Protonic conductivity of (NH4) 4Fe(CN)6·1.5H2O by complex admittance method

The protonic conductivity of ammonium ferrocyanide hydrate has been studied by the complex admittance method. The admittance plots show departures from ideal Debye behaviour. The values of ionic conductivity (sigma = 3.7 X 10(-5) (OMEGA-cm)-1) and diffusion coefficient (D = 3.8 X 10(-10) cm2/s) obtained at room temperature are consistent with the corresponding values estimated by an earlier NMR study.

Symmetry preservation during radiation damage

An examination of radiation-damage processes consequent to high-energy irradiation in certain ammonium salts studied using ESR of free radical together with the structural information available from neutron diffraction studies shows that, other factors being equal/nearly equal, symmetry-related bonds are preserved in preference to those unrelated to one another by any symmetry.

Kinetics of propellant decomposition

Equations for solid-state decompositions which are controlled by the phase-boundary movement and nucleation have been examined using ammonium perchlorate/polystyrene propellant decomposition at 503 K and 533 K. It was found that 3 different equations governed by the nucleation process show a good fit of data at these temperatures. However, the best fit was obtained for the following Avrami-Erofeev equation, [-In (1 - α]1/4=kt.

Seasonal variation in nitrification and nitrate-reduction pathways in coastal sediments in the Gulf of Finland, Baltic Sea

The Baltic Sea is one of the most eutrophic marine areas in the world. The role of nitrogen as a eutrophicating nutrient in the Baltic Sea has remained controversial, due to lack of understanding of nitrogen cycling in the area. We investigated the seasonal variation in sediment nitrification, denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA) at two coastal sites in the Gulf of Finland. In addition to the in situ rates, we assessed the potential for these processes in different seasons. The nitrification and nitrogen removal processes were maximal during the warm summer months, when the sediment organic content was highest. In colder seasons, the in situ rates of the nitrification and nitrate reduction processes decreased, but the potential for nitrification remained equal to or higher than that during the warm months. The denitrification and nitrification rates were usually higher in the accumulation basin, where the organic content of the sediment was higher, but the transportation area, despite lower denitrification rates and potential, typically had higher potential for nitrification than the accumulation basin. Anammox and DNRA were not significant nitrate sinks in any of the seasons sampled. The results also show that the denitrification rates in the coastal Gulf of Finland sediment have decreased, and that benthic denitrification might be a less important sink for fixed nitrogen than previously assumed.

Use of wetland buffer areas to reduce nitrogen transport from forested catchments: Retention capacity, emissions of N2O and CH4 and vegetation composition dynamics

The use of buffer areas in forested catchments has been actively researched during the last 15 years; but until now, the research has mainly concentrated on the reduction of sediment and phosphorus loads, instead of nitrogen (N). The aim of this thesis was to examine the use of wetland buffer areas to reduce the nitrogen transport in forested catchments and to investigate the environmental impacts involved in their use. Besides the retention capacity, particular attention was paid to the main factors contributing to the N retention, the potential for increased N2O emissions after large N loading, the effects of peatland restoration for use as buffer areas on CH4 emissions, as well as the vegetation composition dynamics induced by the use of peatlands as buffer areas. To study the capacity of buffer areas to reduce N transport in forested catchments, we first used large artificial loadings of N, and then studied the capacity of buffer areas to reduce ammonium (NH4-N) export originating from ditch network maintenance areas in forested catchments. The potential for increased N2O emissions were studied using the closed chamber technique and a large artificial N loading at five buffer areas. Sampling for CH4 emissions and methane-cycling microbial populations were done on three restored buffer areas and on three buffers constructed on natural peatlands. Vegetation composition dynamics was studied at three buffer areas between 1996 and 2009. Wetland buffer areas were efficient in retaining inorganic N from inflow. The key factors contributing to the retention were the size and the length of the buffer, the hydrological loading and the rate of nutrient loading. Our results show that although the N2O emissions may increase temporarily to very high levels after a large N loading into the buffer area, the buffer areas in forested catchments should be viewed as insignificant sources of N2O. CH4 fluxes were substantially higher from buffers constructed on natural peatlands than from the restored buffer areas, probably because of the slow recovery of methanogens after restoration. The use of peatlands as buffer areas was followed by clear changes in plant species composition and the largest changes occurred in the upstream parts of the buffer areas and the wet lawn-level surfaces, where the contact between the vegetation and the through-flow waters was closer than for the downstream parts and dry hummock sites. The changes in the plant species composition may be an undesired phenomenon especially in the case of the mires representing endangered mire site types, and therefore the construction of new buffer areas should be primarily directed into drained peatland areas.

