Kloorifenoleja sisältävien jätevesien AOP-käsittely

Kirjallisuustyössä tutkittiin tehostetun hapetuksen menetelmiä (engl. Advanced Oxidation Processes, AOPs) kloorifenolien käsittelyssä. Tutkittava aine valittiin US EPA:n (United States Environmental Protection Agency) ympäristölle haitallisten aineiden listalta. Työssä tutkitut AOP-menetelmät olivat otsonointi kasvatetussa pH:ssa, O3/H2O2-prosessi, fotolyyttinen otsonointi (O3/UV), H2O2/UV-prosessi ja Fenton-prosessi (H2O2+Fe2+). AOP-käsittelyssä OH-radikaalien oletetaan pääosin aiheuttavan epäpuhtauksien hapettumisen. Kirjallisuustyössä tutkittiin OH-radikaaleihin vaikuttavien parametrien, kuten pH:n, lämpötilan sekä hapettimien ja hapetettavan aineen konsentraatioiden vaikutusta kloorifenolien hapetusprosessissa. Työn tarkoituksena oli selvittää tehokkain AOP-käsittely kloorifenoleja sisältävien jätevesien käsittelylle. AOP-käsittelyjen tehokkuutta verrattiin hajoamisnopeusvakioiden, puoliintumisaikojen sekä hapettimen kemikaalikulutuksen ja kustannuksen perusteella. Fenton-prosessin ja otsonoinnin pH:ssa 9 todettiin olevan tehokkaimpia menetelmiä kloorifenolien hapetuksessa. Fenton-prosessin hapetusnopeus oli tehokkaampaa 4-CP:n ja 2,4-DCP:n hapetuksessa, kun taas otsonointi pH:ssa 9 hapetti nopeammin 2,3,4,6-TeCP:n ja 2,4,6-TCP:n. Kustannustehokkuuden perusteella Fenton-prosessi oli otsonointia tehokkaampi. Parhaan menetelmän valinta kloorifenoleiden poistamiseksi oli vaikeaa, sillä useissa tutkimuksissa oli tutkittu vain yhtä menetelmää. Lisäksi eri tutkimuksissa käytetyt prosessiolosuhteet olivat erilaiset, joka hankaloitti tutkimusten vertailua. Lopullinen AOP-menetelmän valinta tulisikin suorittaa vasta laboratoriotutkimusten jälkeen.

Application of capillary electrophoretic methods for determining carbohydrates and aliphatic carboxylic acids formed during wood processing

Knowledge of the behaviour of cellulose, hemicelluloses, and lignin during wood and pulp processing is essential for understanding and controlling the processes. Determination of monosaccharide composition gives information about the structural polysaccharide composition of wood material and helps when determining the quality of fibrous products. In addition, monitoring of the acidic degradation products gives information of the extent of degradation of lignin and polysaccharides. This work describes two capillary electrophoretic methods developed for the analysis of monosaccharides and for the determination of aliphatic carboxylic acids from alkaline oxidation solutions of lignin and wood. Capillary electrophoresis (CE), in its many variants is an alternative separation technique to chromatographic methods. In capillary zone electrophoresis (CZE) the fused silica capillary is filled with an electrolyte solution. An applied voltage generates a field across the capillary. The movement of the ions under electric field is based on the charge and hydrodynamic radius of ions. Carbohydrates contain hydroxyl groups that are ionised only in strongly alkaline conditions. After ionisation, the structures are suitable for electrophoretic analysis and identification through either indirect UV detection or electrochemical detection. The current work presents a new capillary zone electrophoretic method, relying on in-capillary reaction and direct UV detection at the wavelength of 270 nm. The method has been used for the simultaneous separation of neutral carbohydrates, including mono- and disaccharides and sugar alcohols. The in-capillary reaction produces negatively charged and UV-absorbing compounds. The optimised method was applied to real samples. The methodology is fast since no other sample preparation, except dilution, is required. A new method for aliphatic carboxylic acids in highly alkaline process liquids was developed. The goal was to develop a method for the simultaneous analysis of the dicarboxylic acids, hydroxy acids and volatile acids that are oxidation and degradation products of lignin and wood polysaccharides. The CZE method was applied to three process cases. First, the fate of lignin under alkaline oxidation conditions was monitored by determining the level of carboxylic acids from process solutions. In the second application, the degradation of spruce wood using alkaline and catalysed alkaline oxidation were compared by determining carboxylic acids from the process solutions. In addition, the effectiveness of membrane filtration and preparative liquid chromatography in the enrichment of hydroxy acids from black liquor was evaluated, by analysing the effluents with capillary electrophoresis.

