Quantitative elemental analysis of dry-ashed bark and wood samples of birch, spruce and pine from south-western Finland using PIXE

A total of over 200 different samples of bark and wood of Silver birch, Norway spruce and Scots pine were analysed. Samples were taken from several areas in western Finland, some with known sources of atmospheric heavy metal emission (Harjavalta, Ykspihlaja). Also analytical data for pine needles from some sites are reported. The chemical analyses were performed by thick-target particle-induced X-ray emission (PIXE) spectrometry after preconcentration by dry ashing of samples at 550oC. The following elements were quantified in most of the samples: P, S, K, Ca, Mn, Fe, Ni, Cu, Zn, Rb, Sr, Cd, Ba and Pb. The ash percentage and the chemical composition of ashes of different wood materials were also obtained, as dry ashing was used in the analytical procedure. The variations in elemental concentrations in wood and bark of an individual tree, expressed as RSDs, were mostly in the range 10 – 20 %. For several trees of the same species sampled from small areas (< 1 ha), the variations in elemental concentrations were surprisingly high (RSDs 20 – 50 %). In the vicinity of metal plants, effects of strong atmospheric heavy metal pollution (pollution factor above 100) were observed in pine bark. The increase of heavy metal content in wood samples from the same sites was quite small. Elemental concentrations in ashes of bark and wood, from areas with no local source of atmospheric pollution, were relatively uniform. Based on this observation an alternative way of demonstrating atmospheric pollution of tree bark is discussed.

APROS model validation in case of fast transients in a boiling water reactor

This Master´s thesis investigates the performance of the Olkiluoto 1 and 2 APROS model in case of fast transients. The thesis includes a general description of the Olkiluoto 1 and 2 nuclear power plants and of the most important safety systems. The theoretical background of the APROS code as well as the scope and the content of the Olkiluoto 1 and 2 APROS model are also described. The event sequences of the anticipated operation transients considered in the thesis are presented in detail as they will form the basis for the analysis of the APROS calculation results. The calculated fast operational transient situations comprise loss-of-load cases and two cases related to a inadvertent closure of one main steam isolation valve. As part of the thesis work, the inaccurate initial data values found in the original 1-D reactor core model were corrected. The input data needed for the creation of a more accurate 3-D core model were defined. The analysis of the APROS calculation results showed that while the main results were in good accordance with the measured plant data, also differences were detected. These differences were found to be caused by deficiencies and uncertainties related to the calculation model. According to the results the reactor core and the feedwater systems cause most of the differences between the calculated and measured values. Based on these findings, it will be possible to develop the APROS model further to make it a reliable and accurate tool for the analysis of the operational transients and possible plant modifications.

Characterisation of waste for combustion : with special reference to the role of zinc

Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

Analysis of Alpha CA Genes in Early Vertebrates and ; High-Invertebrates

Carbonic anhydrases are enzymes that are ubiquitously found in all organisms that are engaged in catalyzing the hydration of carbon dioxide to form bicarbonate and proton and vice versa. They are crucial in the process of respiration, bone resorption, pH regulation, ion transport, and photosynthesis in plants. Out of the five classes of carbonic anhydrase α, β, γ, δ, ζ this study focused in the α carbonic anhydrases. This class of CAs constitute of 16 subfamilies in mammals that include 3 non-active enzymes known as Carbonic Anhydrase Related Proteins. The inactiveness of these enzymes is due to the loss of one or more Histidine residues in the active site. This thesis was conducted based on the aim of studying evolutionary analysis of carbonic anhydrase sequences from organisms spanning from the Cambrian age. It was carried out in two phases. The first phase was the sequence collection, which involved many biological sequence databases as a source. The scope of this segment included sequence alignments and analysis of the sequence manually and in an automated form incorporating few analysis tools. The second Phase was phylogenetic analysis and exploring the subcellular location of the proteins, which was key for the evolutionary analysis. Through the medium of the methods conducted with respect to the phases mentioned above, it was possible to accomplish the desired result. Certain thought-provoking sequences were come across and analyzed thoroughly. Whereas, Phylogenetics showed interesting results to bolster previous findings and new findings as well which lay bedrock for future intensified studies.

