Analytical methods for analyzing organic peroxides

Työn tarkoituksena oli kehittää analyyttinen erotusmenetelmä eräässä valmistusprosessissa käytettävän hapettavan aineen ja liuottimen välillä syntyvien reaktiotuotteiden tutkimiseen ja analysoimiseen. Lisäksi tarkoituksena oli tutkia prosessiolosuhteiden turvallisuutta. Kirjallisuusosassa käsitellään erilaisia orgaanisia peroksideja, niiden käyttötarkoituksia ja niiden käyttöön liittyviä huomioitavia asioita. Lisäksi tarkastellaan yleisimpiä analyysimenetelmiä, joita on käytetty erilaisten peroksidien analysoinnissa. Näitä analyysimenetelmiä on useimmiten käytetty nestemäisten näytteiden tutkimuksissa. Harvemmin on analysoitu kaasu- ja kiintoainenäytteitä. Kokeellisessa osassa kehitettiin kirjallisuuden perusteella peroksidiyhdisteille identifiointimenetelmä ja tutkittiin prosessin näytteet. Analyysimenetelmiksi valittiin iodometrinen titraus ja HPLC-UV-MS-menetelmä. Lisäksi käytettiin peroksidimittaukseen soveltuvia testiliuskoja. Tutkimus osoitti, että iodometrisen titrauksen ja testiliuskojen perusteella näytteissä oli vähäisiä määriä peroksideja viikon jälkeen peroksidilisäyksestä. HPLC-UV-MS-analyysien perusteella näytteiden analysointia häiritsi selluloosa, jota löytyi jokaisesta näytteestä.

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.

Decentralized management of organic household wastes in the Kathmandu Valley using small-scale composting reactors

The sustainable management of municipal solid waste in the Kathmandu Valley has always been a challenging task. Solid waste generation has gone rapidly high in the Kathmandu Valley over the last decade due to booming population and rapid urbaniza-tion. Finding appropriate landfill sites for the disposal of solid wastes generated from the households of the Kathmandu Valley has always been a major problem for Nepalese government. 65 % of total generated wastes from the households of Nepal consist of organic materials. As large fractions of generated household wastes are organic in na-ture, composting can be considered as one of the best sustainable ways to recycle organ-ic wastes generated from the households of Nepal. Model Community Society Development (MCDS), a non-governmental organization of Nepal carried out its small-scale project in five households of the Kathmandu Valley by installing composting reactors. This thesis is based on this small-scale project and has used secondary data provided by MCDS Nepal for carrying out the study. Proper man-agement of organic wastes can be done at household levels through the use of compost-ing reactors. The end product compost can be used as soil conditioners for agricultural purposes such as organic farming, roof-top farming and gardening. The overall average organic waste generation in the Kathmandu Valley is found to be 0,23 kg/person/day and the total amount of organic household wastes generated in the Kathmandu Valley is around 210 Gg/yr. Produced composts from five composting reac-tors contain high amount of moistures but have sufficient amount of nutrients required for the fertility of land and plant growth. Installation of five composting reactors in five households have prevented 2,74 Mg of organic wastes going into the landfills, thus re-ducing 107 kg of methane emissions which is equivalent to 2,7 Mg of carbondioxide.

Comparative lifecycle assessment on organic and conventional carrots – case: Carrots from South-Savo and imported carrots from Italy

Organic farming is perceived to be an environmental friendly method of food production, thus assumed to be an alternative means of minimizing food-based environmental footprints. However, lower yield and unproductive years in organic crop rotation raise questions of whether it is really an environmentally friendly farming practice. Thus, the aim of this thesis was to examine the carbon footprint and energy demands of organic carrots cultivated and sold in South-Savo, Finland and compare them with those of local and imported conventional carrots using lifecycle assessment (LCA) as a method. From the investigation, it was found that organic carrots produced in South-Savo have the lowest GHG emissions and energy demand. The GHG emissions of local organic, local conventional and imported conventional carrots were found to be 4g CO2 eq. kgcarrots-1, 142g CO2 eq. kgcarrots-1 and 280 g CO2 eq. kgcarrots-1, respectively. On the other hand, energy demand for those carrots was found to be 1,33 MJ, 1,88 MJ and 3,68 MJ kgcarrots-1. Furthermore, it was also found that local organic carrots would have approximately similar GHG emissions as conventional counterpart if soil carbon stock change was excluded from the study.

