Influence of stationary phase and eluent properties on chromatographic separation of carbohydrates

In this thesis, the sorption and elastic properties of the cation-exchange resins were studied to explain the liquid chromatographic separation of carbohydrates. Na+, Ca2+ and La3+ form strong poly(styrene-co-divinylbenzene) (SCE) as well as Na+ and Ca2+ form weak acrylic (WCE) cation-exchange resins at different cross-link densities were treated within this work. The focus was on the effects of water-alcohol mixtures, mostly aqueous ethanol, and that of the carbohydrates. The carbohydrates examined were rhamnose, xylose, glucose, fructose, arabinose, sucrose, xylitol and sorbitol. In addition to linear chromatographic conditions, non-linear conditions more typical for industrial applications were studied. Both experimental and modeling aspectswere covered. The aqueous alcohol sorption on the cation-exchangers were experimentally determined and theoretically calculated. The sorption model includes elastic parameters, which were obtained from sorption data combined with elasticity measurements. As hydrophilic materials cation-exchangers are water selective and shrink when an organic solvent is added. At a certain deswelling degree the elastic resins go through glass transition and become as glass-like material. Theincreasing cross-link level and the valence of the counterion decrease the sorption of solvent components in the water-rich solutions. The cross-linkage or thecounterions have less effect on the water selectivity than the resin type or the used alcohol. The amount of water sorbed is higher in the WCE resin and, moreover, the WCE resin is more water selective than the corresponding SCE resin. Theincreased aliphatic part of lower alcohols tend to increase the water selectivity, i.e. the resins are more water selective in 2-propanol than in ethanol solutions. Both the sorption behavior of carbohydrates and the sorption differences between carbohydrates are considerably affected by the eluent composition and theresin characteristics. The carbohydrate sorption was experimentally examined and modeled. In all cases, sorption and moreover the separation of carbohydrates are dominated by three phenomena: partition, ligand exchange and size exclusion. The sorption of hydrophilic carbohydrates increases when alcohol is added into the eluent or when carbohydrate is able to form coordination complexes with the counterions, especially with multivalent counterions. Decreasing polarity of the eluent enhances the complex stability. Size exclusion effect is more prominent when the resin becomes tighter or carbohydrate size increases. On the other hand,the elution volumes between different sized carbohydrates decreases with the decreasing polarity of the eluent. The chromatographic separation of carbohydrateswas modeled, using rhamnose and xylose as target molecules. The thermodynamic sorption model was successfully implemented in the rate-based column model. The experimental chromatographic data were fitted by using only one adjustable parameter. In addition to the fitted data also simulated data were generated and utilized in explaining the effect of the eluent composition and of the resin characteristics on the carbohydrate separation.

1000 V sähkönjakelujärjestelmän teknistaloudellisen kannattavuuden tarkastelu

Tässä työssä tutkitaan 1000 V pienjännitejakelun taloudellista kannattavuutta. Tutkimus perustuu teoreettiseen tarkasteluun, jossa noudatetaan yleisiä verkostosuunnittelun periaatteita. EU-lainsäädäntö mahdollistaa 1000 V pienjänniteportaan sijoittamisen nykyisen keskijänniteverkon ja pienjänniteverkon väliin lisäten kolmannen jakelujänniteportaan nykyään käytettävien 20 kV ja 0,4 kV väliin. Jakeluverkkojen kehittämiseksi on etsittävä ratkaisu, joka on taloudellinen sekä asiakkaiden että verkonhaltijoiden kannalta. Tällaiset ratkaisut pienentävät verkon käytön kokonaiskustannuksia ja parantavat sähkön laatua. Lisättäessä jakeluverkkoon kolmas jänniteporras, keskijänniteverkon johtopituus lyhenee ja varsinkin lyhyiden haarajohtojen määrä vähenee. Tämä vähentää keskijänniteverkossa esiintyvien keskeytysten määrää ja pienentää keskeytyskustannuksia. Kilovoltin järjestelmä on kannattava korvattaessa sillä osa keskijänniteverkkoa, tai estettäessä perinteisellä järjestelmällä tarvittava muuntopiirin jakaminen. Osana varsinaista pienjänniteverkkoa ei kilovoltinjärjestelmä ole kannattava. Tässä työssä kolmijänniteportaista jakeluverkkoa tutkitaan teoreettisilla verkkosuunnitelmilla, joita tehdään muutamille perusverkkotopologioille. Taloudellista kannattavuutta tutkitaan vertaamalla perinteistä kaksijänniteportaista ja kolmijänniteportaista verkkoratkaisua kustannusten suhteen teknisten reunaehtojen puitteissa. 1000 V pienjännitejakelu vaatii uudenlaisia verkostokomponentteja. Näistä on erityisesti käsitelty 1/0,4 kV pienjännitemuuntajaa. Muuntajasuunnittelun lähtökohtana on 1000 V verkon käyttäminen keskijänniteverkon jatkeena maasta erotettuna verkkona.

