Carbon dynamics in peatlands under changing hydrology : Effects of water level drawdown on litter quality, microbial enzyme activities and litter decomposition rates

Pristine peatlands are carbon (C) accumulating wetland ecosystems sustained by a high water level (WL) and consequent anoxia that slows down decomposition. Persistent WL drawdown as a response to climate and/or land-use change directly affects decomposition: increased oxygenation stimulates decomposition of the old C (peat) sequestered under prior anoxic conditions. Responses of the new C (plant litter) in terms of quality, production and decomposability, and the consequences for the whole C cycle of peatlands are not fully understood. WL drawdown induces changes in plant community resulting in shift in dominance from Sphagnum and graminoids to shrubs and trees. There is increasing evidence that the indirect effects of WL drawdown via the changes in plant communities will have more impact on the ecosystem C cycling than any direct effects. The aim of this study is to disentangle the direct and indirect effects of WL drawdown on the new C by measuring the relative importance of 1) environmental parameters (WL depth, temperature, soil chemistry) and 2) plant community composition on litter production, microbial activity, litter decomposition rates and, consequently, on the C accumulation. This information is crucial for modelling C cycle under changing climate and/or land-use. The effects of WL drawdown were tested in a large-scale experiment with manipulated WL at two time scales and three nutrient regimes. Furthermore, the effect of climate on litter decomposability was tested along a north-south gradient. Additionally, a novel method for estimating litter chemical quality and decomposability was explored by combining Near infrared spectroscopy with multivariate modelling. WL drawdown had direct effects on litter quality, microbial community composition and activity and litter decomposition rates. However, the direct effects of WL drawdown were overruled by the indirect effects via changes in litter type composition and production. Short-term (years) responses to WL drawdown were small. In long-term (decades), dramatically increased litter inputs resulted in large accumulation of organic matter in spite of increased decomposition rates. Further, the quality of the accumulated matter greatly changed from that accumulated in pristine conditions. The response of a peatland ecosystem to persistent WL drawdown was more pronounced at sites with more nutrients. The study demonstrates that the shift in vegetation composition as a response to climate and/or land-use change is the main factor affecting peatland ecosystem C cycle and thus dynamic vegetation is a necessity in any models applied for estimating responses of C fluxes to changes in the environment. The time scale for vegetation changes caused by hydrological changes needs to extend to decades. This study provides grouping of litter types (plant species and part) into functional types based on their chemical quality and/or decomposability that the models could utilize. Further, the results clearly show a drop in soil temperature as a response to WL drawdown when an initially open peatland converts into a forest ecosystem, which has not yet been considered in the existing models.

Drops That Open Worlds : Image of Water in the Poetry of Euphrase Kezilahabi

Euphrase Kezilahabi on tansanialainen kirjailija, joka ensimmäisenä julkaisi swahilinkielisen vapaalla mitalla kirjoitetun runokokoelman. Perinteisessä swahilirunoudessa tiukat muotosäännöt ovat tärkeitä, ja teos synnytti kiivasta keskustelua. Runoteokset Kichomi ( Viilto , Kipu , 1974) ja Karibu Ndani ( Tervetuloa sisään , 1988) sekä Kezilahabin muu tuotanto voidaan nähdä uuden sukupolven taiteena. Kezilahabi on arvostettu runoilija, mutta hänen runojaan ei aiemmin ole käännetty englanniksi (yksittäisiä säkeitä lukuunottamatta), eikä juurikaan tutkittu yksityiskohtaisesti. Yleiskuvaan pyrkivissä lausunnoissa Kezilahabin runouden on hyvin usein määritelty olevan poliittista. Monet Kezilahabin runoista ottavatkin kantaa yhteiskunnallisiin kysymyksiin, mutta niiden pohdinta on kuitenkin runoissa vain yksi taso. Sen lisäksi Kezilahabin lyriikassa on paljon muuta ennen kartoittamatonta tämä tutkimus keskittyy veden kuvaan (the image of water). Kezilahabi vietti lapsuutensa saarella Victoria-järven keskellä, ja hänen vesikuvastonsa on rikasta. Tutkimuskysymyksenä on, mitä veden kuva runoteoksissa Kichomi ja Karibu Ndani esittää. Runojen analysoinnissa ja tulkinnassa on tarkasteltu myös sitä, miten äänteellinen taso osallistuu kuvien luomiseen. Tutkimuksen määritelmä kuvasta pohjautuu osittain Hugh Kennerin näkemykseen, jonka mukaan oleellista kuvassa on kirjaimellinen taso. Kennerin lähtökohtaan on yhdistetty John Shoptawin teoriaa, joka korostaa runon äänteellisen puolen tärkeyttä merkityksen muodostumisessa. Foneemien analyysissä vaikutteena on ollut Reuven Tsurin teoria. Analyysiosio osoittaa, että veden kuva edustaa ja käsittelee teoksissa lukuisia teemoja: elämää, kuolemaa, fyysistä vetovoimaa, runoutta, mielikuvitusta ja (ali)tajuntaa sekä moraalia. Veden kuvan tutkimuksen pohjalta on nähtävissä, että Kezilahabin filosofia asettuu elävä/kuollut- ja elämä/kuolema dikotomioiden ulkopuolelle.