Ultrasonic and Electrokinetic Remediation of Low Permeability Soil Contaminated with Persistent Organic Pollutants

Electrokinetics has emerged as a potential technique for in situ soil remediation and especially unique because of the ability to work in low permeability soil. In electrokinetic remediation, non-polar contaminants like most organic compounds are transported primarily by electroosmosis, thus the process is effective only if the contaminants are soluble in pore fluid. Therefore, enhancement is needed to improve mobility of these hydrophobic compounds, which tend to adsorb strongly to the soil. On the other hand, as a novel and rapidly growing science, the applications of ultrasound in environmental technology hold a promising future. Compared to conventional methods, ultrasonication can bring several benefits such as environmental friendliness (no toxic chemical are used or produced), low cost, and compact instrumentation. It also can be applied onsite. Ultrasonic energy applied into contaminated soils can increase desorption and mobilization of contaminants and porosity and permeability of soil through developing of cavitation. The research investigated the coupling effect of the combination of these two techniques, electrokinetics and ultrasonication, in persistent organic pollutant removal from contaminated low permeability clayey soil (with kaolin as a model medium). The preliminary study checked feasibility of ultrasonic treatment of kaolin highly contaminated by persistent organic pollutants (POPs). The laboratory experiments were conducted in various conditions (moisture, frequency, power, duration time, initial concentration) to examine the effects of these parameters on the treatment process. Experimental results showed that ultrasonication has a potential to remove POPs, although the removal efficiencies were not high with short duration time. The study also suggested intermittent ultrasonication over longer time as an effective means to increase the removal efficiencies. Then, experiments were conducted to compare the performances among electrokinetic process alone and electrokinetic processes combined with surfactant addition and mainly with ultrasonication, in designed cylinders (with filtercloth separating central part and electrolyte parts) and in open pans. Combined electrokinetic and ultrasonic treatment did prove positive coupling effect compared to each single process alone, though the level of enhancement is not very significant. The assistance of ultrasound in electrokinetic remediation can help reduce POPs from clayey soil by improving the mobility of hydrophobic organic compounds and degrading these contaminants through pyrolysis and oxidation. Ultrasonication also sustains higher current and increases electroosmotic flow. Initial contaminant concentration is an essential input parameter that can affect the removal effectiveness.

Working fluid selection and design of small-scale waste heat recovery systems based on organic Rankine cycles

Demand for the use of energy systems, entailing high efficiency as well as availability to harness renewable energy sources, is a key issue in order to tackling the threat of global warming and saving natural resources. Organic Rankine cycle (ORC) technology has been identified as one of the most promising technologies in recovering low-grade heat sources and in harnessing renewable energy sources that cannot be efficiently utilized by means of more conventional power systems. The ORC is based on the working principle of Rankine process, but an organic working fluid is adopted in the cycle instead of steam. This thesis presents numerical and experimental results of the study on the design of small-scale ORCs. Two main applications were selected for the thesis: waste heat re- covery from small-scale diesel engines concentrating on the utilization of the exhaust gas heat and waste heat recovery in large industrial-scale engine power plants considering the utilization of both the high and low temperature heat sources. The main objective of this work was to identify suitable working fluid candidates and to study the process and turbine design methods that can be applied when power plants based on the use of non-conventional working fluids are considered. The computational work included the use of thermodynamic analysis methods and turbine design methods that were based on the use of highly accurate fluid properties. In addition, the design and loss mechanisms in supersonic ORC turbines were studied by means of computational fluid dynamics. The results indicated that the design of ORC is highly influenced by the selection of the working fluid and cycle operational conditions. The results for the turbine designs in- dicated that the working fluid selection should not be based only on the thermodynamic analysis, but requires also considerations on the turbine design. The turbines tend to be fast rotating, entailing small blade heights at the turbine rotor inlet and highly supersonic flow in the turbine flow passages, especially when power systems with low power outputs are designed. The results indicated that the ORC is a potential solution in utilizing waste heat streams both at high and low temperatures and both in micro and larger scale appli- cations.