Myyttinen nainen johtajana – diskurssianalyysi ”naisjohtajan” kuvan rakentumisesta mediatekstissä

Tutkielman tavoitteena on selvittää, minkälaisista näkökulmista naisesta johtajana kirjoitetaan ja löytyykö mediateksteistä viittauksia myytteihin, arkkityyppeihin tai stereotypioihin. Tutkimusmenetelmänä käytetään diskurssianalyysiä, jonka avulla valittuja tekstejä tutkitaan. Tässä tutkimuksessa media on rajattu käsittämään sanoma- ja aikakauslehdet. Media muokkaa, mallintaa ja uusintaa lukijan käsityksiä naisesta johtajana. Mediatekstissä johtajuus määrittyy miehisen maailmankuvan kautta. Roolijako miehen ja naisen välillä on kirjoituksissa selvä. Naiseen johtajana liitetään sukupuoli, perhe ja yksityiselämä, mies mielletään kirjoituksissa pelkästään johtajaksi. Perheen merkitys naisen johtajakuvassa on hyvin voimakas. Asenteiden ja uskomusten muutostarpeet ovat olemassa, mutta muutokset tapahtuvat hyvin hitaasti. Media ylläpitää ja uusintaa vanhoja arvoja ja asenteita. Myytit, arkkityypit ja stereotypiat vaikuttavat alitajuisesti sosiaalisen todellisuuden rakentumiseen. Ne säilyvät ja vaikuttavat kansantaruissa, mytologioissa ja uskomuksissa, kuten myös mediatekstissä. Medialla voidaan katsoa olevan merkitystä ”naisjohtajan” kuvan rakentumiseen.

Franchisingyrittäjä–valmennus ja franchisingin tila Suomessa

Tutkielman tavoitteena oli selvittää: - Miten franchisingvalmennus eroaa klassisesta yrittäjäkoulutuksesta? - Mitä mieltä franchisingyrittäjä-valmennuksen läpikäyneet ovat valmennuksesta? - Mikä on franchisingin tila Suomessa? Yrittäjyyttä tarkasteltaessa huomiota kiinnitettiin käsitteen määrittämiseen yrittäjätypologioiden, motivaatioteorioiden ja toimintaympäristön kautta. Tutkielmassa selvitettiin myös yrittäjäksi ryhtymiseen vaikuttavia tekijöitä ja Suomen yrittäjyysaktiivisuuden tasoa. Franchisingin osalta määriteltiin eri toimintamuodot ja keskityttiin Business Format Franchising-toimintamalliin. Työssä selvitettiin myös franchisingyrittäjyyden eroja klassiseen yrittäjyyteen ja tarkasteltiin franchisingin tilaa Suomessa. Koulutuksen osalta keskityttiin tarkastelemaan aikuiskoulutusta ja vielä tarkemmin työvoimapoliittista yrittäjäkoulutusta sekä koulutuksen arviointia. Työssä tarkasteltiin myös franchisingyrittäjä-valmennusta ja sen tavoitteet käytiin myös läpi. Empiirinen tutkimus koostui 118:ta franchisingyrittäjä-valmennukseen vuosina 1998–2000 osallistuneesta henkilöstä. Tutkimus suoritettiin postikyselynä. Tutkimusaineistoa analysoitiin SPSS for Windows-tietojenkäsittelyohjelmalla ja tutkimusjoukon kuvailuun käytettiin frekvenssejä, prosenttilukuja ja ristiintaulukointia. Franchisingvalmennus ja klassinen yrittäjäkoulutus erosivat siinä vaiheessa, kun tarkasteltiin franchisingantajan ja – ottajan näkökulmaa. Franchisingyrittäjä-valmennuksessa käsiteltiin hyvinkin tarkasti sekä franchisingantajan, että – ottajan roolit, velvollisuudet ja oikeudet. Franchisingyrittäjä-valmennuksessa ei myöskään käsitelty lainkaan tuotekehitystä ja lanseerausta. Franchisingyrittäjä-valmennus oli suurimmalle osalle koulutuksen läpäisseistä positiivinen kokemus. Yhdeksän kymmenestä oli myös valmiita suosittelemaan valmennusta franchisingyrittäjyydestä kiinnostuneille henkilöille. Suomessa franchisingin kehitys on siirtymässä suvantovaiheesta uuden kasvun vaiheeseen. Uusia franchisingketjuja perustetaan ja vanhat ketjut lisäävät toimipaikkojensa määrää. Jatkossa voidaan odottaa naisyrittäjien määrän lisääntyvän, sillä uusimmat Suomeen perustetut ketjut ovat terveys- ja hoiva-alalla, jotka ovat perinteisesti naisvaltaisia aloja.

