Aqueous photocatalytic oxidation of steroid estrogens

Concerns have increased regarding the detection of endocrine-disrupting compounds in the effluents of sewage treatment plants (STPs). These compounds are able to disrupt normal function of the endocrine system of living organisms even at trace concentrations. Natural and synthetic steroid estrogens (SEs) are believed to be responsible for the majority of the endocrine-disrupting effects. Municipal sewage, the main source of SEs in the environment, is a complex mixture of a wide range of pollutants at concentrations much higher than those of SEs. Low concentrations of SEs in the presence of copollutants thus make their removal problematic. The main objectives of the present work were to study the potential of photocatalytic oxidation (PCO) to effectively treat SE-containing aqueous solutions and to identify the optimum conditions for such treatment. The results showed that SEs can be effectively degraded photocatalytically. Due to the adsorption properties of SEs on the TiO2 photocatalyst surface alkaline medium was found to be beneficial for SE oxidation despite the presence of co-pollutants in concentrations characteristic for the sanitary fraction of municipal sewage. The potential of PCO to selectively oxidise SEs was examined in the presence of copollutants of the sanitary fraction of sewage - urea, saccharose and human urine. The impact of ethanol, often used as a solvent in the preparation of SE stock solutions, was also studied and the results indicated the need to use organic solvent-free solutions for the study of SE behaviour. Photocatalytic oxidation of SEs appeared to be indifferent towards the presence of urea in concentrations commonly found in domestic sewage. The effect of other co-pollutants under consideration was far weaker than could be expected from their concentrations, which are from one hundred to a few thousands times higher than those of the SEs. Although higher concentrations can dramatically slow down the PCO of SEs, realistic concentrations of co-pollutants characteristic for the sanitary fraction of domestic sewage allowed selective removal of SEs. This indicates the potential of PCO to be a selective oxidation method for SE removal from the separate sanitary fraction of municipal sewage.

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.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

Effects of Dietary Fat Oxidation Products and Flavonols on Lipoprotein Oxidation

Various studies suggest that oxidative modifications of low density lipoprotein (LDL), and also other lipoproteins, have an important role in the development of atherosclerosis. In addition to the oxidation products formed endogenously, oxidised triacylglycerols (TAG) and oxysterols in the diet contribute to the oxidised lipoproteins found in circulation. However, studies on both the effect of oxidised dietary lipids on lipoprotein lipid oxidation and the reactions that modify oxidised fat after ingestion have been scarce. Studies on the effects of dietary antioxidants on the lipid oxidation in vivo and the risk of atherosclerosis have been inconclusive. More clinical trials are needed to test the importance of lipoprotein oxidation as a cardiovascular risk factor in humans. In the recent years, various methods have been optimised and applied to the analysis of lipid oxidation products in vivo, and information on the molecular structures of oxidised lipids in plasma, lipoproteins and atherosclerotic plaques has started to accumulate. However, specific structures of oxidised TAG molecules present in these tissues and lipoprotein fractions have not been investigated earlier. In the orginal research in this thesis, an approach based on highperformance liquid chromatographyelectrospray ionisationmass spectrometry (HPLCESIMS) and baseline diene conjugation (BDC) methods was used in order to investigate lipid oxidation level and oxidised TAG molecular structures in pig and human lipoproteins after dietary interventions. The approach was optimised with human LDL samples, which contained various oxidation products of TAG. LDL particles of hyperlipidaemic subjects contained an elevated amount of conjugated dienes. In the pig studies, several oxidised TAG structures with hydroxy, keto, epoxy or aldehydic groups were found in chylomicrons and VLDL after diets rich in sunflower seed oil. Also, the results showed that oxidised sunflower seed oil increased the oxidation of lipoprotein lipids and their TAG molecules. TAG hydroperoxides could be detected neither in the small intestinal mucosa of the pigs fed on the oxidised oil nor in their chylomicrons or VLDL.6 In the clinical studies, dietary flavonol aglycones extracted from sea buckthorn berries did not have an effect on lipoprotein lipid oxidation and other potential risk factors of atherosclerosis, but their absorption was demonstrated. Oil supplementation seemed to increase the bioavailability of the flavonols. Oxidised TAG molecules were detected in LDL particles of the subjects after both flavonol and control diets.

