the acid mine drainage (AMD) derived metals from the Orijärvi mine tailings on the diatom communities of the lakes. The Cu (Pb, Zn) mine of Orijärvi (1757 – 1956) was the first one in Finland where flotation techniques (1911 – 1955) were used to enrich ore and large quantities of tailings were produced. The AMD derived metal impact to the lakes was found to be among the heaviest thus far recorded in Finland. Concentrations of Cu, Pb and Zn in Lake Orijärvi sediments are two to three orders of magnitude higher than background values. The metal inputs have affected Lake Orijärvi and Lake Määrjärvi diatom communities at the community levels through shifts in dominant taxa (both lakes) and at the individual level through alteration in frustule morphology (Lake Orijärvi). At present, lake water still has elevated heavy metal levels, indicating that the impact from the tailings area continues to affect both lakes. Lake Orijärvi diatom assemblages are completely dominated by benthic species and are lacking planktonic diatoms. In Lake Määrjärvi the proportion of benthic and tychoplanktonic diatoms has increased and the planktonic taxa have decreased in abundance. Achnanthidium minutissimum Kützing and Brachysira vitrea (Grun.) R. Ross in Hartley were the most tolerant species to increased metal concentrations. Planktonic diatoms are more sensitive to metal contamination than benthic taxa, especially species in the genus Cyclotella (Kützing) Brébisson. The ecological reference conditions assessed in this study for Lake Orijärvi and Lake Määrjärvi comprise diverse planktonic and benthic communitites typical of circumneutral oligotrophic lakes, where the planktonic diatoms belonging to genera Cyclotella , Aulacoseira Thwaites, Tabellaria Ehrenberg and Asterionella Hassall dominate in relative abundances up to ca. 70%. The benthic communities are more diverse than the planktonic consisting of diatoms belonging to the genera Achnanthes Bory, Fragilaria Lyngbye and Navicula St. Vincent. This study clearly demonstrates that palaeolimnological methods, especially diatom analysis, provide a powerful tool for the EU Water Frame Work Directive for defining reference conditions, natural variability and current status of surface waters. The top/bottom approach is a very useful tool in larger-scale studies needed for management purposes. This “before and after” type of sediment sampling method can provide a very time and cost effective assessment of ecological reference conditions of surface waters.