Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

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.

Pasvik Water Quality Report Environmental Monitoring Programme in the Norwegian, Finnish and Russian Border Area

The Pasvik monitoring programme was created in 2006 as a result of the trilateral cooperation, and with the intention of following changes in the environment under variable pollution levels. Water quality is one of the basic elements of the Programme when assessing the effects of the emissions from the Pechenganikel mining and metallurgical industry (Kola GMK). The Metallurgic Production Renovation Programme was implemented by OJSC Kola GMK to reduce emissions of sulphur and heavy metal concentrated dust. However, the expectations for the reduction in emissions from the smelter in the settlement Nikel were not realized. Nevertheless, Kola GMK has found that the modernization programme’s measures do not provide the planned reductions of sulfur dioxide emissions. In this report, temporal trends in water chemistry during 2000–2009 are examined on the basis of the data gathered from Lake Inari, River Pasvik and directly connected lakes, as well as from 26 small lakes in three areas: Pechenganikel (Russia), Jarfjord (Norway) and Vätsäri (Finland). The lower parts of the Pasvik watercourse are impacted by both atmospheric pollution and direct wastewater discharge from the Pechenganikel smelter and the settlement of Nikel. The upper section of the watercourse, and the small lakes and streams which are not directly linked to the Pasvik watercourse, only receive atmospheric pollution. The data obtained confirms the ongoing pollution of the river and water system. Copper (Cu), nickel (Ni) and sulphates are the main pollution components. The highest levels were observed close to the smelters. The most polluted water source of the basin is the River Kolosjoki, as it directly receives the sewage discharge from the smelters and the stream connecting the Lakes Salmijarvi and Kuetsjarvi. The concentrations of metals and sulphates in the River Pasvik are higher downstream from the Kuetsjarvi Lake. There has been no fall in the concentrations of pollutants in Pasvik watercourse over the last 10 years. Ongoing recovery from acidification has been evident in the small lakes of the Jarfjord and Vätsäri areas during the 2000s. The buffering capacity of these lakes has improved and the pH has increased. The reason for this recovery is that sulphate deposition has decreased, which is also evident in the water quality. However, concentrations of some metals, especially Ni and Cu, have risen during the 2000s. Ni concentrations have increased in all three areas, and Cu concentrations in the Pechenganickel and Jarfjord areas, which are located closer to the smelters. Emission levels of Ni and Cu did not fall during 2000s. In fact, the emission levels of Ni compounds even increased compared to the 1990s.

Pasvik Water Quality until 2013 ; Environmental Monitoring Programme in the Norwegian, Finnish and Russian Border Area

The Pasvik monitoring programme was created in 2006 as a result of the trilateral cooperation and with the intention of following changes in the environment under variable pollution levels. Water quality is one of the basic elements of the programme when assessing the effects of the emissions from the Pechenganikel mining end metallurgical industry (Kola GMK). In this report temporal trends of the water chemistry during 2000–2013 are examined on the basis of the data gathered from lake Inari, River Pasvik and directly connected lakes, Lake Kuetsjarvi and 25 small lakes in three areas: Pechenganikel (Russia), Jarfjord (Norway) and Vätsäri (Finland). The lower parts of the Pasvik watercourse are impacted by both atmospheric pollution and direct wastewater discharge from the Pechenganikel smelter and the settlement of Nikel. The upper section of the watercourse and the small lakes and streams which are not directly linked to the Pasvik Watercourse only receive atmospheric pollution. Lake Inari is free of direct emissions from the Pechenganikel and the water quality is excellent. In River Pasvik and the directly connected lakes copper, nickel, and sulphates are the main pollutants. The most polluted water body is the Kolosjoki River as well as the stream connecting the Lakes Salmijarvi and Kuetsjarvi. The concentration of metals and sulphates in the water notably increases downstream the river lower Lake Kuetsjarvi. In Lake Kuetsjarvi copper and nickel concentrations are clearly elevated and have changed insignificantly in the last years of the research period. In the small border area lakes recovery from acidification in Vätsäri and Jarfjord is evident. Nickel and copper oncentrations have fluctuated but remained on clearly elevated level in Jarfjord and Pechenga. Copper concentrations have been slightly rising in the recent years. In Pechenga area nickel concentrations during the last four monitoring years are decreasing in some places but the regional trend through whole time series is still positive.

