Properties of top soil and the relationship between soil and trees in a boreal Scots pine stand

Summary

Effect of data acquisition accuracy on timing of stand harvests and expected net present value

Abstract

Photocatalytic oxidation of humic substances and lignins in aqueous solutions

Tässä tutkimuksessa tarkastellaan kahden yleisen, veden ympäristökuormitusta aiheuttavan kemikaaliryhmän, ligniinin ja humusaineiden, fotokatalyyttistahapetusta (photocatalytic oxidation, PCO) vesiliuoksessa. Fotokatalyyttina käytettiin titaanidioksidia, jota säteilytettiin ultraviolettivalolla. Työssä selvitettiin useiden eri olosuhdeparametrien vaikutusta fotokatalyysiin. Tutkittavia parametreja olivat mm. kontaminanttien alkukonsentraatio, pH, vetyperoksidilisäys, rauta-ionien lisäys, fotokatalyysimenetelmä, fotokatalyytin pintakonsentraatioja titaanidioksidin määrä lasisissa mikropartikkeleissa. Ultraviolettivalon lähteinä käytettiin sekä keinovaloa että auringonvaloa. Katalyytin kantoaineena käytettiin huokoisia lasisia mikropartikkeleita, joiden pintaan kiinnittynyt titaanidioksidi pystyi hyvin vähentämään kontaminanttien määrää vedessä. Fotokatalyysin tehokkuus kasvoi humusaine- ja ligniinikonsentraatioiden kasvaessa. Korkeimmat hapetustehokkuudet kumallakin kontaminantilla saavutettiin neutraaleissa jalievästi emäksisissä olosuhteissa huolimatta siitä, että paras adsorboituminen tapahtui happamissa olosuhteissa. Tämän perusteella voidaan olettaa, että humusaineiden ja ligniinin hapetus tapahtuu pääosin radikaalimekanismilla. Vetyperoksidin lisääminen humusaineliuokseen lisäsi hapettumisnopeutta, vaikka näennäinen hapetustehokkuus ei muuttunut. Tämän perusteella vetyperoksidi hapetti myös humusaineita referenssinäytteessä. Ligniinin fotokatalyyttinen hapettuminen parani vetyperoksidilisäyksellä happamissa olosuhteissa johtuen lisääntyneestä OH-radikaalien muodostumisesta. Ligniini ei hapettunut vetyperoksidilla, jos fotokatalyyttiä ei¿ollut läsnä. Rauta-ionit eivät lisänneet humushappojen fotokatalyyttistähapettumista, mutta Fe2+-ionien lisäys aina konsentraatioon 0.05 mM johti ligniinin hapettumistehokkuuden voimakkaaseen kasvuun. Rauta-ionikonsentraation kasvattaminen edelleen johti ligniinin hapetustehokkuuden alenemiseen.

Magnetic and transport properties of LaMnO3+δ, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1-xSrxMn1-yFeyO3

Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

Studies on membrane properties of cholesterol and 3-beta modified sterol analogs

Cholesterol (Chol) is an important lipid in cellular membranes functioning both as a membrane fluidity regulator, permeability regulator and co-factor for some membrane proteins, e.g. G-protein coupled receptors. It also participates in the formation of signaling platforms and gives the membrane more mechanical strenght to prevent osmotic lysis of the cell. The sterol structure is very conserved and already minor structural modifications can completely abolish its membrane functions. The right interaction with adjacent lipids and the preference of certain lipid structures over others are also key factors in determining the membrane properties of cholesterol. Because of the many important properties of cholesterol it is of value to understand the forces and structural properties that govern the membrane behavior of this sterol. In this thesis we have used established fluorescence spectroscopy methods to study the membrane behavior of both cholesterol and some of its 3β-modified analogs. Using several fluorescent probes we have established how the acyl chain order of the two main lipid species, sphingomyelin (SM) and phosphatidylcholine (PC) affect sterol partitioning as well as characterized the membrane properties of 3β-aminocholesterol and cholesteryl phosphocholine. We concluded that cholesterol prefers SM over PC at equal acyl chain order, indicating that other structural properties besides the acyl chain order are important for sphingomyelin-sterol interactions. A positive charge at the 3β position only caused minor changes in the sterol membrane behavior compared to cholesterol. A large phosphocholine head group caused a disruption in membrane packing together with other membrane lipids with large head groups, but was also able to form stable fluid bilayers together with ceramide and cholesterol. The Ability of the large head group sterol to form bilayers together with ceramide was further explored in the last paper where cholesteryl phosphocholine/ceramide (Chol-PC/Cer) complexes were successfully used to transfer ceramide into cultured cells.