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.

Russian mobile telecommunications market: players and trends

Objective of this work was to clarify the competitive situation of Russian mobile telecommunications market: who are the main players, are there many regional operators, what is the possibility of new entrants and how intensive is the competition. In the beginning the history of Russian mobile telecommunications sector is described. In the next chapter environmental factors of the market are examined with the help of PESTEL analysis. After that, players of the market are introduced to ease the following of next chapters. The main theory for this work was industry analysis of five competitive forces by Michael Porter, which is presented before the theory related industry analysis of Russian mobile telecommunications industry. Research for the industry analysis is mainly based on up-to-date articles describing Russian market. As a result of the industry analysis, competitive situation of Russian mobile telecommunications industry and the future prospects are described with the help of factors coming from the PESTEL-analysis. Finally development and future prospects for Russian 3G are reported. As a result of this work, it can be said that Russian mobile telecommunications market is not likely to maintain the growth of previous years, because the market is near saturation. According to passive SIM-cards it has already received saturated. The saturation will also make the market share game between operators more volatile. The market is dominated by three national operators that covered 88% of the income in the first half of 2007. In addition to these three, there are also several regional operators. Structure of the market is likely to consolidate.

Proportionality and Party Success in Europe

This thesis consists of four articles and an introductory section. The main research questions in all the articles are about proportionality and party success in Europe, at European, national or district levels. Proportionality in this thesis denotes the proximity of seat shares parties receive compared to their respective vote shares, after the electoral system’s allocation process. This proportionality can be measured through numerous indices that illustrate either the overall proportionality of an electoral system or a particular election. The correspondence of a single party’s seat shares to its vote shares can also be measured. The overall proportionality is essential in three of the articles (1, 2 and 4), where the system’s performance is studied by means of plots. In article 3, minority party success is measured by advantage-ratios that reveal single party’s winnings or losses in the votes to seat allocation process. The first article asks how proportional are the European parliamentary (EP) electoral systems, how do they compare with results gained from earlier studies and how do the EP electoral systems treat different sized parties. The reasons for different outcomes are looked for in explanations given by traditional electoral studies i.e. electoral system variables. The countries studied (EU15) apply electoral systems that vary in many important aspects, even though a certain amount of uniformity has been aspired to for decades. Since the electoral systems of the EP elections closely resemble the national elections, the same kinds of profiles emerge as in the national elections. The electoral systems indeed treat the parties differentially and six different profile types can be found. The counting method seems to somewhat determine the profile group, but the strongest variables determining the shape of a countries’ profile appears to be the average district magnitude and number of seats allocated to each country. The second article also focuses on overall proportionality performance of an electoral system, but here the focus is on the impact of electoral system changes. I have developed a new method of visualizing some previously used indices and some new indices for this purpose. The aim is to draw a comparable picture of these electoral systems’ changes and their effects. The cases, which illustrate this method, are four elections systems, where a change has occurred in one of the system variables, while the rest remained unchanged. The studied cases include the French, Greek and British European parliamentary systems and the Swedish national parliamentary system. The changed variables are electoral type (plurality changed to PR in the UK), magnitude (France splitting the nationwide district into eight smaller districts), legal threshold (Greece introducing a three percent threshold) and counting method (d’Hondt was changed to modified Sainte-Laguë in Sweden). The radar plots from elections after and before the changes are drawn for all country cases. When quantifying the change, the change in the plots area that is created has also been calculated. Using these radar plots we can observe that the change in electoral system type, magnitude, and also to some extent legal threshold had an effect on overall proportionality and accessibility for small parties, while the change between the two highest averages counting method had none. The third article studies the success minority parties have had in nine electoral systems in European heterogeneous countries. This article aims to add more motivation as to why we should care how different sized parties are treated by the electoral systems. Since many of the parties that aspire to represent minorities in European countries are small, the possibilities for small parties are highlighted. The theory of consociational (or power-sharing) democracy suggests that, in heterogeneous societies, a proportional electoral system will provide the fairest treatment of minority parties. The OSCE Lund Recommendations propose a number of electoral system features, which would improve minority representation. In this article some party variables, namely the unity of the minority parties and the geographical concentration of the minorities were included among possible explanations. The conclusions are that the central points affecting minority success were indeed these non-electoral system variables rather than the electoral system itself. Moreover, the size of the party was a major factor governing success in all the systems investigated; large parties benefited in all the studied electoral systems. In the fourth article the proportionality profiles are again applied, but this time to district level results in Finnish parliamentary elections. The level of proportionality distortion is also studied by way of indices. The average magnitudes during the studied periodrange from 7.5 to 26.2 in the Finnish electoral districts and this opens up unequal opportunities for parties in different districts and affects the shape of the profiles. The intra-country case allows the focus to be placed on the effect of district magnitude, since all other electoral systems are kept constant in an intra-country study. The time span in the study is from 1962 to 2007, i.e. the time that the districts have largely been the same geographically. The plots and indices tell the same story, district magnitude and electoral alliances matter. The district magnitude is connected to the overall proportionality of the electoral districts according to both indices, and the profiles are, as expected, also closer to perfect proportionality in large districts. Alliances have helped some small parties to gain a much higher seat share than their respective vote share and these successes affect some of the profiles. The profiles also show a consistent pattern of benefits for the small parties who ally with the larger parties.

Photoluminescence of GaAs/AlGaAs quantum wells

In this thesis is studied the influence of uniaxial deformation of GaAs/AlGaAs quantum well structures to photoluminescence. Uniaxial deformation was applied along [110] and polarization ratio of photoluminescence at T = 77 K and 300 K was measured. Also the physical origin of photoluminescence lines in spectrum was determined and the energy band splitting value between states of heavy and light holes was estimated. It was found that the dependencies of polarization ratio on uniaxial deformation for bulk GaAs and GaAs/AlGaAs are different. Two observed lines in photoluminescence spectrum are induced by free electron recombination to energy sublevels of valence band corresponding to heavy and light holes. Those sublevels are splited due to the combination of size quantization and external pressure. The quantum splitting energy value was estimated. Also was shown a method, which allows to determine the energy splitting value of sublevels at room temperature and at comparatively low uniaxial deformation, when the other method for determining of the splitting becomes impossible.