Fluvio-morphological processes of meander bends - Combining conventional field measurements, close-range remote sensing and computational modelling

Meandering rivers have been perceived to evolve rather similarly around the world independently of the location or size of the river. Despite the many consistent processes and characteristics they have also been noted to show complex and unique sets of fluviomorphological processes in which local factors play important role. These complex interactions of flow and morphology affect notably the development of the river. Comprehensive and fundamental field, flume and theoretically based studies of fluviomorphological processes in meandering rivers have been carried out especially during the latter part of the 20th century. However, as these studies have been carried out with traditional field measurements techniques their spatial and temporal resolution is not competitive to the level achievable today. The hypothesis of this study is that, by exploiting e increased spatial and temporal resolution of the data, achieved by combining conventional field measurements with a range of modern technologies, will provide new insights to the spatial patterns of the flow-sediment interaction in meandering streams, which have perceived to show notable variation in space and time. This thesis shows how the modern technologies can be combined to derive very high spatial and temporal resolution data on fluvio-morphological processes over meander bends. The flow structure over the bends is recorded in situ using acoustic Doppler current profiler (ADCP) and the spatial and temporal resolution of the flow data is enhanced using 2D and 3D CFD over various meander bends. The CFD are also exploited to simulate sediment transport. Multi-temporal terrestrial laser scanning (TLS), mobile laser scanning (MLS) and echo sounding data are used to measure the flow-based changes and formations over meander bends and to build the computational models. The spatial patterns of erosion and deposition over meander bends are analysed relative to the measured and modelled flow field and sediment transport. The results are compared with the classic theories of the processes in meander bends. Mainly, the results of this study follow well the existing theories and results of previous studies. However, some new insights regarding to the spatial and temporal patterns of the flow-sediment interaction in a natural sand-bed meander bend are provided. The results of this study show the advantages of the rapid and detailed measurements techniques and the achieved spatial and temporal resolution provided by CFD, unachievable with field measurements. The thesis also discusses the limitations which remain in the measurement and modelling methods and in understanding of fluvial geomorphology of meander bends. Further, the hydro- and morphodynamic models’ sensitivity to user-defined parameters is tested, and the modelling results are assessed against detailed field measurement. The study is implemented in the meandering sub-Arctic Pulmanki River in Finland. The river is unregulated and sand-bed and major morphological changes occur annually on the meander point bars, which are inundated only during the snow-melt-induced spring floods. The outcome of this study applies to sandbed meandering rivers in regions where normally one significant flood event occurs annually, such as Arctic areas with snow-melt induced spring floods, and where the point bars of the meander bends are inundated only during the flood events.

Environmental Challenges in the Joint Border Area of Norway, Finland and Russia

This report examines the human impact on the subarctic environment of the joint border area of Norway, Finland and Russia. The aim is to present the current state and recent changes that have taken place in the region. The main threat to the environment is the Pechenganikel mining and metallurgical industrial combine in the towns of Nikel and Zapolyarny in the Kola Peninsula. Emissions from this complex include high levels of heavy metals, persistent organic pollutants and sulfur dioxide. Pollution, along with climate change, water level regulation and other anthropogenic effects, has affected the aquatic ecosystems in the joint border area. The main heavy metals in the area are copper and nickel, the highest concentrations of which are measured near the combine. Direct discharge of sewage into the river continues and airborne heavy metal particles are also deposited to areas farther away. Climate changeinduced increase in temperature and precipitation in the Kola Peninsula is evident. Water level regulation with seven hydropower plants in the Pasvik River have changed it into a series of lakes and lake-like reservoirs. This report discusses modelling, which was enabled to estimate the effect of climate change on Lake Inarijärvi and the Pasvik River hydrology, water level fluctuation and ecology and to follow the sulfur dioxide emissions emitted from the Pechenganikel. Effects of pollution on the nature and concentrations of the main pollutants were studied and climate change in the border area and its effects on the ecology were estimated. Also the effects of water level regulation on the ecological status of the aquatic ecosystems were addressed.