Electrical and dielectric properties of uncoated and coated wood-free paper for electrophotography

The print substrate influences the print result in dry toner electrophotography, which is a widely used digital printing method. The influence of the substrate can be seen more easily in color printing, as that is a more complex process compared to monochrome printing. However, the print quality is also affected by the print substrate in grayscale printing. It is thus in the interests of both substrate producers and printing equipment manufacturers to understand the substrate properties that influence the quality of printed images in more detail. In dry toner electrophotography, the image is printed by transferring charged toner particles to the print substrate in the toner transfer nip, utilizing an electric field, in addition to the forces linked to the contact between toner particles and substrate in the nip. The toner transfer and the resulting image quality are thus influenced by the surface texture and the electrical and dielectric properties of the print substrate. In the investigation of the electrical and dielectric properties of the papers and the effects of substrate roughness, in addition to commercial papers, controlled sample sets were made on pilot paper machines and coating machines to exclude uncontrolled variables from the experiments. The electrical and dielectric properties of the papers investigated were electrical resistivity and conductivity, charge acceptance, charge decay, and the dielectric permittivity and losses at different frequencies, including the effect of temperature. The objective was to gain an understanding of how the electrical and dielectric properties are affected by normal variables in papermaking, including basis weight, material density, filler content, ion and moisture contents, and coating. In addition, the dependency of substrate resistivity on the electric field applied was investigated. Local discharging did not inhibit transfer with the paper roughness levels that are normal in electrophotographic color printing. The potential decay of paper revealed that the charge decay cannot be accurately described with a single exponential function, since in charge decay there are overlapping mechanisms of conduction and depolarization of paper. The resistivity of the paper depends on the NaCl content and exponentially on moisture content although it is also strongly dependent on the electric field applied. This dependency is influenced by the thickness, density, and filler contents of the paper. Furthermore, the Poole-Frenkel model can be applied to the resistivity of uncoated paper. The real part of the dielectric constant ε’ increases with NaCl content and relative humidity, but when these materials cannot polarize freely, the increase cannot be explained by summing the effects of their dielectric constants. Dependencies between the dielectric constant and dielectric loss factor and NaCl content, temperature, and frequency show that in the presence of a sufficient amount of moisture and NaCl, new structures with a relaxation time of the order of 10-3 s are formed in paper. The ε’ of coated papers is influenced by the addition of pigments and other coating additives with polarizable groups and due to the increase in density. The charging potential decreases and the electrical conductivity, potential decay rate, and dielectric constant of paper increase with increasing temperature. The dependencies are exponential and the temperature dependencies and their activation energies are altered by the ion content. The results have been utilized in manufacturing substrates for electrophotographic color printing.

Structural and optical properties of InAs/GaAs quantum structures

The goal of the thesis was to study fundamental structural and optical properties of InAs islands and In(Ga)As quantum rings. The research was carried out at the Department of Micro and Nanosciences of Helsinki University of Technology. A good surface quality can be essential for the potential applications in optoelectronic devices. For such device applications it is usually necessary to control size, density and arrangement of the islands. In order to study the dependence of the structural properties of the islands and the quantum rings on growth conditions, atomic force microscope was used. Obtained results reveal that the size and the density of the In(Ga)As quantum rings strongly depend on the growth temperature, the annealing time and the thickness of the partial capping layer. From obtained results it is possible to conclude that to get round shape islands and high density one has to use growth temperature of 500 ̊C. In the case of formation of In(Ga)As quantum rings the effect of mobility anisotropy is observed that so the shape of the rings is not symmetric. To exclude this effect it is preferable to use a higher annealing temperature of 570 ̊C. Optical properties were characterized by PL spectroscopy. PL emission was observed from buried InAs quantum dots and In(Ga)As quantum rings grown with different annealing time and temperature and covered with a various thickness of the partial capping layer.

The Effects of Some Furnish and Paper Structure Related Factors on Wet Web Tensile and Relaxation Characteristics

The objective of this thesis was to identify the effects of different factors on the tension and tension relaxation of wet paper web after high-speed straining. The study was motivated by the plausible connection between wet web mechanical properties and wet web runnability on paper machines shown by previous studies. The mechanical properties of wet paper were examined using a fast tensile test rig with a strain rate of 1000%/s. Most of the tests were carried out with laboratory handsheets, but samples from a pilot paper machine were also used. The tension relaxation of paper was evaluated as the tension remaining after 0.475 s of relaxation (residual tension). The tensile and relaxation properties of wet webs were found to be strongly dependent on the quality and amount of fines. With low fines content, the tensile strength and residual tension of wet paper was mainly determined by the mechanical interactions between fibres at their contact points. As the fines strengthen the mechanical interaction in the network, the fibre properties also become important. Fibre deformations caused by the mechanical treatment of pulp were shown to reduce the mechanical properties of both dry and wet paper. However, the effect was significantly higher for wet paper. An increase of filler content from 10% to 25% greatly reduced the tensile strength of dry paper, but did not significantly impair wet web tensile strength or residual tension. Increased filler content in wet web was shown to increase the dryness of the wet web after the press section, which partly compensates for the reduction of fibrous material in the web. It is also presumable that fillers increase entanglement friction between fibres, which is beneficial for wet web strength. Different contaminants present in white water during sheet formation resulted in lowered surface tension and increased dryness after wet pressing. The addition of different contaminants reduced the tensile strength of the dry paper. The reduction of dry paper tensile strength could not be explained by the reduced surface tension, but rather on the tendency of different contaminants to interfere with the inter-fibre bonding. Additionally, wet web strength was not affected by the changes in the surface tension of white water or possible changes in the hydrophilicity of fibres caused by the addition of different contaminants. The spraying of different polymers on wet paper before wet pressing had a significant effect on both dry and wet web tensile strength, whereas wet web elastic modulus and residual tension were basically not affected. We suggest that the increase of dry and wet paper strength could be affected by the molecular level interactions between these chemicals and fibres. The most significant increases in dry and wet paper strength were achieved with a dual application of anionic and cationic polymers. Furthermore, selectively adding papermaking chemicals to different fibre fractions (as opposed to adding chemicals to the whole pulp) improved the wet web mechanical properties and the drainage of the pulp suspension.