Integroitujen laitekaappien tuotannon tehostaminen elektroniikkateollisuudessa

Laitekaappien integrointi koostuu moduulien sekä kaapeleiden liittämisestä mallikohtaisiksi kokonaisuuksiksi. Tämä kokoonpanoprosessi on tilausohjautuva ja tehdään mallikohtaisesti yksittäiskokoonpanona. Mallien integrointityön vaikeus ja kokoonpanoaika vaihtelevat voimakkaasti. Tämä yhdistettynä työvoiman vaihtuvuuteen luo haastavan ympäristön kehittää tuotantoa sekä laadun että kapasiteetin näkökulmasta. Työssä on selvitetty voidaanko näitä kehittää jakamalla tuotantoprosessi pienempiin vaiheisiin, jotka ovat helpompi tasapainottaa ja oppia. Kokoomalinjan soveltaminen tilausohjautuvaan tuotantoon vaatii perinteiseen tahdistettuun kokoomalinjaan nähden suurempien poikkeavuuksien sallimista. Toisistaan merkittävästi poikkeavien työaikojen ja laajan mallivariaation vuoksi linjaa ei pystytä hallitsemaan niin järjestelmällisesti kuin tasapituisilla työvaiheilla. Tehokkaan tuotannon aikaansaaminen tällaiselle linjalle vaatii mahdollisuutta työjärjestyksen suunnitteluun ja sen simulointiin. Tässä työssä on pyritty arvioimaan simuloinnin avulla kokoomalinjan toimivuutta stokastisen kysynnän vallitessa. Malli on luotu hyväksikäyttäen tuotteiden valmistusaikoja, jotka on jaettu mallikohtaisesti kaikkiin mahdollisiin työtehtäviin. Nämä tehtävät on pyritty tasapainottamaan eri työpisteiden tehtäviksi. Tasapainotuksen tavoitteena on ollut minimoida tuotteiden työtehtävien keston voimakasta hajontaa, jota mallien kysynnän satunnaisuus voimistaa. Simulointien perusteella on luotu yksinkertaistettu sääntö työjärjestyksen muodostamiselle. Mallinnuksessa on pyritty maksimoimaan tuotannon tehokkuus minimoiden sekä keskeneräisen tuotannon määrää että läpimenoaikaa. Tehokkaimman vaihtoehdon löydyttyä on arvioitu kokoomalinjan soveltuvuutta laitekaappien integrointiin.

Maritime transportation in the Gulf of Finland in 2007 and in 2015

The Gulf of Finland is said to be one of the densest operated sea areas in the world. It is a shallow and economically vulnerable sea area with dense passenger and cargo traffic of which petroleum transports have a share of over 50 %. The winter conditions add to the risks of maritime traffic in the Gulf of Finland. It is widely believed that the growth of maritime transportation will continue also in the future. The Gulf of Finland is surrounded by three very different national economies with, different maritime transportation structures. Finland is a country of high GDP/per capita with a diversified economic structure. The number of ports is large and the maritime transportation consists of many types of cargoes: raw materials, industrial products, consumer goods, coal and petroleum products, and the Russian transit traffic of e.g. new cars and consumer goods. Russia is a large country with huge growth potential; in recent years, the expansion of petroleum exports has lead to a strong economic growth, which is also apparent in the growth of maritime transports. Russia has been expanding its port activities in the Gulf of Finland and it is officially aiming to transport its own imports and exports through the Russian ports in the future; now they are being transported to great extend through the Finnish, Estonian and other Baltic ports. Russia has five ports in the Gulf of Finland. Estonia has also experienced fast economic growth, but the growth has been slowing down already during the past couples of years. The size of its economy is small compared to Russia, which means the transported tonnes cannot be very massive. However, relatively large amounts of the Russian petroleum exports have been transported through the Estonian ports. The future of the Russian transit traffic in Estonia