Sähkön markkinahintaa selittävät tekijät. Case: Nord Pool 2000-2005

Sähkön markkinahinta on saanut osakseen suurta huomiota viimeaikoina. Sähkömarkkinoiden vapautuminen ja päästökaupan avaaminen Euroopassa onentisestään nostanut sähkömarkkinoita näkyville lehdissä. Tämä tutkielma tutkii erilaisten tekijöiden vaikutusta sähkön markkinahintaan regressioanalyysin avulla. Edellä mainitun päästösopimusten markkinahinnan lisäksi tutkittiin kivihiilen sekä maakaasun markkinahintojen, lämpötilojen, jokien virtaamien, vesivarantojen täyttöasteiden sekä Saksan sähkömarkkinoiden hinnan vaikutusta sähkön markkinahintaan Nord Pool -sähköpörssissä. Työssä luotiin myös sähkön markkinahintaa ennustava malli. Kaikkien selittävien tekijöiden korrelaatiot olivat oletusten mukaiset ja regressioanalyysi onnistui selittämään yli 80 % sähkön markkinahinnan vaih-teluista. Merkittävimpiä selittäviä tekijöitä olivat vesivarannot sekä jokien virtaamat. Ennustavan mallin keskimääräinen suhteellinen virhe oli noin 10 %, joten ennustetarkkuus oli melko hyvä.

Remote sensing for three-dimensional modelling of hydromorphology

Successful management of rivers requires an understanding of the fluvial processes that govern them. This, in turn cannot be achieved without a means of quantifying their geomorphology and hydrology and the spatio-temporal interactions between them, that is, their hydromorphology. For a long time, it has been laborious and time-consuming to measure river topography, especially in the submerged part of the channel. The measurement of the flow field has been challenging as well, and hence, such measurements have long been sparse in natural environments. Technological advancements in the field of remote sensing in the recent years have opened up new possibilities for capturing synoptic information on river environments. This thesis presents new developments in fluvial remote sensing of both topography and water flow. A set of close-range remote sensing methods is employed to eventually construct a high-resolution unified empirical hydromorphological model, that is, river channel and floodplain topography and three-dimensional areal flow field. Empirical as well as hydraulic theory-based optical remote sensing methods are tested and evaluated using normal colour aerial photographs and sonar calibration and reference measurements on a rocky-bed sub-Arctic river. The empirical optical bathymetry model is developed further by the introduction of a deep-water radiance parameter estimation algorithm that extends the field of application of the model to shallow streams. The effect of this parameter on the model is also assessed in a study of a sandy-bed sub-Arctic river using close-range high-resolution aerial photography, presenting one of the first examples of fluvial bathymetry modelling from unmanned aerial vehicles (UAV). Further close-range remote sensing methods are added to complete the topography integrating the river bed with the floodplain to create a seamless high-resolution topography. Boat- cart- and backpack-based mobile laser scanning (MLS) are used to measure the topography of the dry part of the channel at a high resolution and accuracy. Multitemporal MLS is evaluated along with UAV-based photogrammetry against terrestrial laser scanning reference data and merged with UAV-based bathymetry to create a two-year series of seamless digital terrain models. These allow the evaluation of the methodology for conducting high-resolution change analysis of the entire channel. The remote sensing based model of hydromorphology is completed by a new methodology for mapping the flow field in 3D. An acoustic Doppler current profiler (ADCP) is deployed on a remote-controlled boat with a survey-grade global navigation satellite system (GNSS) receiver, allowing the positioning of the areally sampled 3D flow vectors in 3D space as a point cloud and its interpolation into a 3D matrix allows a quantitative volumetric flow analysis. Multitemporal areal 3D flow field data show the evolution of the flow field during a snow-melt flood event. The combination of the underwater and dry topography with the flow field yields a compete model of river hydromorphology at the reach scale.