Logging residues from regeneration fellings for biofuel production - a GIS-based availability and supply cost analysis

Finland has large forest fuel resources. However, the use of forest fuels for energy production has been low, except for small-scale use in heating. According to national action plans and programs related to wood energy promotion, the utilization of such resources will be multiplied over the next few years. The most significant part of this growth will be based on the utilization of forest fuels, produced from logging residues of regeneration fellings, in industrial and municipal power and heating plants. Availability of logging residues was analyzed by means of resource and demand approaches in order to identify the most suitable regions with focus on increasing the forest fuel usage. The analysis included availability and supply cost comparisons between power plant sites and resource allocation in a least cost manner, and between a predefined power plant structure under demand and supply constraints. Spatial analysis of worksite factors and regional geographies were carried out using the GIS-model environment via geoprocessing and cartographic modeling tools. According to the results of analyses, the cost competitiveness of forest fuel supply should be improved in order to achieve the designed objectives in the near future. Availability and supply costs of forest fuels varied spatially and were very sensitive to worksite factors and transport distances. According to the site-specific analysis the supply potential between differentlocations can be multifold. However, due to technical and economical reasons ofthe fuel supply and dense power plant infrastructure, the supply potential is limited at plant level. Therefore, the potential and supply cost calculations aredepending on site-specific matters, where regional characteristics of resourcesand infrastructure should be taken into consideration, for example by using a GIS-modeling approach constructed in this study.

Voimalaitoskytkennän lämpö-ja virtaustekninen optimointi teollisuusprosessiin

Diplomityössä on selvitetty UPM-Kymmene-konserniin kuuluvan Voikkaan paperitehtaan höyryvoimalaitoksen liityntärajapintaa paperikoneprosessiin. Selvitys tehtiin, koska nykyinen voimalaitos on suunniteltu korvattavaksi uudella lähivuosina. Työn teoriaosassa tarkastellaan mm. eri voimalaitostyyppejä, prosessivoimalaitoksen säätöjärjestelmiä sekä väliottovastapaineturbiinilta saatavan sähkötehon laskemiseksi tarvittavaa teoriaa. Käytännössä suurin työ on tehty nykyisen tuotantoprosessin voimalaitokselle asettamien vaatimusten selvittämisessä. Tämä on toteutettu tarkastelemalla online-mittauspositioita hyödyntäen laitoksen eri historiatietokantoja. Tulevan voimalaitoksen väliottovastapaineturbiinilta saatavaa sähkötehoa on tarkasteltu vuoden 2000 prosessihöyryn massavirtoihin perustuen. Kirjalliseen työhön on sisällytetty kuvaajat prosessin tärkeimmistä tila-arvoista. Yksityiskohtainen rajapinnan tarkastelu kuvaajineen ja lukuarvoineen on toimitettu diplomityöpaikalle tiedostomuodossa.

Tehdasalueiden liikenneturvallisuutta kehittävä malli

Työn tavoitteena oli antaa tietoa tehdasalueiden turvallisuuteen vaikuttavista tekijöistä ja luoda malli tehdasalueen liikenteen turvallisuuden parantamiseen päätöksenteon tukivälineitä apuna käyttäen. Työ sai alkunsa todellisen turvallisuutta parantavan investoinnin analysointi-tarpeesta. Aluksi työssä perehdytään yleisesti tehdasalueiden turvallisuuteen tarkastelemalla työturvallisuuden, riskienhallinnan ja turvallisuusjohtamisen asemaa, mittaamista ja taloudellisia vaikutuksia yrityksen toiminnalle. Yleiskatsaus tehdasalueiden turvallisuuteen antaa kuvan, millaiseen toimintaympäristöön turvallisuutta parantavaa mallia ollaan kehittämässä. Malli koostuu viidestä vaiheesta, joita voidaan käyttää kokonaisuutena tai toisistaan erillään. Ensin selvitään tutkittavan alueen kulkuväylät ja liikenne sekä mallinnetaan se. Tämän jälkeen kartoitetaan ongelmakohdat ja etsitään sopivia vaihtoehtoja niiden turvallisuuden parantamiseksi. Vaihtoehtoja analysoidaan SWOT-menetelmän avulla. Turvallisuutta parantavien investointien arvioimiseen esitetään muutamia mittareita, joita voidaan käyttää hankintojen arvioimiseen. Viimeisessä vaiheessa tutustutaan päätöksenteon tukisysteemeihin ja esitetään tietokoneavusteinen päätöksentekomenetelmä AHP. Käytännön soveltaminen on esitetty esimerkein mallin eri vaiheiden yhteydessä.Malli on tarkoitettu suunnittelijoiden, johdon ja työsuojelun työkaluksi, jonka avulla voidaan parantaa tehdasympäristön liikenteen tehokkuutta ja turvallisuutta sekä tutustuttaa käyttäjä päätöksentekomenetelmiin.

