The prehistory of Suomussalmi, eastern Finland; the first billion years as revealed by isotopes and the composition of granitoid suites

The four papers summarized in this thesis deal with the Archean and earliest Paleoproterozoic granitoid suites observed in the Suomussalmi district, eastern Finland. Geologically, the area belongs to the Kianta Complex of the Western Karelian Terrane in the Karelian Province of the Fennoscandian shield. The inherited zircons up to 3440 Ma old together with Sm Nd and Pb Pb data confirm the existence of previously anticipated Paleoarchean protocrust in Suomussalmi. The general timeline of granitoid magmatism is similar to that of the surrounding areas. TTG magmatism occurred in three distinct phases: ca 2.95 Ga, 2.83 2.78 Ga and 2.76 2.74 Ga. In Suomussalmi the TTGs sensu stricto (K2O/Na2O less than 0.5) belong to the low-HREE type and are interpreted as partial melts of garnet amphibolites, which did not significantly interact with mantle peridotites. Transitional TTGs (K2O/Na2O more than 0.5), present in Suomussalmi and absent from surrounding areas, display higher LILE concentrations, but otherwise closely resemble the TTGs sensu stricto and indicate that recycling of felsic crust commenced in Suomussalmi 200 Ma earlier than in surrounding areas. The youngest TTG phase was coeval with the intrusion of the Likamännikkö quartz alkali feldspar syenite (2741 ± 2 Ma) complex. The complex contains angular fragments of ultrabasic rock, which display considerable compositional heterogeneity and are interpreted as cumulates containing clinopyroxene (generally altered to actinolite), apatite, allanite, epidote, and albite. The quartz alkali feldspar syenite cannot be regarded as alkaline sensu stricto, despite clear alkaline affinities. Within Likamännikkö there are also calcite carbonatite patches, which display mantle-like O- and C-isotope values, as well as trace element characteristics consistent with a magmatic origin, and could thus be among the oldest known carbonatites in the world. Sanukitoid (2.73 2.71 Ga) and quartz diorite suites (2.70 Ga) overlap within error margins and display compositional similarities, but can be differentiated from each other on the basis of higher Ba, K2O and LREE contents of the sanukitoids. The Likamännikkö complex, sanukitoids and quartz diorites are interpreted as originating from the metasomatized mantle and mark the diversification of the granitoid clan after 200 Ma of evolution dominated by the TTG suite. Widespread migmatization and the intrusion of anatectic leucogranitoids as dykes and intrusions of varying size took place at 2.70 2.69 Ga, following collisional thickening of the crust. The leucogranitoids and leucosomes of migmatized TTGs are compositionally alike and characterized by high silica contents and a leucocratic appearance. Due to compositional overlap, definitive discrimination between leucogranitoids and transitional TTGs requires isotope datings and/or knowledge of field relationships. Leucogranitoids represent partial melts of the local TTGs, both the sensu stricto and transitional types, mostly derived under water fluxed conditions, with possible fluid sources being late sanukitoids and quartz diorites as well as dehydrating lower crust. The Paleoproterozoic 2.44 2.39 Ga A-type granitoids of the Kianta Complex emplaced in an extensional environment are linked to the coeval and more widespread mafic intrusions and dykes observed over most of the Archean nucleus of the Fennoscandian shield. The A-type intrusions in the Suomussalmi area are interpreted as partial melts of the Archean lower crust and display differences in composition and magnetite content, which indicate differences in the composition and oxidation state of the source.

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.

An infrared spectroscopic study of the low-spin-high-spin transition in FexMn1-x(Phen)2(NCS)2: A composition-induced change in the order of the spin-state transition

Infrared spectroscopy provides a valuable tool to investigate the spin-state transition in Fe(II) complexes of the type Fe(Phen)2(NCS)2. With progressive substitution of Fe by Mn, the first-order transition changes over to a second-order transition, with a high residual population of the high-spin state even at very low temperatures

Channel Volatiles Of South Indian Cordierites As Indicators Of Metamorphic Fluid Composition

The channel volatiles in cordierites of the Precambrian high-grade metapelites from southern and eastern Karnataka northern Tamil Nadu and southern Kerala were analyzed in an attempt to use them as metamorphic fluid fugacity indicators. Infrared powder absorption spectra, used to characterize the channel volatiles, showed that all the 21 analyzed cordierites have H2O and CO2 as the channel volatiles, indicating the predominantly H2O-CO2 composition of the metamorphic fluids. The H2O fraction in the metamorphic fluid was computed using a published thermodynamic method in conjunction with gravimetrically determined cordierite channel H2O content, available P - T estimates and an appropriate equation of state for the H2O - CO2 fluids. The IR data and these calculated X(H2O) values indicate an overall correlation between the variation in the relative proportion of H2O and CO2 in the fluids and the metamorphic grade. The average computed X(H2O) values are: 0.78 for the amphibolite facies eastern Karnataka pelites, 0.36 for the amphibolite facies southern Karnataka pelites, 0.19 for the southern Karnataka transitional zone rocks and 0.13 for the northern Tamil Nadu granulites. Consistently low X(H2O) values, at about 0.2, were obtained for the orthopyroxene-bearing assemblages.

