A recent change in size distribution of blue mussels (Mytilus edulis) in the western part of the Gulf of Finland

Markus Öst & Mikael Kilpi

Virtuaalilähiöstä draaman näyttämöksi. The Sims visuaalisena ja kerronnallisena työkaluna

Tutkimuksen tarkoituksena oli tarkastella ilmiötä, jossa digitaalista peliä ei enää vain pelata, vaan sitä käytetään uusilla innovatiivisilla tavoilla kirjallisten ja visuaalisten tuotosten tekemiseen. Tarkastelun pääkohteena vuonna 2004 julkaistu peli The Sims 2, mutta tutkimus on sovellettavissa myös pelisarjan muihin osiin. Tutkimuksessa tartuttiin yhteen tiettyyn luovan adaptaation muotoon, joista peliyhteisöissä käytetään nimitystä Sims-tarinat. Nämä ovat pelaajien tekemiä narratiivisia ja graafisia esityksiä, joiden toteuttamiseksi peli sovelletaan työkaluksi ja käytetään visuaalisena alustana. Ilmiö on lähtenyt yhteisön tavasta jakaa pelitilaansa kuvakaappausten kautta. Tutkimuksessa tarkasteltiin erityisesti, millaisia nämä tuotokset ovat, miksi niitä tehdään ja millaisessa yhteydessä ne ovat itse pelaamiseen. Aineistona käytettiin ensisijaisesti havainnointia ja verkkokyselyä. Tutkimuksen metodina oli laadullinen sisällönanalyysi, jonka kautta muodostettiin erilaisia tyypittelyjä ilmiöstä. Tarkasteltavana olivat pääasiallisesti sivustot Mod The Sims sekä Livejournalin Sims storytellers, joissa havainnointia toteutettiin satunnaisotannalla. Samoilla sivustoilla julkaistiin myös verkkokysely. Tarinoissa yhdistyy pelistä otetut kuvakaappaukset sekä teksti. Niiden draamallinen sisältö on vaihteleva ja voi käsitellä kaikkia yleisesti tunnettuja kerronnan genrejä. Tarinat voivat olla kiinteä osa itse pelaamista tai siitä irrallisempia. Joillekin peli on yksinomaan alusta, jolla toteuttaa tarinoita, mutta useimmille ne esiintyvät myös pelikokemusta rikastavana ja muokkaavana harrastuksena. Niissä lavastetaan usein tilanteita, jotka eivät itse pelatessa ole mahdollisia, jolloin myös peli saa uusia merkityksiä pelimaailman ulkopuolelta. Tarinat vaikuttavat peliin ja pelin kulku vaikuttaa tarinoihin. Ne ovat esimerkki emergentistä pelattavuudesta ja kuluttajien tavasta muokata kulttuurituotteet omiin tarpeisiin soveltuvaksi, mikä luo uusia pelaamisen muotoja. Sims-tarinoita kirjoittavat etupäässä aikuiset naiset, jotka ovat halunneet yhdistää mieluisat harrastukset. He arvottivat tarinoita pääosin samoin perustein kuin muitakin kirjallisia tuotoksia, mutta uusia elementtejä olivat niiden visuaalisuus ja yhteisöllisyys. Useimmiten motivaatio harrastukseen lähti peliyhteisön esimerkistä. Toinen yleinen teema oli se, kuinka pelaajat pelatessaan alkoivat automaattisesti luoda omaa narratiivisuutta ja kokivat tarvetta tuoda nämä ideat konkreettisen tarinan muotoon, jonka jakaa yhteisössä. Tutkimus osoitti, että pelit sallivat harrastajien toimia omaehtoisina kulttuurintuottajina ja synnyttää uusia innovatiivisia pelaamisen muotoja. Jatkotutkimuksessa on huomionarvoista kuinka nykypäivän mediakulutus ja -tuotanto integroituvat yhä tiiviimmin toisiinsa. Näiden uusien ilmiöiden tutkimus on siten tärkeää ja edellyttää moninäkökulmaista tutkimusotetta.

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

The Sottunga-Jurmo shear zone : structure and deformation history of a crustal-scale ductile shear zone in SW Finland