Functional Genomic Approaches for Deciphering Plant-Virus Interactions

Plant-virus interactions are very complex in nature and lead to disease and symptom formation by causing various physiological, metabolic and developmental changes in the host plants. These interactions are mainly the outcomes of viral hijacking of host components to complete their infection cycles and of host defensive responses to restrict the viral infections. Viral genomes contain only a small number of genes often encoding for multifunctional proteins, and all are essential in establishing a viral infection. Thus, it is important to understand the specific roles of individual viral genes and their contribution to the viral life cycles. Among the most important viral proteins are the suppressors of RNA silencing (VSRs). These proteins function to suppress host defenses mediated by RNA silencing and can also serve in other functions, e.g. in viral movement, transactivation of host genes, virus replication and protein processing. Thus these proteins are likely to have a significant impact on host physiology and metabolism. In the present study, I have examined the plant-virus interactions and the effects of three different VSRs on host physiology and gene expression levels by microarray analysis of transgenic plants that express these VSR genes. I also studied the gene expression changes related to the expression of the whole genome of Tobacco mosaic virus (TMV) in transgenic tobacco plants. Expression of the VSR genes in the transgenic tobacco plants causes significant changes in the gene expression profiles. HC-Pro gene derived from the Potyvirus Y (PVY) causes alteration of 748 and 332 transcripts, AC2 gene derived from the African cassava mosaic virus (ACMV) causes alteration of 1118 and 251transcripts, and P25 gene derived from the Potyvirus X (PVX) causes alterations of 1355 and 64 transcripts in leaves and flowers, respectively. All three VSRs cause similar up-regulation in defense, hormonally regulated and different stress-related genes and down-regulation in the photosynthesis and starch metabolism related genes. They also induce alterations that are specific to each viral VSR. The phenotype and transcriptome alterations of the HC-Pro expressing transgenic plants are similar to those observed in some Potyvirus-infected plants. The plants show increased protein degradation, which may be due to the HC-Pro cysteine endopeptidase and thioredoxin activities. The AC2-expressing transgenic plants show a similar phenotype and gene expression pattern as HC-Pro-expressing plants, but also alter pathways related to jasmonic acid, ethylene and retrograde signaling. In the P25 expressing transgenic plants, high numbers of genes (total of 1355) were up-regulated in the leaves, compared to a very low number of down-regulated genes (total of 5). Despite of strong induction of the transcripts, only mild growth reduction and no other distinct phenotype was observed in these plants. As an example of whole virus interactions with its host, I also studied gene expression changes caused by Tobacco mosaic virus (TMV) in tobacco host in three different conditions, i.e. in transgenic plants that are first resistant to the virus, and then become susceptible to it and in wild type plants naturally infected with this virus. The microarray analysis revealed up and down-regulation of 1362 and 1422 transcripts in the TMV resistant young transgenic plants, and up and down-regulation of a total of 1150 and 1200 transcripts, respectively, in the older plants, after the resistance break. Natural TMV infections in wild type plants caused up-regulation of 550 transcripts and down-regulation of 480 transcripts. 124 up-regulated and 29 down-regulated transcripts were commonly altered between young and old TMV transgenic plants, and only 6 up-regulated and none of the down-regulated transcripts were commonly altered in all three plants. During the resistant stage, the strong down-regulation in translation-related transcripts (total of 750 genes) was observed. Additionally, transcripts related to the hormones, protein degradation and defense pathways, cell division and stress were distinctly altered. All these alterations may contribute to the TMV resistance in the young transgenic plants, and the resistance may also be related to RNA silencing, despite of the low viral abundance and lack of viral siRNAs or TMV methylation activity in the plants.