looks nevertheless uncertain and it remains to be seen how it will develop and if Estonia is able to find replacing cargoes if the Russian transit traffic will come to an end in the Estonian ports. Estonia’s own import and export consists of forestry products, metals or other raw materials and consumer goods. Estonia has many ports on the shores of the Gulf of Finland, but the port of Tallinn dominates the cargo volumes. In 2007, 263 M tonnes of cargoes were transported in the maritime traffic in the Gulf of Finland, of which the share of petroleum products was 56 %. 23 % of the cargoes were loaded or unloaded in the Finnish ports, 60 % in the Russian ports and 17 % in the Estonian ports. The largest ports were Primorsk (74.2 M tonnes) St. Petersburg (59.5 M tonnes), Tallinn (35.9 M tonnes), Sköldvik (19.8 M tonnes), Vysotsk (16.5 M tonnes) and Helsinki (13.4 M) tonnes. Approximately 53 600 ship calls were made in the ports of the Gulf of Finland. The densest traffic was found in the ports of St. Petersburg (14 651 ship calls), Helsinki (11 727 ship calls) and Tallinn (10 614 ship calls) in 2007. The transportation scenarios are usually based on the assumption that the amount of transports follows the development of the economy, although also other factors influence the development of transportation, e.g. government policy, environmental aspects, and social and behavioural trends. The relationship between the development of transportation and the economy is usually analyzed in terms of the development of GDP and trade. When the GDP grows to a certain level, especially the international transports increase because countries of high GDP produce, consume and thus transport more. An effective transportation system is also a precondition for the economic development. In this study, the following factors were taken into consideration when formulating the future scenarios: maritime transportation in the Gulf of Finland 2007, economic development, development of key industries, development of infrastructure and environmental aspects in relation to maritime transportation. The basic starting points for the three alternative scenarios were: • the slow growth scenario: economic recession • the average growth scenario: economy will recover quickly from current instability • the strong growth scenario: the most optimistic views on development will realize According to the slow growth scenario, the total tonnes for the maritime transportation in the Gulf of Finland would be 322.4 M tonnes in 2015, which would mean a growth of 23 % compared to 2007. In the average growth scenario, the total tonnes were estimated to be 431.6 M tonnes – a growth of 64 %, and in the strong growth scenario 507.2 M tonnes – a growth of 93%. These tonnes were further divided into petroleum products and other cargoes by country, into export, import and domestic traffic by country, and between the ports. For petroleum products, the share of crude oil and oil products was estimated and the number of tanker calls in 2015 was calculated for each scenario. However, the future development of maritime transportation in the GoF is dependent on so many societal and economic variables that it is not realistic to predict one exact point estimate value for the cargo tonnes for a certain scenario. Plenty of uncertainty is related both to the degree in which the scenario will come true as well as to the cause-effect relations between the different variables. For these reasons, probability distributions for each scenario were formulated by an expert group. As a result, a range for the total tonnes of each scenario was formulated and they are as follows: the slow growth scenario: 280.8 – 363 M tonnes (expectation value 322.4 M tonnes)