PHOTOCATALYTIC OXIDATION OF AQUEOUS SOLUTIONS OF JET FUEL AND ICING INHIBITORS

The present paper is devoted to the results of experimental research undertaken into photocatalytical oxidation (PCO) of aqueous solutions of de-icing agents and aqueous extract of jet fuel. The report consists of introduction, literature review, description of materials and methods, discussion of results and conclusions. TiO2 was selected as a photocatalyst for the experiments with synthetic solutions of ethylene glycol, 2-ethoxyethanol and aqueous extract of jet fuel. To explain the PCO mechanisms affecting certain behaviour of de-icing agent under distinctive conditions, the following factors were studied: the impact of initial concentration of pollutant, the role of pH, the presence of tert-butanol as OH·-radicals scavenger and mineral admixtures. PCO under solar radiation performed in two ways: catalysed by irradiated TiO2 slurry or by TiO2 attached to buoyant hollow glass micro-spheres. Special attention was paid to the energy-saving PCO with reduced intensity mixing of the slurry. The effect of PCO was assessed by determination of residual chemical oxygen demand of solution (COD) and by measuring of concentration of glycols. The PCO process efficiency was assumed to be dependent on the TiO2 suspension fractional composition. Thus, the following effects of solutions’ media were viewed: presence of organic admixtures, pH influence, mixing mode during the PCO. The effects of mineral admixtures - Ca2+, Fe3+/2+, Mn2+, SO42- - that are often present in natural and wastewater systems or produced during the degradation of organic pollutants and which can affect the rate of PCO of de-icing agents, were also investigated.

Kuparinuuttoliuosten adsorptiopuhdistus

Työssä tutkittiin laboratorio-olosuhteissa yhdeksän eri adsorbentin sopivuutta kuparinuuttoliuosten adsorptiopuhdistukseen eli savikäsittelyyn. Tarkoituksena oli poistaa uuttoliuoksesta laimentimen ja reagenssin hapettumis- ja hajoamistuotteita. Adsorbenttien sopivuus uuttoliuosten puhdistukseen määritettiin adsorptio-, kinetiikka- ja faasien selkeytymisaikakokeilla. Tehdyissä kokeissa käytettiin sekä hapetettua synteettistä uuttoliuosta että teollisuudesta saatuja autenttisia kuparinuuttoliuoksia. Uuttoreagenssit olivat hydroksi-oksiimeihin perustuvia. Teollisuudesta saaduista käytetyistä adsorbenteista eluoidun liuoksen kaasugromatografi- ja massaspektrometrianalyysissä ei havaittu selviä merkkejä reagenssin tai laimentimen hajoamistuotteista. Savikäsittely lyhensi faasien selkeytymisaikaa merkittävästi. Bentoniittipohjaisten savien havaittiin soveltuvan parhaiten uuttoliuosten adsorptiopuhdistukseen. IR-analyysin perusteella niiden pinnalle adsorboitui myös eniten karbonyyliryhmiä sisältäviä yhdisteitä. Faasien selkeytymisajan havaittiin huonontuvan itsestään liuosten seistessä savikäsittelyn jälkeen. Noin vuorokauden jälkeen selkeytymisaika tasaantui tasolle, joka oli kuitenkin huomattavasti parempi kuin käsittelemättömällä liuoksella. Savikäsittelyssä käytettävän saven optimimäärä oli noin 1 p-%:a ja sekoitusaika muutamia minuutteja. Savikäsittelyllä ei ollut merkittävää vaikutusta kuparinuuton kinetiikkaan. Työssä tutkittiin laboratorio-olosuhteissa yhdeksän eri adsorbentin sopivuutta kuparinuuttoliuosten adsorptiopuhdistukseen eli savikäsittelyyn. Tarkoituksena oli poistaa uuttoliuoksesta laimentimen ja reagenssin hapettumis- ja hajoamistuotteita. Adsorbe