Interfacial effects in organic solar cells

Solceller baserade på organiska halvledare erbjuder en möjlighet till storskalig och billig solenergiproduktion. Organiska halvledare har den fördelen att de är lösningsprocesserbara vilket gör att solceller och andra elektroniska komponenter baserade på dessa halvledare kan tillverkas vid låga temperaturer och med liten energiförbrukning. Nackdelen med dessa material är deras strukturella och energetiska oordning som leder till lägre effektivitet. För att organiska solceller ska kunna kommersialiseras krävs grundläggande insikter i de olika processer som begränsar effektiviteten. En stor del av forskningen om dessa processer har varit fokuserad kring egenskaperna av solcellens olika komponenter (de aktiva materialen) som sådana, medan gränsytorna mellan olika material har fått mindre uppmärksamhet. Gränsytor mellan olika material har distinkt olika egenskaper jämfört med ett rent material, och gränsytors olika egenskaper kan ha en väldigt stor inverkan på hur solcellerna fungerar. Syftet med denna avhandling är att klargöra några olika gränsyterelaterade effekter i organiska dioder och solceller. De gränsytor som behandlas är gränsytan mellan kontakten och det aktiva lagret (metall-organisk) och gränsytan mellan donor och acceptor (organisk-organisk). Resultaten visar att metall-organiska gränsytor måste designas noggrant för att begränsa förlust av effektivitet. En icke-idealisk kontakt leder till starkt reducerad effektivitet på grund av att elektronerna extraheras ineffektivt. Även till synes idealiska kontakter kan orsaka förluster genom spontan laddningsöverföring från metallen till det organiska lagret som effektivt sett minskar på den spänning som cellen kan alstra. Den organisk-organiska gränsytan påverkar hur mycket ström cellen kan alstra och beroende på gränsytans beskaffenhet kan de negativa rekombinationsprocesserna i materialet kontrolleras. ------------------------------------------------- Orgaanisille puolijohteille perustuvat aurinkokennot mahdollistavat suurimuotoisen ja edullisen aurinkoenergiatuotannon. Orgaanisten puolijohteiden etu on että ne voidaan liuottaa, jolloin aurinkokennot ja muut näille johteille perustuvat elektroniset komponentit voidaan valmistaa alhaisessa lämpötilassa kuluttaen vähän energiaa. Materiaalien huonona puolena on kuitenkin niiden rakenteellinen ja energeettinen epäjärjestys, jonka seurauksena niiden tehokkuus on huonompi. Orgaanisten aurinkokennojen kaupallistaminen edellyttää perustavanlaatuista ymmärystä tehokkuutta rajoittavista prosesseista. Aurinkokennotutkimus on pääosin keskittynyt aurinkokennon eri komponenttien (aktiivisten materiaalien) ominaisuuksiin, kun taas eri materiaalien rajapinnat ovat jääneet vähemmälle huomiolle. Eri materiaalien välisillä rajapinnoilla on huomattavan erilaisia ominaisuuksia verrattuna puhtaisiin materiaaleihin. Rajapintojen ominaisuudet voivat kuitenkin vaikuttaa merkittävästi aurinkokennojen toimintaan. Tämän väitöstutkimuksen tarkoituksena on selventää joitain rajapintoihin liittyviä toimintoja orgaanisissa diodeissa ja aurinkokennoissa. Käsiteltävät rajapinnat ovat rajapinta kontaktin ja aktiivisen kerroksen välillä (metallis-orgaaninen) ja rajapinta donorin ja akseptorin välillä (orgaanis-orgaaninen). Tutkimustulokset osoittavat, että metallis-orgaaniset rajapinnat tulee suunnitella huolellisesti, jotta tehokkuuden alenemista voidaan rajoittaa. Mikäli kontakti ei ole ideaalisti suunniteltu, vähenee tehokkuus huomattavasti, mikä johtuu elektronien tehottomasta ekstrahoinnista. Jopa ideaalisilta vaikuttavat kontaktit voivat johtaa tehokkuuden alenemiseen, mikäli varaus siirtyy spontaanisti metallista orgaaniseen kerrokseen, sillä tämä alentaa jännitettä jonka kenno voi tuottaa. Kennon orgaanis-orgaaninen rajapinta vaikuttaa siihen, kuinka paljon virtaa kenno pystyy tuottamaan. Rajapinnan ominaisuuksista riippuen materiaalin rekombinaatio on hallittavissa.