A computational study of Compton profiles of water - methanol solutions

The molecular level structure of mixtures of water and alcohols is very complicated and has been under intense research in the recent past. Both experimental and computational methods have been used in the studies. One method for studying the intra- and intermolecular bindings in the mixtures is the use of the so called difference Compton profiles, which are a way to obtain information about changes in the electron wave functions. In the process of Compton scattering a photon scatters inelastically from an electron. The Compton profile that is obtained from the electron wave functions is directly proportional to the probability of photon scattering at a given energy to a given solid angle. In this work we develop a method to compute Compton profiles numerically for mixtures of liquids. In order to obtain the electronic wave functions necessary to calculate the Compton profiles we need some statistical information about atomic coordinates. Acquiring this using ab-initio molecular dynamics is beyond our computational capabilities and therefore we use classical molecular dynamics to model the movement of atoms in the mixture. We discuss the validity of the chosen method in view of the results obtained from the simulations. There are some difficulties in using classical molecular dynamics for the quantum mechanical calculations, but these can possibly be overcome by parameter tuning. According to the calculations clear differences can be seen in the Compton profiles of different mixtures. This prediction needs to be tested in experiments in order to find out whether the approximations made are valid.

Asymmetrical flow field-flow fractionation in the study of water-soluble macromolecules

Asymmetrical flow field-flow fractionation (AsFlFFF) was constructed, and its applicability to industrial, biochemical, and pharmaceutical applications was studied. The effect of several parameters, such as pH, ionic strength, temperature and the reactants mixing ratios on the particle sizes, molar masses, and the formation of aggregates of macromolecules was determined by AsFlFFF. In the case of industrial application AsFlFFF proved to be a valuable tool in the characterization of the hydrodynamic particle sizes, molar masses and phase transition behavior of various poly(N-isopropylacrylamide) (PNIPAM) polymers as a function of viscosity and phase transition temperatures. The effect of sodium chloride salt and the molar ratio of cationic and anionic polyelectrolytes on the hydrodynamic particle sizes of poly (methacryloxyethyl trimethylammonium chloride) and poly (ethylene oxide)-block-poly (sodium methacrylate) and their complexes were studied. The particle sizes of PNIPAM polymers, and polyelectrolyte complexes measured by AsFlFFF were in agreement with those obtained by dynamic light scattering. The molar masses of PNIPAM polymers obtained by AsFlFFF and size exclusion chromatography agreed also well. In addition, AsFlFFF proved to be a practical technique in thermo responsive behavior studies of polymers at temperatures up to about 50 oC. The suitability of AsFlFFF for biological, biomedical, and pharmaceutical applications was proved, upon studying the lipid-protein/peptide interactions, and the stability of liposomes at different temperatures. AsFlFFF was applied to the studies on the hydrophobic and electrostatic interactions between cytochrome c (a basic peripheral protein) and anionic lipid, and oleic acid, and sodium dodecyl sulphate surfactant. A miniaturized AsFlFFF constructed in this study was exploited in the elucidation of the effect of copper (II), pH, ionic strength, and vortexing on the particle sizes of low-density lipoproteins.

