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.

Production of fungal volatile organic compounds in bedding materials

Selostus: Haihtuvien orgaanisten yhdisteiden muodostuminen kuivikkeissa

Kompostointilaitoksen lopputuotteen käyttömahdollisuudet. Case: Himanka

Työssä selvitetään kompostointilaitoksen lopputuotteen erilaisia käyttömahdollisuuksia. Yleisten käyttökohteiden pohjalta on luotu malli Vapo Oy Biotech:n toimittaman Himangan kompostointilaitoksen kompostin hyödyntämiselle. Laitos sijaitsee Himangan kunnassa Keski- Pohjanmaalla. Laitoksella kompostoidaan pääasiassa Himangan ja ympäröivien kuntien jätevesilietteitä turkiseläinlantaa. Jätehuolto Suomessa ja koko EU:n alueella elää voimakasta muutoskautta. Orgaanisten jätteiden vienti kaatopaikoille pyritään tulevaisuudessa lopettamaan kokonaan, mikä on lisännyt niiden käsittelyä mm. kompostoimalla. Kompostoinnin lopputuotteena saadaan ravinteikasta, humuspitoista ainesta. Kompostoinnin yhtenä tavoitteena on tuottaa hyötykäyttöön soveltuvaa tuotetta, joten käyttökohteen löytäminen kompostille on laitoksen toiminnan kannalta erittäin tärkeää. Kompostin käyttömahdollisuuksiin vaikuttavat lainsäädäntö, kompostin ominaisuudet sekä paikalliset olosuhteet. Käyttökohteet on työssä jaettu ei-energiakäyttöön ja energiakäyttöön. Ei-energiakäyttöön kuuluvat maanparannuskäyttö, lannoitekäyttö, käyttö kasvualustassa, maisemointi ja julkinen rakentaminen sekä joitakin erityissovelluksia. Energiakäytön puolella on tarkasteltu kompostin soveltuvuutta erilaisille polttotekniikoille sekä vertailtu kompostia muihin kiinteisiin polttoaineisiin. Kompostien soveltuvuutta eri kohteisiin on arvioitu kompostin analyysi- ja kasvatuskoetulosten pohjalta. Kompostin ei-energiakaytössa on saatu eri tutkimuksissa lupaavia tuloksia. Kompostin on todettu soveltuvan erittäin hyvin mm. perunanviljelyyn, viljan ja nurmikasvien viljelyyn ja erilaisiin maisemointikohteisiin sekä kotipuutarhakäyttöön. Kompostin käyttöä polttoaineena ei ole vielä kokeiltu missään. Kompostin polton suurimmat ongelmat ovat korkea tuhka-, rikki- ja typpipitoisuus sekä epätasainen laatu.

High voltage discharge for degradation of organic contaminants in water

The pulsed dielectric barrier discharge (PDBD) and pulsed corona discharge (PCD) were compared for their efficiency to degrade phenol in water solution. Results show that PCD has higher efficiency than PDBD to degrade phenol. When initial pH of water solution was elevated, phenol degradation in the PCD reactor was significantly enhanced, although no considerable effect was seen in the PDBD reactor. The PCD reactor was also able to degrade lignin significantly, both in synthetically prepared solution and in pulp and paper mill wastewater. Water temperature did not affect phenol degradation; however, lignin was better oxidized at lower temperature.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Importance of considering food waste in the development of sustainable food packaging systems