Molluscan radiations and landscape evolution in Miocene Amazonia

This PhD study aims to exploit the rich archive provided by the Miocene mollusc fauna of the Pebas Formation and other inland Miocene Amazonian formations to reconstruct landscape evolution and biotic development in lowland Amazonia during the Neogene. Over 160 samples from more than 70 Pebas Formation outcrops mostly collected by the author were processed for this study. Additional samples were collected in Andean areas of Colombia and Venezuela and further material from other northwestern South American basins was studied in museums. Pebas Formation samples and well log data made available by Occidental Peru from three wells in the Marañon Basin in Peru were also investigated. During this study four genera and 74 species from the Pebas Formation have been described and a further 13 species have been introduced in open nomenclature, and several species were reported for the first time. The number of mollusc species attributed to the Pebas fauna has increased from around 50 to 156. The Pebas fauna is characterised as aquatic, endemic and extinct, and is a typical representative of a long-lived lake fauna. Fluvial taxa are not common, (marginal) marine taxa are rare. An additional molluscan fauna from the Miocene Solimões Formation of Brazil, containing 13 fresh water species was also described. The newly documented fauna was used to improve biostratigraphic framework of Miocene Amazonian deposits. Twelve mollusc zones were introduced, the upper eleven of which cover a time interval of approximately seven million years covered previously by only three pollen zones. An age model calculated for the borehole data indicates that the Pebas Formation was deposited between c. 24 and 11 Ma. The areal distribution of the outcropping mollusc zones uncovered a broad dome structure, termed here the Iquitos-Araracuara anteclise in the study area. The structure appears to have influenced river courses and also contributed to edaphic heterogeneity that may have been in part responsible for the current high biodiversity in the study area. The Pebas system was a huge system (> one million km2) dominated by relatively shallow lakes, but also containing swamps and rivers. The system was fed by rivers draining the emergent Andes in the west and lowlands and cratons to the east. The Pebas system was located at sea level and was open to marine settings through a northern portal running through the Llanos Basin and East Venezuela Basin towards the Caribbean. Cyclical baselevel changes possibly related to Mylankhovitch cycles, have been documented in depositional sequences of the Pebas Formation. The composition of the Pebasian mollusc fauna implies that the system was mostly a fresh water system. Such an interpretation is matched by strontium isotope ratios as well as very negative δ18O ratios found in the shells, but is at odds with oligohaline and mesohaline ichnofacies found in the same strata. The mollusc fauna of the Pebas Formation diversified through most of the existence of the lake system. The diversification was mostly the result of in-situ cladogenesis. The success of some of the Pebasian endemic clades is explained by adaptation to fresh water, low oxygen, common unconsolidated lake bottoms (soup grounds) as well as high predation intensity. Maximum diversity was reached at the base of the late Middle to early Late Miocene Grimsdalea pollen zone, some 13 Ma. At the time some 85 species co-occurred, 67 of which are considered as Pebasian endemics. A subsequent drop in species richness coincides with indications of elevated salinities, although a causal relation still needs to be established. Apparently the Pebas fauna went (almost) entirely extinct with the replacement of the lake system into a fluvio-tidal system during the Early Late Miocene, some 11 Ma.