Precipitation-induced runoff and leaching from milled peat mining mires by peat types : a comparative method for estimating the loading of water bodies during peat pruduction

Precipitation-induced runoff and leaching from milled peat mining mires by peat types: a comparative method for estimating the loading of water bodies during peat production. This research project in environmental geology has arisen out of an observed need to be able to predict more accurately the loading of watercourses with detrimental organic substances and nutrients from already existing and planned peat production areas, since the authorities capacity for insisting on such predictions covering the whole duration of peat production in connection with evaluations of environmental impact is at present highly limited. National and international decisions regarding monitoring of the condition of watercourses and their improvement and restoration require more sophisticated evaluation methods in order to be able to forecast watercourse loading and its environmental impacts at the stage of land-use planning and preparations for peat production.The present project thus set out from the premise that it would be possible on the basis of existing mire and peat data properties to construct estimates for the typical loading from production mires over the whole duration of their exploitation. Finland has some 10 million hectares of peatland, accounting for almost a third of its total area. Macroclimatic conditions have varied in the course of the Holocene growth and development of this peatland, and with them the habitats of the peat-forming plants. Temperatures and moisture conditions have played a significant role in determining the dominant species of mire plants growing there at any particular time, the resulting mire types and the accumulation and deposition of plant remains to form the peat. The above climatic, environmental and mire development factors, together with ditching, have contributed, and continue to contribute, to the existence of peat horizons that differ in their physical and chemical properties, leading to differences in material transport between peatlands in a natural state and mires that have been ditched or prepared for forestry and peat production. Watercourse loading from the ditching of mires or their use for peat production can have detrimental effects on river and lake environments and their recreational use, especially where oxygen-consuming organic solids and soluble organic substances and nutrients are concerned. It has not previously been possible, however, to estimate in advance the watercourse loading likely to arise from ditching and peat production on the basis of the characteristics of the peat in a mire, although earlier observations have indicated that watercourse loading from peat production can vary greatly and it has been suggested that differences in peat properties may be of significance in this. Sprinkling is used here in combination with simulations of conditions in a milled peat production area to determine the influence of the physical and chemical properties of milled peats in production mires on surface runoff into the drainage ditches and the concentrations of material in the runoff water. Sprinkling and extraction experiments were carried out on 25 samples of milled Carex (C) and Sphagnum (S) peat of humification grades H 2.5 8.5 with moisture content in the range 23.4 89% on commencement of the first sprinkling, which was followed by a second sprinkling 24 hours later. The water retention capacity of the peat was best, and surface runoff lowest, with Sphagnum and Carex peat samples of humification grades H 2.5 6 in the moisture content class 56 75%. On account of the hydrophobicity of dry peat, runoff increased in a fairly regular manner with drying of the sample from 55% to 24 30%. Runoff from the samples with an original moisture content over 55% increased by 63% in the second round of sprinkling relative to the first, as they had practically reached saturation point on the first occasion, while those with an original moisture content below 55% retained their high runoff in the second round, due to continued hydrophobicity. The well-humified samples (H 6.5 8.5) with a moisture content over 80% showed a low water retention capacity and high runoff in both rounds of sprinkling. Loading of the runoff water with suspended solids, total phosphorus and total nitrogen, and also the chemical oxygen demand (CODMn O2), varied greatly in the sprinkling