The aim of this study is to gain a better understanding of the structure and the deformation history of a NW-SE trending regional, crustal-scale shear structure in the Åland archipelago, SW Finland, called the Sottunga-Jurmo shear zone (SJSZ). Approaches involving e.g. structural geology, geochronology, geochemistry and metamorphic petrology were utilised in order to reconstruct the overall deformation history of the study area. The study therefore describes several features of the shear zone including structures, kinematics and lithologies within the study area, the ages of the different deformation phases (ductile to brittle) within the shear zone, as well as some geothermobarometric results. The results indicate that the SJSZ outlines a major crustal discontinuity between the extensively migmatized rocks NE of the shear zone and the unmigmatised, amphibolite facies rocks SW of the zone. The main SJSZ shows overall dextral lateral kinematics with a SW-side up vertical component and deformation partitioning into pure shear and simple shear dominated deformation styles that was intensified toward later stages of the deformation history. The deformation partitioning resulted in complex folding and refolding against the SW margin of the SJSZ, including conical and sheath folds, and in a formation of several minor strike-slip shear zones both parallel and conjugate to the main SJSZ in order to accommodate the regional transpressive stresses. Different deformation phases within the study area were dated by SIMS (zircon U-Pb), ID-TIMS (titanite U-Pb) and 40Ar/39Ar (pseudotachylyte wholerock) methods. The first deformation phase within the ca. 1.88 Ga rocks of the study area is dated at ca. 1.85 Ga, and the shear zone was reactivated twice within the ductile regime (at ca. 1.83 Ga and 1.79 Ga), during which the strain was successively increasingly partitioned into the main SJSZ and the minor shear zones. The age determinations suggest that the orogenic processes within the study area did not occur in a temporal continuum; instead, the metamorphic zircon rims and titanites show distinct, 10-20 Ma long breaks in deformation between phases of active deformation. The results of this study further imply slow cooling of the rocks through 600-700ºC so that at 1.79 Ga, 2 the temperature was still at least 600ºC. The highest recorded metamorphic pressures are 6.4-7.1 kbar. At the late stages or soon after the last ductile phase (ca. 1.79 Ga), relatively high-T mylonites and ultramylonites were formed, witnessing extreme deformation partitioning and high strain rates. After the rocks reached lower amphibolite facies to amphibolite-greenschist facies transitional conditions (ca. 500-550ºC), they cooled rapidly, probably due to crustal uplift and exhumation. The shear zone was reactivated at least once within the semi-brittle to brittle regime between ca. 1.79 Ga and 1.58 Ga, as evidenced by cataclasites and pseudotachylytes. In summary, the results of this study suggest that the Sottunga-Jurmo shear zone (and the South Finland shear zone) defines a major crustal discontinuity, and played a central role in accommodating the regional stresses during and after the Svecofennian orogeny.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

The Sottunga-Jurmo shear zone : structure and deformation history of a crustal-scale ductile shear zone in SW Finland

The aim of this study is to gain a better understanding of the structure and the deformation history of a NW-SE trending regional, crustal-scale shear structure in the Åland archipelago, SW Finland, called the Sottunga-Jurmo shear zone (SJSZ). Approaches involving e.g. structural geology, geochronology, geochemistry and metamorphic petrology were utilised in order to reconstruct the overall deformation history of the study area. The study therefore describes several features of the shear zone including structures, kinematics and lithologies within the study area, the ages of the different deformation phases (ductile to brittle) within the shear zone, as well as some geothermobarometric results. The results indicate that the SJSZ outlines a major crustal discontinuity between the extensively migmatized rocks NE of the shear zone and the unmigmatised, amphibolite facies rocks SW of the zone. The main SJSZ shows overall dextral lateral kinematics with a SW-side up vertical component and deformation partitioning into pure shear and simple shear dominated deformation styles that was intensified toward later stages of the deformation history. The deformation partitioning resulted in complex folding and refolding against the SW margin of the SJSZ, including conical and sheath folds, and in a formation of several minor strike-slip shear zones both parallel and conjugate to the main SJSZ in order to accommodate the regional transpressive stresses. Different deformation phases within the study area were dated by SIMS (zircon U-Pb), ID-TIMS (titanite U-Pb) and 40Ar/39Ar (pseudotachylyte wholerock) methods. The first deformation phase within the ca. 1.88 Ga rocks of the study area is dated at ca. 1.85 Ga, and the shear zone was reactivated twice within the ductile regime (at ca. 1.83 Ga and 1.79 Ga), during which the strain was successively increasingly partitioned into the main SJSZ and the minor shear zones. The age determinations suggest that the orogenic processes within the study area did not occur in a temporal continuum; instead, the metamorphic zircon rims and titanites show distinct, 10-20 Ma long breaks in deformation between phases of active deformation. The results of this study further imply slow cooling of the rocks through 600-700ºC so that at 1.79 Ga, 2 the temperature was still at least 600ºC. The highest recorded metamorphic pressures are 6.4-7.1 kbar. At the late stages or soon after the last ductile phase (ca. 1.79 Ga), relatively high-T mylonites and ultramylonites were formed, witnessing extreme deformation partitioning and high strain rates. After the rocks reached lower amphibolite facies to amphibolite-greenschist facies transitional conditions (ca. 500-550ºC), they cooled rapidly, probably due to crustal uplift and exhumation. The shear zone was reactivated at least once within the semi-brittle to brittle regime between ca. 1.79 Ga and 1.58 Ga, as evidenced by cataclasites and pseudotachylytes. In summary, the results of this study suggest that the Sottunga-Jurmo shear zone (and the South Finland shear zone) defines a major crustal discontinuity, and played a central role in accommodating the regional stresses during and after the Svecofennian orogeny.