Phenyl-Ring-Bearing Cationic Surfactants: Effect of Ring Location on the Micellar Structure

A series of isomeric cationic surfactants (S1-S5) bearing a long alkyl chain that carries a 1,4-phenylene unit and a trimethyl ammonium headgroup was synthesized; the location of the phenyl ring within the alkyl tail was varied in an effort to understand its influence on the amphiphilic properties of the surfactants. The cmc's of the surfactants were estimated using ionic conductivity measurements and isothermal calorimetric titrations (ITC); the values obtained by the two methods were found to be in excellent agreement. The ITC measurements provided additional insight into the various thermodynamic parameters associated with the micellization process. Although all five surfactants have exactly the same molecular formula, their micellar properties were seen to vary dramatically depending on the location of the phenyl ring; the cmc was seen to decrease by almost an order of magnitude when the phenyl ring was moved from the tail end (cmc of S1 is 23 mM) to the headgroup region (cmc of S5 is 3 mM). In all cases, the enthalpy of micellization was negative but the entropy of micellization was positive, suggesting that in all of these systems the formation of micelles is both enthalpically and entropically favored. As expected, the decrease in cmc values upon moving the phenyl ring from the tail end to he headgroup region is accompanied by an increase in the thermodynamic driving force (Delta G) for micellization. To understand further the differences in the micellar structure of these surfactants, small-angle neutron scattering (SANS) measurements were carried out; these measurements reveal that the aggregation number of the micelles increases as the cmc decreases. This increase in the aggregation number is also accompanied by an increase in the asphericity of the micellar aggregate and a decrease in the fractional charge. Geometric packing arguments are presented to account for these changes in aggregation behavior as a function of phenyl ring location.

Bubble formation at closely spaced orifices in aqueous solutions

A filter cloth with 182 holes per 10−4 m2 has been used to generate air bubbles both in pure water and in aqueous solutions of electrolytes and non-electrolytes at various air flow rates. Potassium bromide and ammonium perchlorate were the electrolytes used, while the non-electrolytes were isopropanol, urea and glycerol. Bubble diameters and their size distribution were measured from photographs. The role of solutes in affecting bubble sizes and their distribution compared to that of pure water is discussed in the light of a hypothesis. This hypothesis assumes that if the final bubble diameter is less than the inter-orifice distance, then bubbles do not coalesce; on the other hand, if it is greater, then coalescence occurs when tf greater-or-equal, slantedti+ts, but does not occur when t

The roles of nitrification and nitrate reduction pathways in nitrogen cycling of Baltic Sea

The Baltic Sea is one of the largest brackish water bodies in the world. Primary production in the Baltic Sea is limited by nitrogen (N) availability with the exception of river outlets and the northernmost phosphorus limited basin. The excess human induced N load from the drainage basin has caused severe eutrophication of the sea. The excess N loads can be mitigated by microbe mediated natural N removal processes that are found in the oxic-anoxic interfaces in sediments and water column redoxclines. Such interfaces allow the close coupling between the oxic nitrification process, and anoxic denitrification and anaerobic ammonium oxidation (anammox) processes that lead to the formation of molecular nitrogen gas. These processes are governed by various environmental parameters. The effects of these parameters on N processes were investigated in the northern Baltic Sea sediments. During summer months when the sediment organic content is at its highest, nitrification and denitrification reach their maximum rates. However, nitrification had no excess potential, which was probably because of high competition for molecular oxygen (O2) between heterotrophic and nitrification microbes. Subsequently, the limited nitrate (NO3-) availability inhibited denitrification. In fall, winter and spring, nitrification was limited by ammonium availability and denitrification limited by the availability of organic carbon and occasionally by NO3-. Anaerobic ammonium oxidation (anammox) was not an important N removal process in the northern Baltic Sea. Modeling studies suggest that when hypoxia expands in the Baltic Sea, N removal intensifies. However, the results of this study suggest the opposite because bottom water hypoxia (O2< 2 ml l-1) decreased the denitrification rates in sediments. Moreover, N was recycled by the dissimilatory nitrate reduction to ammonium (DNRA) process instead of being removed from the water ecosystem. High N removal potentials were found in the anoxic water column in the deep basins of the Baltic Proper. However, the N removal in the water column appeared to be limited by low substrate availability, because the water at the depths at which the substrate producing nitrification process occurred, rarely mix with the water at the depths at which N removal processes were found. Overall, the natural N removal capacity of the northern Baltic Sea decreased compared to values measured in mid 1990s and early 2000. The reason for this appears to be increasing hypoxia.