experiment, depending on the peat type and degree of humification, but concentrations of the same substances in the two sprinklings were closely or moderately closely correlated and these correlations were significant. The concentrations of suspended solids in the runoff water observed in the simulations of a peat production area and the direct surface runoff from it into the drainage ditch system in response to rain (sprinkling intensity 1.27 mm/min) varied c. 60-fold between the degrees of humification in the case of the Carex peats and c. 150-fold for the Sphagnum peats, while chemical oxygen demand varied c. 30-fold and c. 50-fold, respectively, total phosphorus c. 60-fold and c. 66-fold, total nitrogen c. 65-fold and c. 195-fold and ammonium nitrogen c. 90-fold and c. 30-fold. The increases in concentrations in the runoff water were very closely correlated with increases in humification of the peat. The correlations of the concentrations measured in extraction experiments (48 h) with peat type and degree of humification corresponded to those observed in the sprinkler experiments. The resulting figures for the surface runoff from a peat production area into the drainage ditches simulated by means of sprinkling and material concentrations in the runoff water were combined with statistics on the mean extent of daily rainfall (0 67 mm) during the frost-free period of the year (May October) over an observation period of 30 years to yield typical annual loading figures (kg/ha) for suspended solids (SS), chemical oxygen demand of organic matter (CODmn O2), total phosphorus (tot. P) and total nitrogen (tot. N) entering the ditches with respect to milled Carex (C) and Sphagnum (S) peats of humification grades H 2.5 8.5. In order to calculate the loading of drainage ditches from a milled peat production mire with the aid of these annual comparative values (in kg/ha), information is required on the properties of the intended production mire and its peat. Once data are available on the area of the mire, its peat depth, peat types and their degrees of humification, dry matter content, calorific value and corresponding energy content, it is possible to produce mutually comparable estimates for individual mires with respect to the annual loading of the drainage ditch system and the surrounding watercourse for the whole service life of the production area, the duration of this service life, determinations of energy content and the amount of loading per unit of energy generated (kg/MWh). In the 8 mires in the Köyhäjoki basin, Central Ostrobothnia, taken as an example, the loading of suspended solids (SS) in the drainage ditch networks calculated on the basis of the typical values obtained here and existing mire and peat data and expressed per unit of energy generated varied between the mires and horizons in the range 0.9 16.5 kg/MWh. One of the aims of this work was to develop means of making better use of existing mire and peat data and the results of corings and other field investigations. In this respect combination of the typical loading values (kg/ha) obtained here for S, SC, CS and C peats and the various degrees of humification (H 2.5 8.5) with the above mire and peat data by means of a computer program for the acquisition and handling of such data would enable all the information currently available and that deposited in the system in the future to be used for defining watercourse loading estimates for mires and comparing them with the corresponding estimates of energy content. The intention behind this work has been to respond to the challenge facing the energy generation industry to find larger peat production areas that exert less loading on the environment and to that facing the environmental authorities to improve the means available for estimating watercourse loading from peat production and its environmental impacts in advance. The results conform well to the initial hypothesis and to the goals laid down for the research and should enable watercourse loading from existing and planned peat production to be evaluated better in the future and the resulting impacts to be taken into account when planning land use and energy generation. The advance loading information available in this way would be of value in the selection of individual peat production areas, the planning of their exploitation, the introduction of water protection measures and the planning of loading inspections, in order to achieve controlled peat production that pays due attention to environmental considerations.