Persistent organic pollutants in sediments and fish from Lake Victoria, Uganda

This thesis describes the occurrence and sources of selected persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorocyclohexanes (HCHs) in the northern watershed of Lake Victoria. Sediments and fish were collected from three highly polluted embayments (i.e. Murchison Bay, Napoleon Gulf and Thurston Bay) of the lake. The analysis for PCDD/Fs, PCBs and PBDEs was done using a high resolution mass spectrometer coupled to a gas chromatograph (GC), and a GC equipped with an electron capture detector was used for HCHs. Total (Σ) PCDD/Fs, PCBs and PBDEs in sediments ranged from 3.19 to 478, 313 to 4325 and 60.8 to 179 pg g-1 dry weight (dw), respectively. The highest concentrations of pollutants were found at sites close to industrial areas and wastewater discharge points. The maximum concentrations of PCDD/Fs, PCBs, PBDEs and HCHs in fish muscle homogenates were 49, 779, 495 and 45,900 pg g-1 wet weight (ww), respectively. The concentrations of the pollutants in Nile perch (Lates niloticus) were significantly greater than those in Nile tilapia (Oreochromis niloticus), possibly due to differences in trophic level and dietary feeding habits among fish species. World Health Organization-toxic equivalency quotient (WHO2005-TEQ) values in the sediments were up to 4.24 pg g-1 dw for PCDD/Fs and 0.55 pg TEQ g-1 dw for the 12 dioxin-like PCBs (dl-PCBs). 23.1% of the samples from the Napoleon Gulf were above the interim sediment quality guideline value of 0.85 pg WHO-TEQ g-1 dw set by the Canadian Council for Ministers of the Environment. The WHO2005-TEQs in fish were 0.001-0.16 pg g-1 for PCDD/Fs and 0.001-0.31 pg g-1 ww for dl- PCBs. The TEQ values were within a permissible level of 3.5 pg g−1 ww recommended by the European Commission. Based on the Commission set TEQs and minimum risk level criteria formulated by the Agency for Toxic Substances and Disease Registry, the consumption of fish from Lake Victoria gives no indication of health risks associated to PCDD/Fs and PCBs. Principal component analysis (PCA) indicated that anthropogenic activities such as agricultural straw open burning, medical waste incinerators and municipal solid waste combustors were the major sources of PCDD/Fs in the watershed of Lake Victoria. The ratios of α-/γ-HCH varied from 0.89 to 1.68 suggesting that the highest HCH residues mainly came from earlier usage and fresh γ-HCH (lindane). In the present study, the concentration of POPs in fish were not significantly related to those in sediments, and the biota sediment accumulation factor (BSAF) concept was found to be a poor predictor of the bioavailability and bioaccumulation of environmental pollutants.

Optical spectroscopy of organic material based on C60

The structure and optical properties of thin films based on C60 materials are studied. Reproducible vacuum method of thin fullerene films production with Cd impurity on Si, glass and mica surfaces is developed. Surface morphology of the films are investigated by AFM and SEM methods. The ab initio quantum - chemical calculations of the geometry, total energy and excited energy states of complex fullerene- cadmium telluride supramolecules are performed. Photoluminescence spectra of composite thin films based on C60 before and after X-ray irradiation were measured. The intensity of additional peaks is defined as the charge composition due to the type of substrate. These results are interpreted as an appearance of the dipole-allowed transitions in the fullerene excited singlet states spectrum cause of an interference with cadmium telluride. X-ray irradiated films were investigated, and additional peaks in photoluminescence spectra were detected. These peaks appear as a result of molecular complexes formation from C60CdTe mixture and dimerization of the films. Density functional B3LYP quantum-chemical calculations for C60CdTe, molecular complexes, (C60)2 and C120O dimers were performed to elucidate some experimental results.

Perfluorattuja yhdisteitä sisältävien jätevesien puhdistus- ja analyysimenetelmät