On the effect of molecular structure and composition on the photofragmentation of biomolecules

The research on the interaction between radiation and biomolecules pro-vides valuable information for both radiobiology and molecular physics. While radiobiology is interested in the damage inflicted on the molecule upon irradiation, molecular physics exploits these studies to obtain infor-mation about the physical properties of the molecule and the quantum me-chanical processes involved in the interaction. This thesis work investigated how a small change in the structure or composition of a biomolecule changes the response of the molecule to ioniz-ing radiation. Altogether eight different biomolecules were studied: nucleo-sides uridine, 5-methyluridine and thymidine; amino acids alanine, cysteine and serine; and halogenated acetic acids chloro- and bromoacetic acids. The effect of ionizing radiation on these molecules was studied on molecular level, investigating the samples in gas phase. Synchrotron radiation of VUV or soft x-ray range was used to ionize sample molecules, and the subsequent fragmentation processes were investigated with ion mass spectroscopy and ion-ion-electron coincidence spectroscopy. The comparison between the three nucleosides revealed that adding or removing a single functional group can affect not only the bonds from which the molecule ruptures upon ionization but also the charge localiza-tion in the formed fragments. Studies on amino acids and halogenated acetic acids indicated that one simple substitution in the molecule can dramatical-ly change the extent of fragmentation. This thesis work also demonstrates that in order to steer the radiation-induced fragmentation of the molecules, it is not always necessary to alter the amount of energy deposited on the molecules but selecting a suitable substitution may suffice.

Influence of stationary phase and eluent properties on chromatographic separation of carbohydrates

In this thesis, the sorption and elastic properties of the cation-exchange resins were studied to explain the liquid chromatographic separation of carbohydrates. Na+, Ca2+ and La3+ form strong poly(styrene-co-divinylbenzene) (SCE) as well as Na+ and Ca2+ form weak acrylic (WCE) cation-exchange resins at different cross-link densities were treated within this work. The focus was on the effects of water-alcohol mixtures, mostly aqueous ethanol, and that of the carbohydrates. The carbohydrates examined were rhamnose, xylose, glucose, fructose, arabinose, sucrose, xylitol and sorbitol. In addition to linear chromatographic conditions, non-linear conditions more typical for industrial applications were studied. Both experimental and modeling aspectswere covered. The aqueous alcohol sorption on the cation-exchangers were experimentally determined and theoretically calculated. The sorption model includes elastic parameters, which were obtained from sorption data combined with elasticity measurements. As hydrophilic materials cation-exchangers are water selective and shrink when an organic solvent is added. At a certain deswelling degree the elastic resins go through glass transition and become as glass-like material. Theincreasing cross-link level and the valence of the counterion decrease the sorption of solvent components in the water-rich solutions. The cross-linkage or thecounterions have less effect on the water selectivity than the resin type or the used alcohol. The amount of water sorbed is higher in the WCE resin and, moreover, the WCE resin is more water selective than the corresponding SCE resin. Theincreased aliphatic part of lower alcohols tend to increase the water selectivity, i.e. the resins are more water selective in 2-propanol than in ethanol solutions. Both the sorption behavior of carbohydrates and the sorption differences between carbohydrates are considerably affected by the eluent composition and theresin characteristics. The carbohydrate sorption was experimentally examined and modeled. In all cases, sorption and moreover the separation of carbohydrates are dominated by three phenomena: partition, ligand exchange and size exclusion. The sorption of hydrophilic carbohydrates increases when alcohol is added into the eluent or when carbohydrate is able to form coordination complexes with the counterions, especially with multivalent counterions. Decreasing polarity of the eluent enhances the complex stability. Size exclusion effect is more prominent when the resin becomes tighter or carbohydrate size increases. On the other hand,the elution volumes between different sized carbohydrates decreases with the decreasing polarity of the eluent. The chromatographic separation of carbohydrateswas modeled, using rhamnose and xylose as target molecules. The thermodynamic sorption model was successfully implemented in the rate-based column model. The experimental chromatographic data were fitted by using only one adjustable parameter. In addition to the fitted data also simulated data were generated and utilized in explaining the effect of the eluent composition and of the resin characteristics on the carbohydrate separation.