Evolutionary Ecology of Mountain Birch in Subarctic Stress Gradients: Interplay of Biotic and Abiotic Factors in Plant-Plant Interactions and Evolutionary Processes

In nature, variation for example in herbivory, wind exposure, moisture and pollution impact often creates variation in physiological stress and plant productivity. This variation is seldom clear-cut, but rather results in clines of decreasing growth and productivity towards the high-stress end. These clines of unidirectionally changing stress are generally known as ‘stress gradients’. Through its effect on plant performance, stress has the capacity to fundamentally alter the ecological relationships between individuals, and through variation in survival and reproduction it also causes evolutionary change, i.e. local adaptations to stress and eventually speciation. In certain conditions local adaptations to environmental stress have been documented in a matter of just a few generations. In plant-plant interactions, intensities of both negative interactions (competition) and positive ones (facilitation) are expected to vary along stress gradients. The stress-gradient hypothesis (SGH) suggests that net facilitation will be strongest in conditions of high biotic and abiotic stress, while a more recent ‘humpback’ model predicts strongest net facilitation at intermediate levels of stress. Plant interactions on stress gradients, however, are affected by a multitude of confounding factors, making studies of facilitation-related theories challenging. Among these factors are plant ontogeny, spatial scale, and local adaptation to stress. The last of these has very rarely been included in facilitation studies, despite the potential co-occurrence of local adaptations and changes in net facilitation in stress gradients. Current theory would predict both competitive effects and facilitative responses to be weakest in populations locally adapted to withstand high abiotic stress. This thesis is based on six experiments, conducted both in greenhouses and in the field in Russia, Norway and Finland, with mountain birch (Betula pubescens subsp. czerepanovii) as the model species. The aims were to study potential local adaptations in multiple stress gradients (both natural and anthropogenic), changes in plant-plant interactions under conditions of varying stress (as predicted by SGH), potential mechanisms behind intraspecific facilitation, and factors confounding plant-plant facilitation, such as spatiotemporal, ontogenetic, and genetic differences. I found rapid evolutionary adaptations (occurring within a time-span of 60 to 70 years) towards heavy-metal resistance around two copper-nickel smelters, a phenomenon that has resulted in a trade-off of decreased performance in pristine conditions. Heavy-metal-adapted individuals had lowered nickel uptake, indicating a possible mechanism behind the detected resistance. Seedlings adapted to heavy-metal toxicity were not co-resistant to others forms of abiotic stress, but showed co-resistance to biotic stress by being consumed to a lesser extent by insect herbivores. Conversely, populations from conditions of high natural stress (wind, drought etc.) showed no local adaptations, despite much longer evolutionary time scales. Due to decreasing emissions, I was unable to test SGH in the pollution gradients. In natural stress gradients, however, plant performance was in accordance with SGH, with the strongest host-seedling facilitation found at the high-stress sites in two different stress gradients. Factors confounding this pattern included (1) plant size / ontogenetic status, with seedling-seedling interactions being competition dominated and host-seedling interactions potentially switching towards competition with seedling growth, and (2) spatial distance, with competition dominating at very short planting distances, and facilitation being strongest at a distance of circa ¼ benefactor height. I found no evidence for changes in facilitation with respect to the evolutionary histories of plant populations. Despite the support for SGH, it may be that the ‘humpback’ model is more relevant when the main stressor is resource-related, while what I studied were the effects of ‘non-resource’ stressors (i.e. heavy-metal pollution and wind). The results have potential practical applications: the utilisation of locally adapted seedlings and plant facilitation may increase the success of future restoration efforts in industrial barrens as well as in other wind-exposed sites. The findings also have implications with regard to the effects of global change in subarctic environments: the documented potential by mountain birch for rapid evolutionary change, together with the general lack of evolutionary ‘dead ends’, due to not (over)specialising to current natural conditions, increase the chances of this crucial forest-forming tree persisting even under the anticipated climate change.