Rasvasuodatus UV-valon avulla

Tämä kandidaatintyö käsittelee rasva-aerosolien vähentämistä liesituulettimissa ultraviolettivalon (UV) ja titaanioksidin avulla (TiO2). Työssä käsitellään rasva-aerosolien aiheuttamia haittoja julkisissa keittiöissä ja liesituulettimen merkitystä rasva-aerosolipitoisuuksiin. Työn tavoitteena on selvittää, miten rasva-aerosolit käyttäytyvät kun niitä suodatetaan UV-valon ja TiO2-katalyytin avulla. Työssä myös pohditaan onko UV/TiO2-menetelmä tehokas liesituulettimen rasvan vähentäjä.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

UV-LED -lamppujen soveltuminen laivojen painolastivesien käsittelyyn

Painolastivesien mukana kulkeutuvien lajien leviäminen on yksi vakavimmista globaaleista ympäristöuhkista. Kansainvälinen merenkulkujärjestö IMO määritteli vuonna 2004 kansainvälisen painolastivesiyleissopimuksen, jonka tarkoituksena on ehkäistä laivojen painolastivesien mukana kulkeutuvien lajien leviämistä. Sopimus velvoittaa aluksia käsittelemään niiden painolastivedet ja se sisältää myös käsittelyjärjestelmiltä edellytetyt vaatimukset. Vaikka sopimus ei ole vielä astunut voimaan, painolastivesien käsittelyyn löytyy markkinoilta jo useita kymmeniä IMO:n hyväksymiä käsittelyjärjestelmiä, jotka hyödyntävät erilaisia mekaanisia, fysikaalisia ja kemiallisia menetelmiä. Yksi yleisimmin käytetyistä menetelmistä on UV-säteilytys. UV-säteily tuotetaan elohopealampuilla, jotka kuitenkin kuluttavat paljon energiaa ja sisältävät myrkyllistä elohopeaa. Tämän työn tarkoituksena oli selvittää, voisiko elohopealamput korvata lähitulevaisuudessa UV-LED -lampuilla. UV-LED –lamppujen etuja ovat muun muassa energiatehokkuus, kestävä rakenne ja myrkyttömyys. Työn tärkeimpänä tavoitteena oli tutkia laboratoriomittausten avulla, millainen UV-annosmäärä 10-50 µm kokoisten kasviplanktonien inaktivoimiseen tarvitaan. Mittausjärjestelyt vastasivat suurelta osin IMO:n vaatimuksia. Laboratoriomittauksissa käytettiin 265 nm:n aallonpituudella toimivia UV-LED -lamppuja. Näytteiden analysoinnissa käytettiin sekä PAM-fluorometriä että virtaussytometriä. Saatujen tulosten perusteella tutkimuksessa käytettyjen lajien Asterionellopsis glacialis ja Thalassiosira sp. täydelliseen inaktivoitumiseen tarvittiin noin 600 mJ/cm2 suuruinen UV-annos. Tulos vastasi ennakko-odotuksia ja se oli vertailukelpoinen muiden aiheesta tehtyjen tutkimusten kanssa. Koska nykyisten UV-LED –lamppujen teho on hyvin alhainen, ne eivät vielä sovellu painolastivesien käsittelyyn. UV-LED –lamppujen kehitystyö on kuitenkin käynnissä ja on arvioitu, että niitä voitaisiin käyttää suurten virtaamien käsittelyssä 5-10 vuoden kuluttua.