Undervattensmiljön i norra Östersjön : Viktigt att tänka på vid havsnära planering

Undervattensmiljön i skärgårdarna och de kustnära områdena i norra Östersjön är mångformiga och produktiva. Arternas levnadsmil-jöer styrs bl.a. av bottentyp, exponeringsgrad och ljustillgång. Kunskap och information om undervattensarterna är av stor vikt för en hållbar planering av kust- och havsmiljön. Denna rapport beskriver indelningen av de viktigaste undervattenshabitaten i norra Östersjöns kustvatten samt hur ett naturvärde på dessa miljöer kan uppskattas på basen av de olika ekologiska funktioner som habitatet uppfyller. De mest inflytelserika mänskliga hoten, både små- och storskaliga, som allvarligt kan hota habitatens fortbestånd behandlas också. Habitaten som beskrivs är både av typen hårdbotten och mjukbotten. Hårdbottenssamhällena bildar distinkta bälten från ytan mot bott-nen: trådalgszonen, zonen med stora fleråriga brunalger (Fucus vesiculosus, F. radicans), rödalgszonen och blåmusselzonen (Mytilus edulis/trossulus). Mjukbottensamhällena är uppbyggda kring ålgräs (Zostera marina), andra vattenlevande kärlväxter eller kransalger. En stor del av både de grunda och djupa mjukbottnarna saknar vegetation och samhällena struktureras då av ryggradslösa djur i och på sedi-mentytan. Habitaten har klassificerats och värderats enligt en tvåstegsmodell. Först har habitaten namngivits efter den dominerande arten eller artgruppen som bestämts enligt täckningsgrad. Därefter har varje habitat getts ett värde enligt sin ekologiska betydelse. Naturvärdet är indelat i skalan 1-5. Projektet NANNUT – The Nature and Nurture in the Northern Baltic Sea – har gjort inventeringar av undervattensmiljön på olika håll av kusterna och skärgårdarna i Finland 2010-2011. Målsättningen har varit att utveckla enkla och kostnadseffektiva metoder både för kartering och värdering av undervattenshabitat. Det huvudsakliga undersökningsområdet var förlagt till Raseborgsstad i södra Finland.

Pohjois-Itämeren vedenalainen luonto : Huomioon otettavaa merenläheisten alueiden suunnittelussa

Saaristojen ja rannikkoalueiden vedenalainen luonto pohjoisella Itämerellä on monimuotoista ja tuottavaa. Lajien elinympäristöjen erilaisuutta säätelee mm. pohjan laatu, avoimuus ja valonsaanti. Vedenalaislajiston tuntemus on hyvin tärkeää kestävässä rannikko- ja merialueiden suunnittelussa. Tämä raportti kuvailee tärkeimpien pohjoisen Itämeren rannikkovesien vedenalaiselinympäristöjen jaottelun sekä miten näiden ympäristöjen luontoarvoa voidaan luokitella kyseisen ympäristön ekologisten toimintojen perusteella. Myös elinympäristöjen säilymistä uhkaavat ihmisen aiheuttamat laajat ja pienemmät uhat esitellään raportissa. Kuvaillut elinympäristöt edustavat sekä pehmeän että kovan pohjan vedenalaisluontoa. Kovan pohjan elinympäristöt muodostavat erillisiä vyöhykkeitä mentäessä meren pinnasta pohjaan: rihmalevävyöhyke, monivuotisten, suurien ruskolevien vyöhyke (Fucus vesiculosus, F. radicans), punalevävyöhyke ja sinisimpukkavyöhyke (Mytilus edulis/trossulus). Kuvaillut pehmeän pohjan elinympäristöt rakentuvat meriajokkaan (Zostera marina),muiden vedessä elävien putkilokasvien tai näkinpartaislevien ympärille. Suuressa osassa sekä matalista että syvistä pehmeistä pohjista ei ole ollenkaan kasvillisuutta ja silloin eliöyhteiskunnan muodostaa hienoaineksen päällä ja sisällä elävät selkärangattomat eläimet. Elinympäristöt on luokiteltu ja arvotettu kaksiportaisen mallin mukaan. Ensin elinympäristö on nimetty peittävyyden perusteella vallitsevan lajin tai lajiryhmän mukaan. Tämän jälkeen jokaisella elinympäristölle annettiin arvo sen ekologisen tärkeyden perusteella. Luontoarvot on luokiteltu asteikoilla 1-5. NANNUT-hanke (The Nature and Nurture in the Northern Baltic Sea) on tehnyt vedenalaiskartoituksia eri puolilla Suomen rannikkoa ja saaristossa vuosina 2010 – 2011. Tavoitteena on ollut kehittää yksinkertaisia ja kustannustehokkaita menetelmiä sekä vedenalaisluonnon kartoittamiseen että sen arvottamiseen. Pääasiallinen tutkimus alue sijaitsi Raaseporin kunnan alueella Etelä-Suomessa.

Surface characterization of chemically modified fiber, wood and paper

Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.