Research of wood fuel market in North-West of Russia

The main purposes of this study are analyzing of forest sector of North-West and research of potentials of wood fuel market in this region. Research is focused on definition of the most perspective areas for export of wood fuel: logging residues, industrial wood processing residues, pellets and briquettes. Russian wood energy industry is very young in comparison with European countries. Nowadays there are no support and serious attention from the government to this sector. Hence almost all wood fuel market is oriented to the Western Europe. Export of wood fuel is dominated over the internal consumption. Pellet production in North –West is rapidly growing. Despite internal market has been developed the lion's share of pellets goes to export. Part of industrial wood processing residues is used by producers for their own goals, part goes to the export and rest of them is not used at all. Logging residues as raw materials for fuel have great potentials; most of them are left in a forest. Special techniques for their processing are too expensive for Russian entrepreneur. Some parts of North –West, which are situated close to the border with European countries, are potential for export. Political, economical and logistical challenges are complicated facilities for foreign customer to purchase wood fuel in remote parts of North-West. However some decisions for solving this problem exist and Russian manufactures are still interested in export of their products.

NMR in Crystals and Powders of Topazes with Different Colours

The present work is a part of the large project with purpose to investigate microstructure and electronic structure of natural topazes using NMR method. To reach this task we determined the relative contents of fluorine and hydrogen in crystals blue, colorless, wine and wine irradiated topazes. Then we determined the electric field gradients in site of aluminium atoms by NMR method, calculated EFG using ab initio method, and measured relaxation time dependence on heating temperature for blue, colorless, Swiss blue and sky blue topazes. Nuclear magnetic resonance (NMR) is an effective method to investigate the local structure in the crystal. The NMR study of the single crystal gives detailed information especially about the local crystal structure. As a result of this work we have received practical data, which is possible to use in future for making personal dosimetry and for preparation of mullite, which is widely used in traditional and advanced ceramic materials.

Thylakoid Protein Phosphorylation in Regulation of Photosynthesis

Once the seed has germinated, the plant is forced to face all the environmental changes in its habitat. In order to survive, plants have evolved a number of different acclimation systems. The primary reaction behind plant growth and development is photosynthesis. Photosynthesis captures solar energy and converts it into chemical form. Photosynthesis in turn functions under the control of environmental cues, but is also affected by the growth, development, and metabolic state of a plant. The availability of solar energy fluctuates continuously, requiring non-stop adjustment of photosynthetic efficiency in order to maintain the balance between photosynthesis and the requirements and restrictions of plant metabolism. Tight regulation is required, not only to provide sufficient energy supply but also to prevent the damage caused by excess energy. The very first reaction of photosynthesis is splitting of water into the form of oxygen, hydrogen, and electrons. This most fundamental reaction of life is run by photosystem II (PSII), and the energy required for the reaction is collected by the light harvesting complex II (LHCII). Several proteins of the PSII-LHCII complex are reversibly phosphorylated according to the energy balance between photosynthesis and metabolism. Thylakoid protein phosphorylation has been under extensive investigation for over 30 years, yet the physiological role of phosphorylation remains elusive. Recently, the kinases behind the phosphorylation of PSII-LHCII proteins (STN7 and STN8) were identified and the knockout mutants of these kinases became available, providing powerful tools to elucidate the physiological role of PSII-LHCII phosphorylation. In my work I have used the stn7 and stn8 mutants in order to clarify the role of PSII-LHCII phosphorylation in regulation and protection of the photosynthetic machinery according to environmental cues. I show that STN7- dependent PSII-LHCII protein phosphorylation is required to balance the excitation energy distribution between PSII and PSI especially under low light intensities when the excitation energy transfer from LHC to PSII and PSI is efficient. This mechanism differs from traditional light quality-induced “state 1” – “state 2” transition and ensures fluent electron transfer from PSII to PSI under low light, yet having highest physiological relevance under fluctuating light intensity. STN8-dependent phosphorylation of PSII proteins, in turn, is required for fluent turn-over of photodamaged PSII complexes and has the highest importance upon prolonged exposure of the photosynthetic apparatus to excess light.