タンデトロン加速器質量分析計業績報告

Natural archives such as lake sediments allow us to assess contemporary ecosystem responses to climate and environmental changes in a long-term context beyond the few decades to at most few centuries covered by monitoring or historical data. To achieve a comprehensive view of the changes preserved in sediment records, multi-proxy studies – ideally in high resolution – are necessary. However, this combination of including a range of analyses and high resolution constrains the amount of material available for analyses and increases the analytical costs. Infrared spectroscopic methods are a cost-efficient alternative to conventional methods because they offer a) a simple sample pre-treatment, b) a rapid measurement time, c) the non- or minimal consumption of sample material, and d) the potential to extract quantitative and qualitative information about organic and inorganic sediment components from a single measurement. The main objective of this doctoral thesis was twofold. The first part was to further explore the potential of Fourier transform infrared (FTIR) and visible-near infrared (VNIR) spectroscopy in paleolimnological studies as a) an alternative tool to conventional methods for quantifying biogenic silica (bSi) – a common proxy of paleoproductivity in lakes – in sediments and b) as a tool to infer past lake-water total organic carbon (TOC) levels from sediments. In a methodological study, I developed an independent application of FTIR spectroscopy and PLS modeling for determining bSi in sediments by using synthetic sediment mixtures with known bSi content. In contrast to previous models, this model is independent from conventional wet-chemical techniques, which had thus far been used as the calibration reference, and their inherent measurement uncertainties. The second part of the research was to apply these techniques as part of three multi-proxy studies aiming to a) improve our understanding of long-term element cycling in boreal and arctic landscapes in response to climatic and environmental changes, and b) to assess ongoing changes, particularly in lake-water TOC, on a centennial to millennial time scale. In the first applied study, high-resolution FTIR measurements of the 318-m long sediment record of Lake El’gygytgyn provided a detailed insight into long-term climate variability in the Siberian Arctic over the past 3.6 million years. Highest bSi accumulation occurred during the warm middle Pliocene (3.6-3.3 Ma), followed by a gradual but variable decline, which reflects the first onset of glacial periods and then the finally full establishment of glacial–interglacial cycles during the Quaternary. The second applied study investigated the sediment record of Torneträsk in subarctic northern Sweden also in relation to climate change, but only over the recent post-glacial period (~10 ka). By comparing responses to past climatic and environmental forcings that were recorded in this large-lake system with those recorded in small lakes from its catchment, I determined the significance and magnitude of larger-scale changes across the study region. Three different types of response were identified over the Holocene: i) a gradual response to the early landscape development following deglaciation (~10000-5300 cal yr BP); ii) an abrupt but delayed response following climate cooling during the late Holocene, which occurred c. 1300 cal yr BP – about 1000-2000 years later than in smaller lakes from the area; and iii) an immediate response to the ongoing climate change during the past century. The rapid, recent response in a previously rather insensitive lake-ecosystem emphasizes the unprecedented scale of ongoing climate change in northern Fennoscandia. In the third applied study, VNIR-inferred lake-water TOC concentrations from lakes across central Sweden showed that the ongoing, observed increase in surface water TOC in this region was in fact preceded by a long-term decline beginning already AD 1450-1600. These dynamics coincided with early human land use activities in the form of widespread summer forest grazing and farming that ceased over the past century. The results of this study show the strong impact of past human activities on past as well as ongoing TOC levels in surface waters, which has thus far been underestimated. The research in this thesis demonstrates that infrared spectroscopic methods can be an essential component in high-resolution, multi-proxy studies of past environmental and climate changes.