Anomalous behaviour in the composition dependence of the photoacoustic properties of Si---As---Te glasses

The optical bandgap and thermal diffusivity of Si10AsxTe90−x (10 ≤ x ≤ 50) and Si15AsxTe85−x (5 ≤ x ≤ 40) glasses have been measured using the photoacoustic technique. The anomalous behaviour observed in these properties at the mean coordination number left angle bracketrright-pointing angle bracket = 2.60 is interpreted by reference to the formation and development of a layered structure in these glasses.

The effects of charge density and concentration on the composition of polyelectrolyte complexes

Polyelectrolyte complex formation involving carboxymethylcellulose and quaternized poly(vinylpyridine) as the polyions has been studied using viscosity and u.v. spectroscopic methods. The influence of charge density and molecular weight of two polycations on the composition of the complex has been investigated at two different concentrations. The charge density of the polycation is found to have different influences on the composition at different concentrations. The molecular weight of the polycation and the location of the ionic site on the polycation do not show any effect on the composition. A drastic increase in the viscosity of the polyion mixture containing quaternized poly(2-vinylpyridine) in the non-stoichiometric ratio shows evidence for the existence of the soluble polyelectrolyte complex. The results are analysed on the basis of the relative extension of the polyelectrolyte chains.

High-pressure studies on the critical composition in Ge—As—Te glasses

High-pressure resistivity measurements have been performed on G37.5AsxTe92.5-x (x = 20, 40, 45, 50 and 55) and Ge10AsxTe90-x (x = 15, 20, 35, 40, 45 and 50) glasses. The glasses show reversible metallization behaviour under pressure. The pressure derivative of the logarithm of the resistivity of the glasses is a minimum at glass compositions corresponding to the average coordination number [r] = 2.60. This behaviour is interpreted on the basis of the existence of a critical composition in glasses with a layered structure.

Composition Driven Monolayer to Bilayer Transformation in a Surfactant Intercalated Mg-Al Layered Double Hydroxide

The structure and organization of dodecyl sulfate (DDS) surfactant chains intercalated in an Mg-Al layered double hydroxide (LDH), Mg(1-x)Alx(OH)(2), with differing Al/Mg ratios has been investigated. The Mg-Al LDHs can be prepared over a range of compositions with x varying from 0.167 to 0.37 and therefore provides a simple system to study how the organization of the alkyl chains of the intercalated DDS anions change with packing density; the Al/Mg ratio or x providing a convenient handle to do so. Powder X-ray diffraction measurements showed that at high packing densities (x >= 0.3) the alkyl chains of the intercalated dodecyl sulfate ions are anchored on opposing LDH sheets and arranged as bilayers with an interlayer spacing of similar to 27 angstrom. At lower packing densities (x < 0.2) the surfactant chains form a monolayer with the alkyl chains oriented flat in the galleries with an interlayer spacing of similar to 8 angstrom. For the in between compositions, 0.2 <= x < 0.3, the material is biphasic. MD simulations were performed to understand how the anchoring density of the intercalated surfactant chains in the Mg-Al LDH-DDS affects the organization of the chains and the interlayer spacing. The simulations are able to reproduce the composition driven monolayer to bilayer transformation in the arrangement of the intercalated surfactant chains and in addition provide insights into the factors that decide the arrangement of the surfactant chains in the two situations. In the bilayer arrangement, it is the dispersive van der Waals interactions between chains in opposing layers of the anchored bilayer that is responsible for the cohesive energy of the solid whereas at lower packing densities, where a monolayer arrangement is favored, Coulomb interactions between the positively charged Mg-Al LDH sheets and the negatively charged headgroup of the DDS anion dominate.

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Substrate-dependent structure, microstructure, composition and properties of nanostructured TiN films

Titanium nitride films of a thickness of similar to 1.5 mu m were deposited on amorphous and crystalline substrates by DC reactive magnetron sputtering at ambient temperature with 100% nitrogen in the sputter gas. The growth of nanostructured, i.e. crystalline nano-grain sized, films at ambient temperature is demonstrated. The microstructure of the films grown on crystalline substrates reveals a larger grain size/crystallite size than that of the films deposited on amorphous substrates. Specular reflectance measurements on films deposited on different substrates indicate that the position of the Ti-N 2s band at 2.33 eV is substrate-dependent, indicating substrate-mediated stoichiometry. This clearly demonstrates that not only structure and microstructure, but also chemical composition of the films is substrate-influenced. The films deposited on amorphous substrates display lower hardness and modulus values than the films deposited on crystalline substrates, with the highest value of hardness being 19 GPa on a lanthanum aluminate substrate. (C) 2011 Elsevier Ltd. All rights reserved.

Structure and composition related properties of titania thin films

The dependence of optical constants, structure and composition of titania thin films on the process parameters has been investigated. Films were deposited using both reactive electron beam evaporation and ion Assisted Deposition(IAD). If has been observed that the refractive index of IAD films is higher than that for the reactively deposited films, without much difference in the extinction coefficient. Electron paramagnetic resonance has been used to estimate qualitatively the presence of non-stoichiometry in the films. It has been found that these spectra correlate very well the optical behaviour of the films. X-ray diffraction studies revealed that the neutral oxygen deposited films were stress free, while the IAD films showed tensile stress. The lattice parameters showed anisotropic change with ion beam parameters.