Effects of anthropogenic and natural hydrological changes on the behavior of the acidic metal discharge from acid sulfate soils in a river- and lake system in western Finland

Larsmo-Öjasjön i Österbotten skapades genom invallningar på 1960-talet pga. industrins behov av sötvatten. Sedan dess har vattenområdet drabbats av återkommande försurning och fiskdöd, och invallningen har ofta beskyllts för problemen. Avhandlingen undersöker syrabelastningen i området; bl.a. hur markanvändning, hydrologi och klimatförändringen påverkar belastningen. Konsekvenserna undersöks med fiskyngel som bioindikator, och olika miljömetoder testas och diskuteras. Ökad kunskap om försurningen hjälper oss att tillämpa effektiva miljömetoder och få förbättrad vattenkvalitet i framtiden. Den primära orsaken till den försämrade vattenkvaliteten under de senaste 40 åren är intensiv dikning av svavelrika sediment. Detta leder till oxidering av svavlet till svavelsyra och uppkomst av sura sulfatjordar. Syran löser upp mängder med toxiska metaller som spolas ut i vattendragen. Undersökningen visar att tiotusentals ton svavelsyra tillsammans med stora mängder metaller rinner till Larsmo-Öjasjön per år från sura sulfatjordar. Åarna bidrar med mest belastning, men den sammanlagda belastningen från de otaliga dikena och bäckarna är oväntat stor. Andra potentiella källor till försurningen, t.ex. muddringar och humussyror, beräknas vara obetydliga. Syra- och metallbelastningen varierar kraftigt med hydrologin, dvs. störst belastning sker under vår- och höstflöden. En eventuell klimatförändring kan ändra på avrinningsmönstret och orsaka mera belastning vintertid. Den årligt återkommande syra- och metallbelastningen kan ofta hindra lakens förökning, vilket kan ha större långtgående konsekvenser för fiskpopulationerna än de relativt sällsynta stora surchockerna med synlig fiskdöd. För att förebygga skador på vattendragen bör man undvika att dränera svavelrika sedimenten. På redan existerande sura sulfatjordar visade sig kontroll av grundvattennivån kunna möjliggöra en effektiverad markanvändning utan märkbart ökade miljökonsekvenser.

Map of the sources of Snake River : with its tributaries together with portions of the headwaters of the Madison and Yellowstone from surveys and observations of the Snake River Expedition

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Map of the sources of Snake River : with its tributaries together with portions of the headwaters of the Madison and Yellowstone from surveys and observations of the Snake River Expedition

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Man and the Milieu: Ecocritical analysis of Ernest Hemingway’s “Big Two-Hearted River” and “Indian Camp

Pro Gradu -tutkielmassani tarkastelen Ernest Hemingwayn alun perin vuonna 1925 julkaistuja kahta novellia ”Big Two-Hearted River” ja ”Indian Camp”. Molemmat teokset kuuluvat Nick Adams -tarinoihin, jotka ovat kokoelma novelleja, joissa Hemingway kuvaa Nick Adamsin elämää pojasta mieheksi. Nick Adams on usein tulkittu Hemingwayn alter egoksi ja monet tapahtumat ovatkin suoraa heijastusta Hemingwayn elämästä. Päähenkilön lisäksi monia Nick Adams -tarinoita yhdistää luonnon vahva läsnäolo ja Hemingwayn kuuluisan maalauksellinen miljöön deskriptiivisyys. Käyttämäni ekokriittisen teorian avulla pyrin osoittamaan tutkielmassani, että Nick Adamsin hahmo peilautuu miljöökuvauksessa syventyen dynaamiseksi hahmoksi ja että Hemingwayn luonto- ja ympäristökuvaus peilaa hahmon sisäistä maailmaa hyvinkin läheisesti. Tutkimukseni teoreettinen viitekehys, ekokritiikki, on kirjallisuudentutkimuksen suuntaus, joka tutkii ihmisen ja fyysisen ympäristön suhdetta toisiinsa. Lisäksi hyödynnän tutkielmassani dikotomioita, joiden avulla tarkastelen ja analysoin novelleista nousevia aiheita. Esimerkiksi seuraavat dikotomiat ovat keskeisiä molemmissa novelleissa: kulttuuri vs. luonto, pastoraali vs. erämaa, matka vs. oleskelu, keho vs. mieli, vesi vs. maa, tuli tai valo vs. vesi ja elämä vs. kuolema.