Das künstliche Radionuklid 137Cs wurde seit über einem halben Jahrhundert in die Natur eingebracht. Sein erstes Erscheinen in Sedimenten der zentraleuropäischen Seen korrespondiert mit den Nuklearwaffentests in den 60er-Jahren des 20. Jahrhunderts. Die stärkste Kontaminierung der europäischen Seen und Flüsse entstand als Folge des radioaktiven Niederschlags nach dem Unfall in Tschernobyl im Frühjahr 1986. In dieser Arbeit wurde das Migrationsverhalten des künstlichen 137Cs im Lago Maggiore und anderen Seen im Alpenvorland als Folge dieses Niederschlags untersucht. Der Lago Maggiore zählt zu den größten Trinkwasserreservoiren südlich der Alpen. Nach dem Unfall in Tschernobyl gingen ungefähr 20 kBq•m-2 des 137Cs auf die Oberfläche des Sees nieder. Im Zeitraum von 2003 bis 2005 wurden Sedimentkerne und Wasserproben an sieben unterschiedlichen Stellen des Lago Maggiore entnommen. Diese Arbeit beschäftigt sich mit Daten über die Verteilung des 137Cs in den Zuflüssen, dem Wasser des Sees, in Schwebstoffen und Bodensedimenten und mit der Assoziierung von 137Cs mit verschiedenen geochemischen Fraktionen. Um den Abfluss des 137Cs aus dem Wassereinzugsgebiet in den Fluss zu modellieren, wurde ein Compartmentmodell verwendet. Zur Modellierung der Aufnahmemenge von 137Cs im Sediment und der vertikalen Verteilung innerhalb dessen wurde ein Diffusions-Konvektions-Modell entwickelt. Dieses Modell berücksichtigt die Aufnahme von Aktivität durch Sedimentation, Fixierung und Rücklösung, retardierte Diffusion, die Verdichtung des Sediments sowie den Einfluss konkurrierender Ionen auf die retardierte Diffusion innerhalb des Sediments. Die Ergebnisse der Parameteroptimierung – im Wesentlichen die Sedimentationsrate und der 137Cs-Verteilungskoeffizient Kd, welcher die Aufnahme der Aktivität in das Sediment determiniert – werden erörtert und mit denen anderer europäischer Seen, die eine ähnliche 137Cs-Deposition, aber unterschiedliche limnologische Eigenschaften aufweisen, verglichen. Zur Beurteilung der Bioverfügbarkeit von 137Cs wurde die 137Cs-Aktivitätskonzentrationen von Fischproben aus dem Lago Maggiore gemessen. Aus bereits existierenden Daten und unseren Messergebnissen wurden 137Cs Fisch-Wasser Konzentrations-Verhältnisse errechnet und mit denen für andere Seen, die von ähnlichen 137Cs-Kontaminationen betroffen sind, verglichen. / Artificial Cs-137 has been introduced into the environment for more than half a century. Its first appearance in central European lake sediments corresponds to the nuclear weapons testing in the 1960s. The largest contamination of European lakes and rivers occurred as a consequence of the fallout after the Chernobyl accident in spring 1986. In this work the migration behaviour of artificial Cs-137 in Lago Maggiore and other pre-alpine lakes as a consequence of these fallouts was studied. Lago Maggiore is one of the largest drinking water reservoirs in the south of the Alps. After the Chernobyl accident roughly 20 kBq•m-2 of 137Cs were deposited onto the lake surface. From 2003 to 2005 bottom sediment cores and water samples were collected at 7 different locations of Lago Maggiore. Data on the 137Cs distribution in tributaries, lake water, suspended matter, bottom sediments, and the 137Cs association to different geochemical fractions are presented in this work. To model the run-off of 137Cs from the watershed into the lake a compartment model was used. For modeling the input of 137Cs into and the vertical distribution within the sediment a diffusion–convection type model was developed. This model takes into account the uptake of activity by sedimentation, fixation and redissolution, retarded diffusion, the influence of competing ions on the retarded diffusion within the sediments, and compaction of sediments. The results of the parameter optimization – mainly the sedimentation rate and the 137Cs distribution coefficient Kd, which determines the uptake of activity into the sediment – are discussed and compared with those of other European lakes characterized by similar 137Cs deposition levels but different limnological properties. To estimate the bioavailability of 137Cs, its activity concentrations in fish samples from Lago Maggiore were measured. Combining the existing data with our measurements, 137Cs fish–water concentration ratios were calculated and compared with those for other lakes which were affected by similar 137Cs contamination.