Local structure of water studied by Compton scattering

This thesis presents a novel application of x-ray Compton scattering to structural studies of molecular liquids. Systematic Compton-scattering experiments on water have been carried out with unprecedented accuracy at third-generation synchrotron-radiation laboratories. The experiments focused on temperature effects in water, the water-to-ice phase transition, quantum isotope effects, and ion hydration. The experimental data is interpreted by comparison with both model computations and ab initio molecular-dynamics simulations. Accordingly, Compton scattering is found to provide unique intra- and intermolecular structural information. This thesis thus demonstrates the complementarity of the technique to traditional real-space probes for studies on the local structure of water and, more generally, molecular liquids.

Effect of water vapour stabilization of raw materials on the quality of the inhalation product

Generation of raw materials for dry powder inhalers by different size reduction methods can be expected to influence physical and chemical properties of the powders. This can cause differences in particle size, size distribution, shape, crystalline properties, surface texture and energy. These physical properties of powders influence the behaviour of particles before and after inhalation. Materials with an amorphous surface have different surface energy compared to materials with crystalline surface. This can affect the adhesion and cohesion of particles. Changes in the surface nature of the drug particles results in a change in product performance. By stabilization of the raw materials the amorphous surfaces are converted into crystalline surfaces. The primary aim of the study was to investigate the influence of the surface properties of the inhalation particles on the quality of the product. The quality of the inhalation product is evaluated by measuring the fine particle dose (FPD). FDP is the total dose of particles with aerodynamic diameters smaller than 5,0 μm. The secondary aim of this study was to achieve the target level of the FPD and the stability of the FPD. This study was also used to evaluate the importance of the stabilization of the inhalation powders. The study included manufacturing and analysing drug substance 200 μg/dose inhalation powder batches using non-stabilized or stabilized raw materials. The inhaler formulation consisted of micronized drug substance, lactose <100μm and micronized lactose <10μm. The inhaler device was Easyhaler®. Stabilization of the raw materials was done in different relative humidity, temperature and time. Surface properties of the raw materials were studied by dynamic vapour sorption, scanning electron microscopy and three-point nitrogen adsorption technique. Particle size was studied by laser diffraction particle size analyzer. Aerodynamic particle size distribution from inhalers was measured by new generation impactor. Stabilization of all three raw materials was successful. A clear difference between nonstabilized and stabilized raw materials was achieved for drug substance and lactose <10μm. However for lactose <100μm the difference wasn’t as clear as wanted. The surface of the non-stabilized drug substance was more irregular and the particles had more roughness on the surface compared to the stabilized drug substances particles surface. The surface of the stabilized drug particles was more regular and smoother than non-stabilized. Even though a good difference between stabilized and non-stabilized raw materials was achieved, a clear evidence of the effect of the surface properties of the inhalation particles on the quality of the product was not observed. Stabilization of the raw materials didn’t lead to a higher FPD. Possible explanations for the unexpected result might be too rough conditions in the stabilization of the drug substance or smaller than wanted difference in the degree of stabilization of the main component of the product <100μm. Despite positive effects on the quality of the product were not seen there appears to be some evidence that stabilized drug substance results in smaller particle size of dry powder inhalers.

Lyophilized disaccharides – the effect of water during storage

Nearly one fourth of new medicinal molecules are biopharmaceutical (protein, antibody or nucleic acid derivative) based. However, the administration of these compounds is not always that straightforward due to the fragile nature of aforementioned domains in GI-tract. In addition, these molecules often exhibit poor bioavailability when administered orally. As a result, parenteral administration is commonly preferred. In addition, shelf-life of these molecules in aqueous environments is poor, unless stored in low temperatures. Another approach is to bring these molecules to anhydrous form via lyophilization resulting in enhanced stability during storage. Proteins cannot most commonly be freeze dried by themselves so some kind of excipients are nearly always necessary. Disaccharides are commonly utilized excipients in freeze-dried formulations since they provide a rigid glassy matrix to maintain the native conformation of the protein domain. They also act as "sink"-agents, which basically mean that they can absorb some moisture from the environment and still help to protect the API itself to retain its activity and therefore offer a way to robust formulation. The aim of the present study was to investigate how four amorphous disaccharides (cellobiose, melibiose, sucrose and trehalose) behave when they are brought to different relative humidity levels. At first, solutions of each disaccharide were prepared, filled into scintillation vials and freeze dried. Initial information on how the moisture induced transformations take place, the lyophilized amorphous disaccharide cakes were placed in vacuum desiccators containing different relative humidity levels for defined period, after which selected analyzing methods were utilized to further examine the occurred transformations. Affinity to crystallization, water sorption of the disaccharides, the effect of moisture on glass transition and crystallization temperature were studied. In addition FT-IR microscopy was utilized to map the moisture distribution on a piece of lyophilized cake. Observations made during the experiments backed up the data mentioned in a previous study: melibiose and trehalose were shown to be superior over sucrose and cellobiose what comes to the ability to withstand elevated humidity and temperature, and to avoid crystallization with pharmaceutically relevant moisture contents. The difference was made evident with every utilized analyzing method. In addition, melibiose showed interesting anomalies during DVS runs, which were absent with other amorphous disaccharides. Particularly fascinating was the observation made with polarized light microscope, which revealed a possible small-scale crystallization that cannot be observed with XRPD. As a result, a suggestion can safely be made that a robust formulation is most likely obtained by utilizing either melibiose or trehalose as a stabilizing agent for biopharmaceutical freeze-dried formulations. On the other hand, more experiments should be conducted to obtain more accurate information on why these disaccharides have better tolerance for elevating humidities than others.