Meeting the needs of both present and future generations forms the foundation of sustainable development. Concern about food demand is increasing alongside the continuously growing population. In the pursuit of food security preventing food waste is one solution avoiding the negative environmental impacts that result from producing food unnecessarily. Packages offer one answer to preventing food waste, as they 1) preserve and protect food, 2) introduce the user to the correct way to handle and use the food and package and 3) allow the user to consume the food in its entirety. This thesis aims to enhance the sustainability of food packages by giving special emphasis to preventing food waste. The focus of this thesis is to assist the packaging designer in being able to take into account the requirements for the sustainability of food packages and to be able to integrate these requirements into the product development process. In addition, life cycle methods that can be used as a tool in the packaging design process or in assessing the sustainability of finished food-packaging combinations are evaluated. The methods of life cycle costing (LCC) and life cycle working environment (LCWE) are briefly discussed. The method of life cycle assessment (LCA) is examined more thoroughly through the lens of the literature review of food-package LCA case studies published in the 21st century in three relevant journals. Based on this review and on experiences learned from conducting LCAs, recommendations are given as to how the LCA practitioner should conduct a food packaging study to make most of the results. Two case studies are presented in this thesis. The first case study relates the results of a life cycle assessment conducted for three food items (cold cut (ham), sliced dark bread (rye) and Soygurt drink) and the alternative packaging options of each. Results of this study show that the packaging constitutes only 1–12 % of the total environmental impacts of the food-packaging combination. The greatest effect is derived from the food itself and the wasted food. Even just a small percentage of wasted food causes more environmental impacts than does the packaging. The second case study presents the results of LCC and LCWE analysis done for fruit and vegetable transport packages. In this thesis, the specific results of the study itself are not the focus, but rather the study methods and scope are analysed based on how these complement the sustainability assessment of food packages. This thesis presents reasons why prevention of food waste should be more thoroughly taken into account in food packaging design. In addition, the task of the packaging designer is facilitated by the requirements of sustainable food packaging, by the methods and step-by-step guidance on how to integrate sustainability issues into the design process, and by the recommendations on how to assess the sustainability of food packages. The intention of this thesis is to express the issues that are important in the field of the food packaging industry. Having recognised and implemented these issues, businesses can better manage the risks that could follow from neglecting these sustainability aspects.

Jätteen rinnakkaispolton rooli ja rajaehdot Suomen jätestrategiassa

Suomen jätehuolto on kokemassa murrosta kuluvina aikoina. Pienimuotoinen jätteen rinnakkaispoltto, joka on ollut Suomen jätehuollolle ominaista, uhkaa koitua kannattamattomaksi ja loppua kokonaan. Tässä työssä pyritään selvittämään jätteen rinnakkaispolton rooli ja rajaehdot Suomen jätestrategiassa nytkun jätehuolto on muuttunut uusien direktiivien voimaan astumisen myötä. Työssäkäsitellään rinnakkaispolttoa koskevaa lainsäädäntöä ja sen vaikutusta polton tulevaisuuteen. Rajaehtoja on tarkasteltu savukaasupäästöjen, päästörajojen ja tuhkan ominaisuuksien muuttumisen avulla polttosuhteen muuttuessa. Lisäksi työssä on arvioitu jätteenpolttoasetuksen aiheuttamat lisäkustannukset jätettä polttaville voimalaitoksille ja pohdittu, miten kustannukset on kompensoitavissa. Työn perusteella vaikuttaa siltä, että jätteen rinnakkaispoltolla voi tulevaisuudessakin olla merkittävä rooli Suomen jätehuollossa. Jätteen energiahyödyntämistä joudutaan lisäämään tulevaisuudessa rutkasti, jotta saavutettaisiin vaadittu jätteen hyötykäyttötaso. Rinnakkaispolton alalta on Suomessa huippuosaamista ja laitospotentiaalia on valmiina, joten rinnakkaispoltto tarjoaa helpon mahdollisuuden jätteen hyödyntämisasteen parantamiseen. Kriittiseksi tekijäksimuodostuu se, voiko yhdyskuntajätteistä valmistettua polttoainetta polttaa sähkön ja lämmön yhteistuotantoon tarkoitetuilla laitoksilla. Mikäli se olisi mahdollista, voisi tämän työn perusteella rinnakkaispoltolla olla suuri rooli suomalaisessa jätehuollossa ja sen tulevaisuudessa.

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.