This study explores shallow lake numerical hydrodynamic processes that support model development and validation, extreme events and effects of water circulation in Lake Victoria. Lake Victoria is the second largest freshwater lake in the world, and the largest in East Africa. It is the major freshwater reservoir and source for domestic, agriculture, industrial, fishery, and transport. The resources support livelihoods and ecosystem services for over 40 million people. The lake is severely affected by water quality degradation by pollution. This thesis aims at improving the understanding by following recommendation of the Lake Victoria Environment Management Project, Lake Victoria Basin Commission climate change adaptation strategy and action plan 2018-2023, Lake Victoria Basin Commission operational plan 2015-2020, and Lake Victoria Basin Commission report. These reports suggested detailed lake bathymetry survey, modelling of lake flow, study of lake hydrometeorological processes by modelling and simulation, to identify extreme weather events, assess water circulation effect, and study lake pollution near the shore. A numerical hydrodynamic model was built in the COMSOL Multiphysics (CM) software for assessing lake flows and water turn-over from river inflows which carry pollution. The work included the development of systematic methods for lake bathymetry that are relevant for lake numerical and hydrodynamic modelling. The hydrometeorological driven simulation model was employed to assess lake water balance, water circulation and soluble transport. Paper 1 creates a bathymetry from several methods and from several data sources, and a vertically integrated free surface flow model was implemented in CM. The model was used to investigate outflow conditions, mean velocities driven by river inflow, outflow, precipitation and evaporation. It is shown to be exactly conservative and give water level variation in reasonable agreement with measurements. The results indicate that the shallow water model is close to linear. An outflow model, linear in water level, predicts water level reasonable agreement with measurements. The findings suggest that the model should consider wind stress driven flow to provide more accurate lake flow behavior. Paper 2 performed an assessment of the hydro-meteorological processes and extreme weather events that are responsible for changing the characteristics of lake water balance, and changing streamflow variations, and lake transportation. We compare historical data over a long time with data from the model including water balance, sources of data uncertainty, correlations, extreme rain and inflow years, and seasonal variations. Solute loading and transportation was illustrated by tracing the water from the river inflows. The results indicate that the lake rainfall has a strong seasonal variation with strong correlations between tributary inflows and precipitation, and between lake outflow and water level. The tracer transport by mean flow is very slow. Flow increases somewhat in wet periods and is faster in the shallow Kenya lake zone than in the deeper Uganda and Tanzanian lake zones, where the major inflow, from the Kagera River, appears to strongly influence transportation. / Denna studie undersöker med numerisk metodik hydrodynamiska processer i den mycket grundaVictoriasjön och hur de påverkas av extrem väderlek, inflöden, och nederbörd. Victoriasjön är denandra största sötvattensjön i världen, och den största i Afrika. Den är färskvattenförråd och källa förhushåll, jordbruk, industri, fiske och transporter. Resurserna ger livsuppehåll och ekosystemtjänsterför mer än 40 miljoner människor. Sjön är utsatt för allvarliga föroreningar som försämrarvattenkvaliteten. Detta arbete avser att förbättra förståelsen genom att följa rekommendationer somgivits ut av Lake Victoria Environment Management Project (LVEMP), och Lake Victoria BasinCommissions (LVBC) rapporter om strategi för anpassning till klimatförändringar, åtgärdsplan2018-2023 och översiktsplan 2015-2020. Rapporterna föreslår detaljerad genomgång avdjupkartor, modellering av strömning i sjön i syfte att identifiera extrema väderhändelser,undersöka vattencirkulationen, och studera föroreningarna nära stränder. En hydrodynamisknumerisk modell har byggts i simuleringspaketet COMSOL Multiphysics (CM) för uppskattning avströmning och vattenutbyte från förorenade inflöden. Arbetet innefattade utveckling av metoder förvattendjups-modeller för hydrodynamiska studier. Simuleringsmodellen drivs avhydrometeorologiska data och används för vattenmängds-balans, cirkulation ochföroreningstransport.Artikel 1 skapar vattendjupskartan från flera data-mängder med olika metoder. En vertikaltintegrerad modell med fri yta implementerades i CM. Modellen ger vertikalt medelvärdesbildadehastigheter drivna av flodinflöden, utflöde, nederbörd och avdunstning. Modellen representerarvattenbalansen exakt och ger variationer i vattennivå i rimlig överensstämmelse med mätningar.Resultaten antyder att modellen är nära linjär och tids-invariant. En