A thermodynamic protocol for explaining subcriticality and other subtle features in self-deflagrating solids

A novel universal approach to understand the self-deflagration in solids has been attempted by using basic thermodynamic equation of partial differentiation, where burning mte depends on the initial temperature and pressure of the system. Self-deflagrating solids are rare and are reported only in few compounds like ammonium perchlorate (AP), polystyrene peroxide and tetrazole. This approach has led us to understand the unique characteristics of AP, viz. the existence of low pressure deflagration limit (LPL 20 atm), hitherto not understood sufficiently. This analysis infers that the overall surface activation energy comprises of two components governed by the condensed phase and gas phase processes. The most attractive feature of the model is the identification of a new subcritical regime I' below LPL where AP does not burn. The model is aptly supported by the thermochemical computations and temperature-profile analyses of the combustion train. The thermodynamic model is further corroborated from the kinetic analysis of the high pressure (1-30 atm) DTA thermograms which affords distinct empirical decomposition rate laws in regimes I' and 1 (20-60 atm). Using Fourier-Kirchoff one dimensional heat transfer differential equation, the phase transition thickness and the melt-layer thickness have been computed which conform to the experimental data.

Crystallization and Preliminary X-ray Diffraction Analysis of Crystals of Thermoascus aurantiacus Xylanase

Crystals suitable for high resolution X-ray diffraction analysis have been grown of the 29,774-Da protein, xylanase (1,-4-beta-xylan xylanohydrolase EC 3.2.1.8) from the thermophilic fungus Thermoascus aurantiacus. This protein, an endoxylanase demonstrates the hydrolysis of β-(1-4)-Image -xylose linkage in xylans and crystallizes as monoclinic pinacoids in the presence of ammonium sulphate buffered at pH 6·5, and also with neutral polyethylene glycol 6000. The crystals belong to space group P 21 and have cell dimensions, a = 41·2 Å, b = 67·76 Å, c = 51·8 Å; β = 113·2°.

Kinetics of ceric ion oxidation of naphthalene and its derivatives. Formation of the radical cation intermediate in the rate limiting step

Ceric ammonium sulfate, CAS, oxidizes naphthalene to 1,4-naphthoquinone in essentially quantitative yield in CH3CN-dil. H2SO4. Stoichiometric studies indicate that 6 mol of CAS are required for the oxidation of 1 mol of naphthalene to 1,4-naphthoquinone. Kinetic investigations reveal that the reaction takes place through initial formation of a 1:1 complex of naphthalene and cerium(IV) in an equilibrium step followed by slow decomposition of the complex to naphthalene radical cation. Kinetic results on the effects of acid strength, polarity of the medium, temperature and substituents are in accordance with this mechanism. Further conversion of the radical cation into 1,4-naphthoquinone takes place in fast steps involving a further 5 mol of cerium(IV) and 2 mol of H2O.

Veden ja järvisedimenttien laatu Vihtamonjoen valuma-alueella Sotkamossa

The study area, Vihtamonjoki catchment area, is 55 square kilometres and a third of it has been ditched. The largest ditchings have been done in years 1959-1970. The water system in the catchment area builds up of several lake basins, brooks and rivers. This study tries to discover the water quality at present. It also tries to determine the sedimentation rate and the changes on the sediment quality during the past decades. The water samples were collected in August 2003 and in March 2004 from several places in the catchment area. On March 2004 the sediment samples were collected from four lake basins. Organic matter, total phosphorus, iron, manganese, Fe/Mn-ratio, zinc and copper were determined from sediment samples. The water quality was determined by electric conductivity, alkalinity, pH, oxygen content and the content of sodium, potassium, magnesium, calcium, sulphate, chlorine and fluoride. Also the nutrients, nitrate, ammonium and phosphate, were determined. Chemical analyses and loss on ignition analyses showed clear changes in sediment quality in samples taken from 15-25 cm depth, thus showing the time of the ditching. In most cases the forest ditching had caused increase in mineral matter, iron, zinc and copper and decrease in total phosphorus and organic matter. Sedimentation rates vary between 4,1 to 6,7 mm/year in lakes after the forest ditching. Sedimentation rates have probably increased due to the forest ditching. The Fe/Mn-ratio shows that there has been a lack of oxygen in the lakes for some years after the forest ditching. The water quality proved to be normal in the Vihtamonjoki catchment area. Oxygen content in March 2004 pointed to the conclusion that there might be lack of oxygen in winter. Other analysis showed the water quality to be typical for the Kainuu area.

