Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Effect of fertilizer treatment on the biomass production and nutrient uptake of short-rotation willow on cut-away peatlands

Summary

Biomass production and nutrient uptake of short-rotation plantations

Summary

Uptake of heavy metals by plants from airborne deposition and polluted soils

Selostus: Kasvien raskasmetallien otto ilmasta ja saastuneesta maasta

Effects of sodium sulphate and potassium chloride fertilizers on the nutritive value of timothy grown on different soils

Selostus: Natrium- ja kaliumlannoituksen vaikutus timotein ravintoarvoon

Sodium reduction in cooked meat products by using commercial potassium phoshate mixtures

Selostus: Natriumpitoisuuden pienentäminen lihavalmisteissa korvaamalla natriumfosfaatti kaliumfosfaatilla

Harvesting strategy and N fertilization influence ¹³⁴Cs uptake by forage plants

Selostus: Korjuuaika ja typpilannoitus vaikuttavat rehukasvien radiocesiumpitoisuuteen

Surface characterization of chemically modified fiber, wood and paper

Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.

Chromium mass balance in sodium chlorate process

Kuudenarvoista kromia käytetään natriumkloraatin valmistuksessa prosessin tuotantotehokkuuden ja turvallisuuden parantamiseksi. Kromia kuitenkin poistuu prosessista muutamaa reittiä pitkin. Koska kuuudenarvoisella kromilla on syöpää aiheuttavia, mutageenisiä sekä lisääntymiselle myrkyllisiä ominaisuuksia, olisi tärkeää ymmärtää, miten kromi kulkeutuu prosessin eri osiin, ja kuinka paljon sitä poistuu prosessista. Tämä on tärkeää, jotta osataan hallita kromin käytöstä aiheutuvat riskit, sekä toisaalta myös tehostaa kromin käyttöä prosessissa. Työn tarkoituksena oli tuottaa tietoa kromin käytöstä natriumkloraattiprosessissa. Työssä tutkittiin kromitasetta prosessin keskeisimmissä yksikköoperaatioissa. Myös kromin saostumista katodien pinnalle arvioitiin määrällisesti. Eri prosessinäytteistä tutkittiin lisäksi kromin hapetusasteita. Edellä mainittuja tutkimuskohteita varten määritettiin prosessinäytteiden kromipitoisuus. Eri prosessioperaatioille suoritettiin lisäksi taselaskelmat. Työn tuloksena esitettiin kromitase sekä yksikköoperaatioille että koko prosessille. Erinäisten epätarkkuustekijöiden vuoksi tasetta ei kuitenkaan pystytty määrittämään halutulla tarkkuudella, ja siksi työssä esitettyä tasetta voidaan pitää vain suuntaa antavana laskelmana. Katodien pinnalle saostunutta kromin määrää pidettiin kuitenkin oikean suuruusluokan tuloksena. Prosessinäytteiden hapetusasteita ei voitu arvioida, sillä saadut kokonaiskromitulokset eivät olleet täysin luotettavia. Huolimatta tulosten epätarkkuudesta, työ tuotti tärkeää tietoa prosessin toiminnasta kromin suhteen. Työtä voidaan hyödyntää jatkossa monin tavoin prosessin kromitaseen seurannassa.

Stability and properties of cellulose-sodium hydroxide solution systems

Since cellulose is a linear macromolecule it can be used as a material for regenerated cellulose fiber products e.g. in textile fibers or film manufacturing. Cellulose is not thermoformable, thus the manufacturing of these regenerated fibers is mainly possible through dissolution processes preceding the regeneration process. However, the dissolution of cellulose in common solvents is hindered due to inter- and intra-molecular hydrogen bonds in the cellulose chains, and relatively high crystallinity. Interestingly at subzero temperatures relatively dilute sodium hydroxide solutions can be used to dissolve cellulose to a certain extent. The objective of this work was to investigate the possible factors that govern the solubility of cellulose in aqueous NaOH and the solution stability. Cellulose-NaOH solutions have the tendency to form a gel over time and at elevated temperature, which creates challenges for further processing. The main target of this work was to achieve high solubility of cellulose in aqueous NaOH without excessively compromising the solution stability. In the literature survey an overview of the cellulose dissolution is given and possible factors contributing to the solubility and solution properties of cellulose in aqueous NaOH are reviewed. Furthermore, the concept of solution rheology is discussed. In the experimental part the focus was on the characterization of the used materials and properties of the prepared solutions mainly concentrating on cellulose solubility and solution stability.

Excavation-drier method of energy-peat extraction reduces long-term climatic impact

Climatic impacts of energy-peat extraction are of increasing concern due to EU emissions trading requirements. A new excavation-drier peat extraction method has been developed to reduce the climatic impact and increase the efficiency of peat extraction. To quantify and compare the soil GHG fluxes of the excavation drier and the traditional milling methods, as well as the areas from which the energy peat is planned to be extracted in the future (extraction reserve area types), soil CO2, CH4 and N2O fluxes were measured during 2006–2007 at three sites in Finland. Within each site, fluxes were measured from drained extraction reserve areas, extraction fields and stockpiles of both methods and additionally from the biomass driers of the excavation-drier method. The Life Cycle Assessment (LCA), described at a principal level in ISO Standards 14040:2006 and 14044:2006, was used to assess the long-term (100 years) climatic impact from peatland utilisation with respect to land use and energy production chains where utilisation of coal was replaced with peat. Coal was used as a reference since in many cases peat and coal can replace each other in same power plants. According to this study, the peat extraction method used was of lesser significance than the extraction reserve area type in regards to the climatic impact. However, the excavation-drier method seems to cause a slightly reduced climatic impact as compared with the prevailing milling method.

Separation of lignin in Pulp Mill process and its effect on sodium sulphur balance

The aim of this thesis is to define effects of lignin separation process on Pulp mill chemical balance especially on sodium/sulphur-balance. The objective is to develop a simulation model with WinGEMS Process Simulator and use that model to simulate the chemical balances and process changes. The literature part explains what lignin is and how kraft pulp is produced. It also introduces to the methods that can be used to extract lignin from black liquor stream and how those methods affect the pulping process. In experimental part seven different cases are simulated with the created simulation model. The simulations are based on selected reference mill that produces 500 000 tons of bleached air-dried (90 %) pulp per year. The simulations include the chemical balance calculation and the estimated production increase. Based on the simulations the heat load of the recovery boiler can be reduced and the pulp production increased when lignin is extracted. The simulations showed that decreasing the waste acid stream intake from the chlorine dioxide plant is an effective method to control the sulphidity level when about 10 % of lignin is extracted. With higher lignin removal rates the in-mill sulphuric acid production has been discovered to be a better alternative to the sulphidity control.