Biogas production in regional integrated biodegradable waste treatment – Possibilities for improving energy performance and reducing GHG emissions

The greatest threat that the biodegradable waste causes on the environment is the methane produced in landfills by the decomposition of this waste. The Landfill Directive (1999/31/EC) aims to reduce the landfilling of biodegradable waste. In Finland, 31% of biodegradable municipal waste ended up into landfills in 2012. The pressure of reducing disposing into landfills is greatly increased by the forthcoming landfill ban on biodegradable waste in Finland. There is a need to discuss the need for increasing the utilization of biodegradable waste in regional renewable energy production to utilize the waste in a way that allows the best possibilities to reduce GHG emissions. The objectives of the thesis are: (1) to find important factors affecting renewable energy recovery possibilities from biodegradable waste, (2) to determine the main factors affecting the GHG balance of biogas production system and how to improve it and (3) to find ways to define energy performance of biogas production systems and what affects it. According to the thesis, the most important factors affecting the regional renewable energy possibilities from biodegradable waste are: the amount of available feedstock, properties of feedstock, selected utilization technologies, demand of energy and material products and the economic situation of utilizing the feedstocks. The biogas production by anaerobic digestion was seen as the main technology for utilizing biodegradable waste in agriculturally dense areas. The main reason for this is that manure was seen as the main feedstock, and it can be best utilized with anaerobic digestion, which can produce renewable energy while maintaining the spreading of nutrients on arable land. Biogas plants should be located close to the heat demand that would be enough to receive the produced heat also in the summer months and located close to the agricultural area where the digestate could be utilized. Another option for biogas use is to upgrade it to biomethane, which would require a location close to the natural gas grid. The most attractive masses for biogas production are municipal and industrial biodegradable waste because of gate fees the plant receives from them can provide over 80% of the income. On the other hand, directing gate fee masses for small-scale biogas plants could make dispersed biogas production more economical. In addition, the combustion of dry agricultural waste such as straw would provide a greater energy amount than utilizing them by anaerobic digestion. The complete energy performance assessment of biogas production system requires the use of more than one system boundary. These can then be used in calculating output–input ratios of biogas production, biogas plant, biogas utilization and biogas production system, which can be used to analyze different parts of the biogas production chain. At the moment, it is difficult to compare different biogas plants since there is a wide variation of definitions for energy performance of biogas production. A more consistent way of analyzing energy performance would allow comparing biogas plants with each other and other recovery systems and finding possible locations for further improvement. Both from the GHG emission balance and energy performance point of view, the energy consumption at the biogas plant was the most significant factor. Renewable energy use to fulfil the parasitic energy demand at the plant would be the most efficient way to reduce the GHG emissions at the plant. The GHG emission reductions could be increased by upgrading biogas to biomethane and displacing natural gas or petrol use in cars when compared to biogas CHP production. The emission reductions from displacing mineral fertilizers with digestate were seen less significant, and the greater N2O emissions from spreading digestate might surpass the emission reductions from displacing mineral fertilizers.

Metaanin muodostumisen mallintaminen kaatopaikalla

Methane-rich landfill gas is generated when biodegradable organic wastes disposed of in landfills decompose under anaerobic conditions. Methane is a significant greenhouse gas, and landfills are its major source in Finland. Methane production in landfill depends on many factors such as the composition of waste and landfill conditions, and it can vary a lot temporally and spatially. Methane generation from waste can be estimated with various models. In this thesis three spreadsheet applications, a reaction equation and a triangular model for estimating the gas generation were introduced. The spreadsheet models introduced are IPCC Waste Model (2006), Metaanilaskentamalli by Jouko Petäjä of Finnish Environment Institute and LandGEM (3.02) of U.S. Environmental Protection Agency. All these are based on the first order decay (FOD) method. Gas recovery methods and gas emission measurements were also examined. Vertical wells and horizontal trenches are the most commonly used gas collection systems. Emission measurements chamber method, tracer method, soil core and isotope measurements, micrometeorological mass-balance and eddy covariance methods and gas measuring FID-technology were discussed. Methane production at Ämmässuo landfill of HSY Helsinki Region Environmental Services Authority was estimated with methane generation models and the results were compared with the volumes of collected gas. All spreadsheet models underestimated the methane generation at some point. LandGEM with default parameters and Metaanilaskentamalli with modified parameters corresponded best with the gas recovery numbers. Reason for the differences between evaluated and collected volumes could be e.g. that the parameter values of the degradable organic carbon (DOC) and the fraction of decomposable degradable organic carbon (DOCf) do not represent the real values well enough. Notable uncertainty is associated with the modelling results and model parameters. However, no simple explanation for the discovered differences can be given within this thesis.

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.