Veden desinfiointi UV-LED-valolla

Veden riittämätön puhdistus aiheuttaa riskin veden käyttäjille. Miljoonia kuolemia vuosittain aiheuttavien vesiteitse leviävien sairauksien ehkäisemiseksi vaaditaan tehokkaita juomaveden desinfiointimenetelmiä. Kuivuuden ja väestönkasvun myötä veden tarve on lisääntynyt ja vedenkulutus tulee yhä kasvamaan. Tästä syystä mahdollisuus kierrättää vettä hyödyntäen sitä esimerkiksi kasteluun on saanut yhä enemmän huomiota. Kierrätettävä vesi on kuitenkin käsiteltävä huolellisesti sen sisältämän mikrobiologisen kontaminaatioriskin vuoksi. Ultraviolettisäteily luokitellaan fysikaaliseksi desinfiointimenetelmäksi. Sen tehokkuus perustuu mikro-organismien absorboimaan UV-säteilyyn, jonka aiheuttamien DNA:ssa tai RNA:ssa tapahtuvien muutoksien seurauksena mikro-organismi inaktivoituu ja estyy lisääntymästä. UV-desinfioinnissa on tyypillisesti käytetty elohopeahöyrylamppuja. Vaihtoehtoinen UV-säteilyn lähde ovat LEDit eli valoa emittoivat diodit. Matalapaine-elohopeahöyrylamppujen emittoima säteily on aallonpituudella 254 nm ja keskipaine-elohopeahöyrylamppujen emittoima säteily on laajakaistaista säteilyä. Energiatehokkuuden lisäksi LEDien etuna on, että niillä voidaan tuottaa kapeakaista säteilyä aallonpituudella, joka parhaiten absorboituu DNA:han. Tämän diplomityön tarkoituksena oli tutkia, onko UVC-alueen aallonpituuksien yhdistelmillä synergistisiä etuja LEDien desinfiointitehokkuuteen, kun desinfioidaan virtaavaa vettä useilla säteilyannoksilla ja indikaattorimikrobina käytetään kolibakteeria. Tavoitteena oli myös tutkia tällä hetkellä saatavissa olevien LEDien desinfiointitehokkuutta energiatehokkuuden näkökulmasta. Yksittäisistä aallonpituuksista desinfiointitehokkuudeltaan parhaimmaksi osoittautui 260 nm, aallonpituuksien yhdistelmistä tehokkain oli 265 nm:n ja 260 nm:n yhdistelmä. Muilla aallonpituuksien yhdistelmillä ei saavutettu odotettua parempaa desinfiointitehokkuutta. Optiselta teholtaan parhaimmat LEDit, 265 nm, 270 nm ja 275 nm olivat kokeiden perusteella myös energiatehokkuuden kannalta tarkasteltuina parhaimmat sekä yksittäin että yhdistelminä. UVC-aallonpituuksia emittoivien LEDien optisen tehokkuuden paraneminen on edellytys LEDien hyödyntämiselle desinfioinnissa.

The Combined treatment of UV Light and Titanium Dioxide (TiO2) in Grease Filtration Technique

The aim of this thesis was to identify the best grease removal technique with the application of low power of UV light to TiO2 coated grease filters. The treatment with various power series of ozone generating and ozone free lamps to normal grease filters and TiO2 coated grease filters were examined and the obtained results are compared to each other in this paper. The effect of ozone reaction was observed and compared with the effect of TiO2. The experiments were solely based on the photo oxidation and photo catalytic oxidation reactions. TiO2 is a green catalyst used in the photocatalytic reaction. Sunflower oil was used for grease production and tetracholoroethylene as a solvent. Grease samples were collected from the ventilation duct connected to the cooking hood system. Sample extraction was done in ultrasonic bath with the principle of sonication. The sample analysis was done by FTIR machine. The result determining the concentration of grease was the quantification of saturated C-H bonds in the chosen peak group of the spectrum. A very low power of UVC light functions perfectly with the Titanium dioxide. The experimental results have shown the combined treatment of titanium dioxide and UV light is an effective method in grease removal process. The photocatalytic reaction with titanium dioxide is better than photo oxidation reaction with ozone treatment. Photocatalytic reaction is environmentally friendly, energy efficient and economical.