Biovoimalaitoksen energiatehokkuuden parantaminen ja osakuorma-ajon optimointi

Energiatehokkuus on nykyaikana yksi tärkeimmistä energiataloudellisista tekijöistä voimalaitosten sähköntuotannossa. Varsinkin yhteistuotantolaitoksissa joissa sähkö on lämpöenergian lisänä saatava sivutuote, sähkön tuotannon optimointi voi merkitä laitostalouden ja yrityksen kannalta huomattavia lisätuloja tai -säästöjä. Kaukaan Voima Oy:n biovoimalaitos on vuonna 2009 kaupalliseen käyttöön valmistunut moderni yhteistuotantolaitos, joka sijaitsee Lappeenrannassa UPM Kaukas sellutehtaan tehdasalueella. Voimalaitos tuottaa kaukolämpöä ja sähköä Lappeenrannan kaupungille sekä prosessihöyryä ja sähköä UPM Kaukaan tehtaille. Tämän työn tavoitteena on tarkastella biovoimalaitoksen omakäyttösähkön kulutusta kuukausitasolla verrattuna laitoksella tuotettavan höyryn määrään sekä etsiä voimalaitokselta kohteita, joiden omakäyttösähkön kulutusta voidaan vähentää vaikuttamatta höyryntuotantoon ja näin parantaa laitoksen energiatehokkuutta ja hyötysuhdetta. Työ rajataan käsittelemään voimalaitoksen apulaitteiden ja -järjestelmien omakäyttösähkön kulutusta. Työssä tarkastellaan vuodenaikojen vaihtelun ja kaukolämmön sekä prosessihöyryn tarpeen muutoksen vaikutusta voimalaitoksen ajomalliin sekä höyryntuotannon ja omakäyttösähkön kulutuksen suhteisiin. Työssä esiin nousseiden kohteiden potentiaaliset sähköenergian säästöt ovat noin 2500 MWh vuodessa joka tarkoittaa keskimäärin 3,7 % vähennystä voimalaitoksen kuukausittaiseen omakäyttösähkön kulutukseen. Kohteet eivät käytännössä vaadi minkaanlaista investointirahaa, vaan uusia ajojärjestelyitä. Keskeisimmiksi säästökohteiksi valikoitui laitoksen pumppausjärjestelmien paineenalennukset.

Urbaania energiaa. Suvilahden, Hanasaaren A- ja Vuosaaren voimalaitokset osana helsinkiläistä kaupunkiympäristöä

Tutkimus koostuu kolmen Helsingissä sijaitsevan, kolmena eri aikakautena, 1910-, 1950- ja 1990-luvuilla, rakennetun voimalaitoksen arkkitehtuurista ja rakennustyypistä sekä niiden eroista ja erityisyyksistä samoin kuin näiden voimalaitosten roolista ja vaikutuksesta Helsingin kaupunkisuunnitteluun ja -rakentamiseen, kaupunkikuvaan sekä ympäristöestetiikkaan. Tutkimus on rajattu koskemaan erityyppisten voimalaitosten osalta yksinomaan kolmea helsinkiläistä kaupungissa sijaitsevaa voimalaitosta, Suvilahtea, Hanasaari-A:ta ja Vuosaaren A- ja B-laitoksia. Tutkimuksen tarkoituksena on ensinnäkin selvittää sekä periaatteessa että edellä mainittujen kolmen esimerkkikohteen kautta seikkoja, jotka ovat vaikuttaneet kunkin voimalaitoksen arkkitehtuuriin ja rakennustyyppiin kunakin aikakautena. Kaupunkivoimalan olennaiset elementit ovat korkea savupiippu, mittava polttoainevarasto sekä massiiviset rakennusmassat, jotka vaativat runsasta maankäyttöä. Toiseksi tutkimuksessa paneudutaan kaupunkisuunnitteluun laitoksen sijoittumisen osalta sekä ajallisesti että paikallisesti. Kolmanneksi selvitetään kaupunkikuvallisia ja ympäristöesteettisiä seikkoja, sekä niiden vaikutusten kehitystä voimalaitoksen toteutuksen ja nykyhetken kesken. Tutkimuksessa haetaan vastausta kysymykseen, miten Helsingissä sijaitseva voimalaitos arkkitehtuuriltaan, rakennustyypiltään ja sijoitukseltaan on soveltunut ja jatkossa soveltuu kaupunkisuunnittelun kannalta kaupunkikuvallisesti sekä ympäristöesteettisesti kyseiseen kaupunkiympäristöön. Tutkimus selvittää myös sitä ilmeistä ristiriitaa, joka syntyy kaupungin kehittyessä ja laajentuessa, jolloin voimalaitos infrastruktuurinsa ja useimmiten suunnattoman kokonsa vuoksi edustaa pysyvyyttä rakentuvan alueen sisällä. Tässä yhteydessä tutkimuksessa pohditaan esimerkkikohteiden avulla voimalaitoksen säilyttämistä puoltavia rakennustaiteellisia arvoja, mahdollista korvattavuutta, ja siinä yhteydessä haetaan vastauksia jäljelle jäävälle laitosrakennukselle kaupunkisuunnittelun kannalta asetettavista uusiokäytön vaatimuksista ja mahdollisuuksista. Tutkimuksen metodologia on sekä kvantitatiivisesti että kvalitatiivisesti historiallinen, esimerkkikohteita käsiteltäessä tarvittavassa määrin myös mikrohistoriallinen.

Growth, crown structure and seed production of birch seedlings, grafts and micropropagated plants

Summary