Wet Oxidation of Paper Mill Evaporation Concentrates

Tämän työn tarkoituksena oli tutkia lämpötilan pH:n ja vetyperoksidin vaikutusta kuorimoveden haihdutuskonsentraatin märkähapetuksessa. Kirjallisuusosassa esitellään massan ja paperin valmistusta sekä kuorintaprosessi. Lisäksi tarkastellaan kuoren kemiallista koostumusta, jäteveden ja prosessiveden käsittelymenetelmiä sekä märkähapetuksen periaatteita. Kokeellinen osa käsittää erään suomalaisen paperitehtaan kuorimoveden haihdutuskonsentraatin märkähapetuskokeet. Hapetuskokeet tehtiin useammassa eri lämpötilassa, pH:ssa ja vetyperoksidikonsentraatiossa. Em. muuttujien vaikutusta tutkittiin kemialliseen hapenkulutukseen (COD), biologiseen hapenkulutukseen (BOD), välittömästi saatavana olevan biologiseen hapenkulutukseen (IABOD), orgaaniseen kokonaishiileen (TOC) ja tanniini/ligniini pitoisuuteen. Koetulokset osoittivat, että korkeimmat COD- ja TOC-reduktiot saavutettiin H2O2-katalysoidulla märkähapetuksella jäteveden alkuperäisessä pH:ssa (60 % reduktio COD:lla ja 45 % reduktio TOC:lla lämpötilassa 170 °C ja 0.2 g H2O2/g COD). Toisaalta, parhaat tulokset biohajoavuuden paranemisen suhteen saavutettiin emäksisissä olosuhteissa, jossa 170 °C:ssa saavutettiin BOD/COD-arvo 76 %. Emäksisissä olosuhteissa saavutettiin lähes täydellinen tanniinin reduktio lämpötila-alueella 130-170 °C, mutta näissä lämpötiloissa orgaanisen kuorman alenemista ei havaittu.

Removal of Lipophilic Wood Extractives from TMP Process Waters by Wet Oxidation

Työssä tutkittiin kokeellisesti rasvaliukoisten uuteaineiden poistamista TMP -prosessin vesikierroista märkähapetuksen avulla. Työn tavoitteena oli tutkia mahdollisuudet hyödyntää TMP -prosessissa vallitsevaa korkeaa lämpötilaa rasvaliukoisten uuteaineiden poistamiseen hapettamalla niitä puhtaalla hapella. Kirjallisuusosassa tarkasteltiin märkähapetuksen teknologiaa, reaktiomekanismia, käytettyjä katalyyttejä, käyttökohteita sekä kustannuksia. Kokeita suoritettiin autoklaavireaktorissa lämpötiloissa 140 °C, 160 °C ja 180 °C. Vetyperoksidia käytettiin katalyyttinä lisätyn vetyperoksidin määrän ollessa 100 - 1800 mg/l ja hapen osapaineen ollessa 0 ( typpiatmosfääri) - 15 baria. Kokeissa tarkasteltiin kemiallisen hapenkulutuksen (COD), rasvaliukoisten uuteaineiden konsentraation, orgaanisen kokonaishiilen (TOC) ja värin muutoksia kokeiden aikana eri lämpötiloilla, hapen osapaineilla ja lisätyn vetyperoksidin määrillä. Kokeissa saavutettiin 30 %:n COD:n vähenemä sekä 90 %:n vähenemä rasvaliukoisissa uuteaineissa lämpötiloissa 160 °C ja 180 °C. Lisäämällä vetyperoksidia katalyyttinä saavutettiin lähes sama tulos lämpötilassa 140 °C. Suurin tässä työssä havaittu ongelma oli lisääntynyt värinmuodostus vedessä olevassa hienojakoisessa kiintoaineessa hapetuksen aikana. Tämän vuoksi lisätutkimukset ovat tarpeellisia sen seikan selvittämiseksi, voidaanko muodostunut väri mahdollisesti poistaa massan valkaisussa.