utflödesmodell ansatt somlinjär i vatten-nivån kan anpassas noggrant till historiska data. Bättre realism kan uppnås omvindens pådrivande verkan inkluderas.Artikel 2 går igenom de hydro-meteorologiska processer och extrema väder-händelser som ändrarvattenbalans, strömningsmönster och transport. Vi har jämfört data över femtio år med modellens,inkluderande vattennivå, källor för osäkerhet i data, korrelationer, år med extrema regn ochinflöden, och årstidsvariationer. Resultaten tyder på att nederbörden varierar kraftigt medårstiderna, och signifikanta korrelationer ses mellan nederbörd och inflöden, och mellan utflöde ochvattennivå.Transport av lösliga föroreningar illustrerades genom spårning av vatten från de olika inflödena.Spårämnestransport med vertikalt medelvärdesbildade hastigheter är mycket långsam.Strömningen ökar något i våta årstider och är snabbare i den grunda zonen i Kenya än i de djuparedelarna i Uganda och Tanzania. Det största inflödet som kommer från Kagera tycks ha stor inverkanpå transporten. / <p>QC 20191106</p>

La neurotoxine β-N-méthyl-amino-l-alanine (BMAA) et ses isomères, notamment la N-(2- aminoéthyl glycine) (AEG), la β-amino-N-méthyl alanine (BAMA) et l'acide 2,4- diaminobutyrique (DAB), ont été détectés précédemment dans des échantillons de cyanobactéries. Cependant, il existe des rapports contradictoires concernant leur présence dans les eaux de surface. Dans cette étude, nous avons évalué l'impact de l'acide trichloracétique (TCA 0,1M) sur la détection des isomères de BMAA, par rapport aux protocoles préexistants. Une méthode instrumentale sensible a été utilisée pour l'étude, avec des limites de détection de l'ordre de 5-10 ng L-1. Des meilleures limites de détection plus élevés et des niveaux significativement plus importants (test des rangs signés de Wilcoxon appariés, p < 0,001) d'isomères de BMAA ont été observés dans les échantillons traités par le TCA, avec des augmentations relatives allant jusqu'à +725 % pour l'AEG et +1450 % pour le DAB, et des augmentations de concentration absolue allant jusqu'à +15 000 ng L-1 pour l'AEG et +650 ng L-1 pour le DAB. Nous avons également documenté les tendances de la présence des isomères de BMAA dans plusieurs lacs de différents pays tels que le Brésil, le Canada, la France, le Mexique et le Royaume-Uni. Les données obtenues au cours de cette étude (n = 390 provenant de 45 sites d'échantillonnage) indiquent des détections fréquentes des isomères AEG et DAB, avec des taux de détection de 30 % et 43 % et des niveaux maximums de 19 000 ng L-1 et 1 100 ng L-1, respectivement. En revanche, le BAMA a été trouvé dans moins de 8 % des échantillons d'eau, et la BMAA n'a été trouvée dans aucun échantillon. Ces résultats appuient les analyses des cyanobactéries libres, dans lesquelles la BMAA a souvent été détectée avec des concentrations inférieures de 2 à 4 ordres de grandeur à celles de l'AEG et du DAB. Les mesures saisonnières effectuées dans deux lacs impactés par des efflorescences ont indiqué des corrélations limitées entre les isomères de la BMAA et les microcystines totales ou la chlorophylle-a, ce qui mériterait une étude plus approfondie. / The neurotoxic alkaloid β-N-methyl-amino-l-alanine (BMAA) and related isomers, including N-(2-aminoethyl glycine) (AEG), β-amino-N-methyl alanine (BAMA) and 2,4-diaminobutyric acid (DAB), have been reported previously in cyanobacterial samples. However, there are conflicting reports regarding their occurrence in surface waters. In this study, we evaluated the impact of amending lake water samples with trichloroacetic acid (0.1M TCA) on the detection of BMAA isomers, compared with pre-existing protocols. A sensitive instrumental method was enlisted for the survey, with limits of detection in the range of 5-10 ng L-1. Higher detection limits ans significantly greater levels (paired Wilcoxon’s signed-rank tests, p < 0.001) of BMAA isomers were observed TCA-amended samples (method B) compared to samples without TCA (method A). The overall range of B/A ratios was 0.67-8.25 for AEG (up to +725 %) and 0.69-15.5 for DAB (up to +1450 %), with absolute concentration increases TCA-amended samples up to +15,000 ng L-1 for AEG and +650 ng L-1 for DAB. We also documented the trends in the occurrence of BMAA isomers for a large breadth of field-collected lakes from Brazil, Canada, France, Mexico, and the United Kingdom. Data gathered during this overarching campaign (overall n = 390 within 45 lake sampling sites) indicate frequent detections of AEG and DAB isomers, with detection rates of 30 % and 43 % and maximum levels of 19,000 ng L-1 and 1,100 ng L- 1, respectively. In contrast, BAMA was found in less than 8 % of the water samples, and BMAA not found in any sample. These results support analyses of free-living cyanobacteria, wherein BMAA was often reported at concentrations 2-4 orders of magnitude lower than AEG and DAB. Seasonal measurements conducted at two bloom-impacted lakes indicated limited correlations of BMAA isomers with total microcystins or chlorophyll-a, which deserves further investigation.