Ultraviolet light protection and weathering properties of wood-polypropylene composites

The main aim of this thesis is to study the effect of pigments on the weathering properties of wood-polypropylene composites (WPC). The studied properties are color change, water absorption, thickness swelling and Charpy impact strength. The impact of weathering and UV exposure on WPCs was studied by using pigments and minerals as protective agents. The study shows that the pigments and/or mineral fillers can be used to improve the weathering properties of WPCs. The effect of pigments was found to vary with the type of pigment and the method of weathering. The black pigment, an inorganic carbon black master-batch, was found to be the most effective one in reduction of the discoloration of WPCs. By preventing discoloration, and further reducing the degradation of the surface of the WPC, the pigments were found to reduce the decrease in the impact strength after weathering. As well as UV protection, the moisture resistance is a significant factor affecting the durability of WPCs. The addition of mineral fillers was found to improve the moisture-related properties, such as water absorption and thickness swelling, of WPC significantly. According to the findings, addition of pigments and mineral fillers to wood-polypropylene composites appears to be beneficial: color stability and moisture resistance can be enhanced especially in outdoor weathering. The combined effect of black pigment (carbon black master-batch) and wollastonite as a mineral filler was found to bring about the most effective properties against weathering.

Bacterial community structure and petroleum hydrocarbon degradation in the Baltic Sea

The Baltic Sea is unique by its biological, geochemical and physical features. The number of species of larger organisms is small and the species composition is distinctive. On the contrary microbial communities are diverse. Because of the low salinity levels, bacterial communities differ from the ones in the oceans. Knowing the structure of these communities better and how they response to different environmental conditions helps us to estimate how different factors affect the balance and function of the Baltic Sea ecosystem. Bacteria are the key players when it comes to natural biogeochemical processes and human-induced phenomena like eutrophication, oil spills or disposal of other harmful substances to the sea ecosystem. In this thesis, bacterial community structure in the sea surface microlayer and subsurface water of the Archipelago Sea were compared. In addition, the effect of diatom derived polyunsaturated aldehydes on bacterial community structure was studied by a mesocosm experiment. Diesel, crude oil and polycyclic aromatic hydrocarbon degradation capacity of the Baltic Sea bacteria was studied in smaller scale microcosm experiments. In diesel oil experiments bacteria from water phase of the Archipelago Sea was studied. Sediment and iron manganese concretions collected from the Gulf of Finland were used in the crude oil and polycyclic aromatic hydrocarbon experiments. The amount of polycyclic aromatic hydrocarbon degradation genes was measured in all of the oil degradation experiments. The results show how differences in bacterial community structure can be seen in the sea surface when compared to the subsurface waters. The mesocosm experiment demonstrated how diatom-bacteria interactions depend on other factors than diatom derived polyunsaturated aldehydes, which do not seem to have an effect on the bacterial community structure as has been suggested in earlier studies. The dominant bacterial groups in the diesel microcosms differed in samples taken from a pristine site when compared to a site with previous oil exposure in the Archipelago Sea area. Results of the study with sediment and iron-manganese concretions indicate that there are diverse bacterial communities, typical to each bottom type, inhabiting the bottoms of the Gulf of Finland capable to degrade oil and polycyclic aromatic hydrocarbon compounds.  

Recovery and purification of anthocyanins from purple-blue potato

The aim of this work was to study techniques to extract and purify of anthocyanins from purple-blue potato. This topic was determined as a master’s thesis and it was done in collaboration with the Food Chemistry and Food Development Department of University of Turku and Department of Chemical and Process Engineering at Lappeenranta University of Technology. At first, purple-blue potatoes were pretreated in four types of boiled, raw, freeze-dried and dried boiled potato for extraction. They were mixed with aqueous acidified ethanol (ethanol:water:acetic acid 40%:53%:7% v/v) for conventional extraction. Boiled potato was selected as a best pretreated potato. Different ethanol concentration and extraction time were examined and the mixture of 80% in 24 h resulted in maximum anthocyanin content (132.23 mg/L). As conventional extraction method of anthocyanins was non-selective, some of impurities such as free sugars might accelerate anthocyanin degradation. Therefore, to obtain anthocyanins in purified form, adsorption as a promising selective method was used to recovery and isolate anthocyanins. It was carried out with six adsorbents. Among those, Amberlite XAD-7HP, a nonionic acrylic ester adsorbent, was found to have the best performance. In an adsorption column, flow rate of 3 mL/min was selected as the loading flow rate among four tested flow rates. Eluent volume and flow rate were 3 BV of aqueous acidified ethanol (75%, v/v) and 1 mL/min for desorption. The quantification of the total anthocyanin contents was performed by pH-differential method using UV-vis spectrophotometer. The resulting anthocyanin solution after purification was almost free from free sugars which were the major cause for degradation of anthocyanins. The average anthocyanin concentration in the purified and concentrated sample was obtained 1752.89 mg/L.