Perfluoratut alkyyliyhdisteet eli PFAS-yhdisteet ovat synteettisiä orgaanisia yhdisteitä, joissa on fluorattu hiiliketju. Hiilen ja fluorin väliset vahvat sidokset ovat muodostuneet ongelmaksi jätevedenpuhdistamoilla, sillä yhdisteet eivät hajoa puhdistamoilla käytössä olevilla vedenpuhdistusmenetelmillä. Yhdisteitä kertyy luontoon jätevesien mukana. Kandidaatintyössä on vertailtu yhdisteitä sisältävien vesien käsittelymenetelmiä parhaiten soveltuvan menetelmän löytämiseksi. Menetelmien kustannuksia tai soveltuvuutta vedenpuhdistamomittakaavan prosessiksi ei ole arvioitu. Lisäksi työssä on koottu yhdisteitä sisältävien jätevesien analysointiin sopivia analyysimenetelmiä. Soveltuvat puhdistus- ja analyysimenetelmät on esitelty uusien tieteellisten artikkelien pohjalta. Mahdollisia erotusmenetelmiä ovat membraanierotus ja sorptio. Membraaneista soveltuvimpia ovat nanosuodatus- ja käänteisosmoosimembraanit, joilla erottuvat jopa 0,0001 μm:n kokoiset partikkelit. PFAS-yhdisteet voidaan erottaa sorptiolla muun muassa aktiivihiileen. Yhdisteiden rakenne hajoaa nykyaikaisilla hapetusmenetelmillä ja polttamalla lietteen mukana. Hapettaminen permanganaatin avulla ei tuottanut hyvää tulosta, mutta fotokemiallisella hapetuksella ja alhaisen lämpötilan plasmatekniikalla (NTP) yhdisteiden rakenne hajosi lähes kokonaan. Fotokemiallinen hapetus onnistui erityisesti perfluorokarboksyylihapoilla, joiden rakenne hajosi jopa kolmessa tunnissa. Yleisimmin käytetty analyysimenetelmä on nestekromatografin ja massaspektrometrin yhdistelmä (LC-MS/MS) ja matriisivaikutus minimoidaan tyypillisesti kiinteäfaasiuutolla (SPE). Työssä esitellyistä käsittelymenetelmistä parhaiten soveltuva on NTP-menetelmä, koska sillä saatiin tutkimusten mukaan hajotettua yhdisteiden rakenne muita menetelmiä lyhyemmässä ajassa ja se soveltuu parhaiten kaikille PFAS-yhdisteille. NTP-menetelmässä ei tarvita katalyyttiä tai lisäkemikaaleja. Voimakkaana hapettimena toimivat epästabiilit hydroksyyliradikaalit, jotka syntyvät koronapurkauksen kautta. Koronapurkauksessa muodostuu myös otsonia ja lisäksi vapaa happi voi tehostaa hapettumista. Menetelmässä muodostuvien hajoamistuotteiden hallinta vaatii lisätutkimusta. Mahdollinen hallintakeino voisi olla esimerkiksi hapettumisessa vapautuvien fluoridi-ionien saostaminen. Muodostuvien hajoamistuotteiden toksisuutta voitaisiin tarkkailla biosensorilla.

Two-dimensional drift-diffusion simulation of organic solar cells

The aim of this master's thesis is to develop a two-dimensional drift-di usion model, which describes charge transport in organic solar cells. The main bene t of a two-dimensional model compared to a one-dimensional one is the inclusion of the nanoscale morphology of the active layer of a bulk heterojunction solar cell. The developed model was used to study recombination dynamics at the donor-acceptor interface. In some cases, it was possible to determine e ective parameters, which reproduce the results of the two-dimensional model in the one-dimensional case. A summary of the theory of charge transport in semiconductors was presented and discussed in the context of organic materials. Additionally, the normalization and discretization procedures required to nd a numerical solution to the charge transport problem were outlined. The charge transport problem was solved by implementing an iterative scheme called successive over-relaxation. The obtained solution is given as position-dependent electric potential, free charge carrier concentrations and current densities in the active layer. An interfacial layer, separating the pure phases, was introduced in order to describe charge dynamics occurring at the interface between the donor and acceptor. For simplicity, an e ective generation of free charge carriers in the interfacial layer was implemented. The pure phases simply act as transport layers for the photogenerated charges. Langevin recombination was assumed in the two-dimensional model and an analysis of the apparent recombination rate in the one-dimensional case is presented. The recombination rate in a two-dimensional model is seen to e ectively look like reduced Langevin recombination at open circuit. Replicating the J-U curves obtained in the two-dimensional model is, however, not possible by introducing a constant reduction factor in the Langevin recombination rate. The impact of an acceptor domain in the pure donor phase was investigated. Two cases were considered, one where the acceptor domain is isolated and another where it is connected to the bulk of the acceptor. A comparison to the case where no isolated domains exist was done in order to quantify the observed reduction in the photocurrent. The results show that all charges generated at the isolated domain are lost to recombination, but the domain does not have a major impact on charge transport. Trap-assisted recombination at interfacial trap states was investigated, as well as the surface dipole caused by the trapped charges. A theoretical expression for the ideality factor n_id as a function of generation was derived and shown to agree with simulation data. When the theoretical expression was fitted to simulation data, no interface dipole was observed.