Kaupunkipurot Helsingissä - Veden laatu vuonna 2004

In recent years urban hydrology and individual urban streams have been in focus and subjects to research also in Helsinki. However, until now there has been lack of research covering simultaneously the whole area of the city of Helsinki. The aim of this study was to find out the general state of water quality in small urban streams in the city of Helsinki. 21 streams were studied: Mätäjoki, Korppaanoja, Mätäpuro, Näsinoja-Tuomarinkylänoja, Tuomarinkartanonpuro, Kumpulanpuro, Tapaninkylänpuro, Tapaninvainionpuro, Puistolanpuro, Longinoja, Säynäslahdenpuro, Viikinoja, Porolahdenpuro, Mustapuro, Marjaniemenpuro, Mellunkylänpuro, Vuosaarenpuro, Rastilanpuro, Ramsinkannaksenpuro, Skatanpuro and Yliskylänpuro. Water samples were collected from 48 sampling points, each stream having at least one point. Four water samples were collected from each point, sampling periods being 9.-11.2., 26.-28.4., 29.6.-1.7. and 25.-27.10.2004. Field measurements associated with water sampling included water temperature, oxygen concentration, pH and electrical conductivity. Water samples were analysed in the Laboratory of Physical Geography in the University of Helsinki and in the Environmental Laboratory of the City of Helsinki Environment Centre for following properties: suspended solids, dissolved substances, alkalinity, principal anions and cations (Na+, K+, Mg2+, Ca2+, F-, Cl-, NO3-, PO43- and SO42-), colour, turbidity, biological and chemical oxygen demand (BOD7 and CODMn-values), nutrient concentrations and bacterial indicators of hygienic quality. The main water quality issues found in this study were low oxygen levels in many streams and poor hygienic quality at least occasionally. E.g. in summer oxygen levels were under 60 % in every stream. Amount of total dissolved substances and nutrients were high in some of the streams studied. Compared to other Finnish streams the values of alkalinity and pH were higher. Although these problems were common, the variation between different streams and sampling points was significant. This was probably due to local conditions. Best overall water quality was found in Mätäpuro and Tuomarinkartanonpuro streams. Seasonal variation was evident in almost all water quality properties. For example the total amount of dissolved substances was largest in winter and decreased during the year. Colour and turbidity were smallest in winter and increased towards the end of the year. The same was true for suspended solids, which had smallest concentration in winter and greatest in autumn. It must be kept in mind that the spring samples were collected after the spring flood otherwise the largest suspended solid concentrations would have been expected in spring. Finnish general water quality classification was used to assess the quality of urban stream waters. Its suitability for small urban streams is not, however, completely trouble-free. This classification does not take into account the quick changes in such small streams but evaluates only the yearly mean values. This can oversimplify the picture of the water quality situation in the streams. Also in order to better reflect the urban environment the analysed water quality properties should also include total dissolved substances and e.g. concentrations of chloride and sodium.

Spectroscopic investigations of phase transitions in complex solids

Spectroscopic methods have provided information of seminal importance in understanding phase transitions in solids. After briefly examining some fundamental concept related to phase transitions, we shall discuss several case studies particularly involving the use of vibrational (IR and Raman) spectroscopy. Examples will include both order-disorder and displacive transitions. Under the former are included transitions in nitrates, ammonium halides, alkylammonium salts, plastic state of C60 and superionic conductors (specially CsHSO4). In addition, we shall discuss some aspects of incommensurate phase transitions, the glass transition and electronic phase transitions. Transitions of phosphonitrilic halide tetramers and alkane dicarboxylic acids are also examined

Structure of Sesbania Mosaic Virus at 4·7 Å Resolution and Partial Sequence of the Coat Protein

Sesbania mosaic virus (SMV) is a plant virus infecting Sesbania grandiflora plants in Andhra Pradesh, India. Amino acid sequence of the tryptic peptides of SMV coat protein were determined using a gas phase sequenator. These sequences showed identical amino acids at 69% of the positions when aligned with the corresponding residues of southern bean mosaic virus (SBMV).Crystals diffracting to better than 3 Å resolution were obtained by precipitating the virus with ammonium sulphate. The crystals belonged to rhombohedral space group R3 with α = 291·4 Å and α = 61·9°. Three-dimensional X-ray diffraction data on these crystals were collected to a resolution of 4·7 Å, using a Siemens-Nicolet area detector system. Self-rotation function studies revealed the icosahedral symmetry of the virus particles, as well as their precise orientation in the unit cell. Cross-rotation function and modelling studies with SBMV showed that it is a valid starting model for SMV structure determination. Low resolution phases computed using a polyalanine model of SBMV were subjected to refinement and extension by real-space electron density averaging and solvent flattening. The final electron density map revealed a polypeptide fold similar to SBMV. The single disulphide bridge of SBMV coat protein is retained in SMV. Four icosahedrally independent cation binding sites have been tentatively identified. Three of these sites, related by a quasi threefold axis, are also found in SBMV. The fourth site is situated on the quasi threefold axis. Aspartic acid residues, which replace Ile218 of SBMV from the quasi threefold-related subunits are suitable ligands to the cation at this site