Blue and Uv-Emitting Upconversion Nanoparticles: Synthesis and (Bio) Analytical Applications.

Rare-earth based upconverting nanoparticles (UCNPs) have attracted much attention due to their unique luminescent properties. The ability to convert multiple photons of lower energy to ones with higher energy through an upconversion (UC) process offers a wide range of applications for UCNPs. The emission intensities and wavelengths of UCNPs are important performance characteristics, which determine the appropriate applications. However, insufficient intensities still limit the use of UCNPs; especially the efficient emission of blue and ultraviolet (UV) light via upconversion remains challenging, as these events require three or more near-infrared (NIR) photons. The aim of the study was to enhance the blue and UV upconversion emission intensities of Tm3+ doped NaYF4 nanoparticles and to demonstrate their utility in in vitro diagnostics. As the distance between the sensitizer and the activator significantly affect the energy transfer efficiency, different strategies were explored to change the local symmetry around the doped lanthanides. One important strategy is the intentional co-doping of active (participate in energy transfer) or passive (do not participate in energy transfer) impurities into the host matrix. The roles of doped passive impurities (K+ and Sc3+) in enhancing the blue and UV upconversions, as well as in influencing the intense UV upconversion emission through excess sensitization (active impurity) were studied. Additionally, the effects of both active and passive impurity doping on the morphological and optical performance of UCNPs were investigated. The applicability of UV emitting UCNPs as an internal light source for glucose sensing in a dry chemistry test strip was demonstrated. The measurements were in agreement with the traditional method based on reflectance measurements using an external UV light source. The use of UCNPs in the glucose test strip offers an alternative detection method with advantages such as control signals for minimizing errors and high penetration of the NIR excitation through the blood sample, which gives more freedom for designing the optical setup. In bioimaging, the excitation of the UCNPs in the transparent IR region of the tissue permits measurements, which are free of background fluorescence and have a high signal-to-background ratio. In addition, the narrow emission bandwidth of the UCNPs enables multiplexed detections. An array-in-well immunoassay was developed using two different UC emission colours. The differentiation between different viral infections and the classification of antibody responses were achieved based on both the position and colour of the signal. The study demonstrates the potential of spectral and spatial multiplexing in the imaging based array-in-well assays.

Performance Degradation Modelling and Techno-Economic Analysis of Lithium-Ion Battery Energy Storage Systems

Transmission system operators and distribution system operators are experiencing new challenges in terms of reliability, power quality, and cost efficiency. Although the potential of energy storages to face those challenges is recognized, the economic implications are still obscure, which introduce the risk into the business models. This thesis aims to investigate the technical and economic value indicators of lithium-ion battery energy storage systems (BESS) in grid-scale applications. In order to do that, a comprehensive performance lithium-ion BESS model with degradation effects estimation is developed. The model development process implies literature review on lifetime modelling, use, and modification of previous study progress, building the additional system parts and integrating it into a complete tool. The constructed model is capable of describing the dynamic behavior of the BESS voltage, state of charge, temperature and capacity loss. Five control strategies for BESS unit providing primary frequency regulation are implemented, in addition to the model. The questions related to BESS dimensioning and the end of life (EoL) criterion are addressed. Simulations are performed with one-month real frequency data acquired from Fingrid. The lifetime and cost-benefit analysis of the simulation results allow to compare and determine the preferable control strategy. Finally, the study performs the sensitivity analysis of economic profitability with variable size, EoL and system price. The research reports that BESS can be profitable in certain cases and presents the recommendations.