Sinkkirikasteen liuotusprosessin kineettinen mallinnus

Työssä on tehty kineettinen simulointimalli sinkkirikasteen liuotusprosessista. Prosessi on pieni osa Kokkolan sinkinvalmistusprosessia, jonka muita osia ovat: pasutus, neutraaliliuotus, konversio, liuospuhdistus ja elektrolyysi. Rikasteen liuotukseen tulee konversioprosessin liuos ja liuotuksesta lähtevä neste menee takaisin neutraaliliuotukseen. Saostunut jarosiitti läjitetään. Kokkolan liuotusprosessi koostuu liettoreaktorista ja kahdesta neljän liuotusreaktorin sarjasta. Liuotukseen syötetään paluuhappoa liettoreaktoriin ja liuotuspiirien ensimmäisiin liuotusreaktoreihin. Happea syötetään kaikkiin liuotusreaktoreihin. Prosessin mallintamiseen käytettiin Aspen Plus-simulointiohjelmaa, johon pystyttiin syöttämään kineettisiä yhtälöitä. Reaktionopeusyhtälöitä käytettiin raudan hapetuksen, sulfidien liuotuksen ja jarosiitiin saostumisen mallintamiseen, eli kaikkiin liuotusreaktoreissa tapahtuviin reaktioihin. Kineettiset yhtälöt etsittiin kirjallisuudesta. Liettoreaktori puolestaan mallinnettiin syöttämällä ohjelmaan reaktioyhtälöt ja antamalla niille etenemisasteet. Jarosiitin liukenemisesta työssä on tehty laboratoriokokeita, koska aiheesta ei kirjallisuudesta löytynyt kineettistä tietoa. Liuotuskokeissa käytetyn kiintoaineen kuitenkin todettiin sisältävän liikaa götiittiä, että tuloksista olisi voitu laskea kinetiikkaa jarosiitin liukenemiselle. Simulointimallilla laskettiin yksi tapaus vertailukohdaksi, johon malliin tehtyjä muutoksia verrattiin. Mallilla tutkittiin konversiosta tulevan jarosiitin määrän vaikutusta, reaktorikoon merkitystä ja rikasteen liuotuksen sekä jarosiitin saostuksen reaktionopeuksien muutoksen vaikutuksia. Käytetyillä kineettisillä yhtälöillä reaktioiden todettiin tarvitsevan vain ¾ käytetystä reaktiotilavuudesta, rikasteen liuotusnopeuden kohtalaisen pienellä hidastamisen todettiin vähentävän sinkin saantoa ja jarosiitin saostuksen reaktionopeuden kasvulla todettiin myös olevan negatiivinen vaikutus sinkin saantoon. Simulointimallissa käytettyjen reaktionopeusyhtälöiden varmentaminen kokeilla todettiin tarpeelliseksi, sillä jo kohtalaisen pienillä muutoksilla havaittiin olevan merkitystä prosessin toimivuuteen. Lisäksi todettiin jarosiitin liukenemisen huomioimisen olevan tarpeen.

The initial oxidation of transition metal surfaces

Due to their numerous novel technological applications ranging from the example of exhaust catalysts in the automotive industry to the catalytic production of hydro- gen, surface reactions on transition metal substrates have become to be one of the most essential subjects within the surface science community. Although numerous applications exist, there are many details in the different processes that, after many decades of research, remain unknown. There are perhaps as many applications for the corrosion resistant materials such as stainless steels. A thorough knowledge of the details of the simplest reactions occuring on the surfaces, such as oxidation, play a key role in the design of better catalysts, or corrosion resistant materials in the future. This thesis examines the oxidation of metal surfaces from a computational point of view mostly concentrating on copper as a model material. Oxidation is studied from the initial oxidation to the oxygen precovered surface. Important parameters for the initial sticking and dissociation are obtained. The saturation layer is thoroughly studied and the calculated results arecompared with available experimental results. On the saturated surface, some open questions still remain. The present calculations demonstrate, that the saturated part of the surface is excluded from being chemically reactive towards the oxygen molecules. The results suggest, that the reason for the chemical activity of the saturated surface is due to a strain effect occuring between the saturated areas of the surface.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.