Urban energy fluxes in Helsinki and their high frequency spectral corrections

Inadvertent climate modification has led to an increase in urban temperatures compared to the surrounding rural area. The main reason for the temperature rise is the altered energy portioning of input net radiation to heat storage and sensible and latent heat fluxes in addition to the anthropogenic heat flux. The heat storage flux and anthropogenic heat flux have not yet been determined for Helsinki and they are not directly measurable. To the contrary, turbulent fluxes of sensible and latent heat in addition to net radiation can be measured, and the anthropogenic heat flux together with the heat storage flux can be solved as a residual. As a result, all inaccuracies in the determination of the energy balance components propagate to the residual term and special attention must be paid to the accurate determination of the components. One cause of error in the turbulent fluxes is the fluctuation attenuation at high frequencies which can be accounted for by high frequency spectral corrections. The aim of this study is twofold: to assess the relevance of high frequency corrections to water vapor fluxes and to assess the temporal variation of the energy fluxes. Turbulent fluxes of sensible and latent heat have been measured at SMEAR III station, Helsinki, since December 2005 using the eddy covariance technique. In addition, net radiation measurements have been ongoing since July 2007. The used calculation methods in this study consist of widely accepted eddy covariance data post processing methods in addition to Fourier and wavelet analysis. The high frequency spectral correction using the traditional transfer function method is highly dependent on relative humidity and has an 11% effect on the latent heat flux. This method is based on an assumption of spectral similarity which is shown not to be valid. A new correction method using wavelet analysis is thus initialized and it seems to account for the high frequency variation deficit. Anyhow, the resulting wavelet correction remains minimal in contrast to the traditional transfer function correction. The energy fluxes exhibit a behavior characteristic for urban environments: the energy input is channeled to sensible heat as latent heat flux is restricted by water availability. The monthly mean residual of the energy balance ranges from 30 Wm-2 in summer to -35 Wm-2 in winter meaning a heat storage to the ground during summer. Furthermore, the anthropogenic heat flux is approximated to be 50 Wm-2 during winter when residential heating is important.

Infrared spectral assignments of methyl and ethyl xanthato complexes of nickel(II)

Assignments of the infrared frequencies of methyl and ethyl xanthato complexes of nickel(II) have been made with the aid of normal coordinate analyses. The assignments are discussed in relation to those in related molecules.

Jordan Waterfall

Digital image

Jordan Waterfall

Digital image

Dagania On Jordan

Digital image

Infrared spectral assignments for transition metal thioxanthates

The i.r. frequencies of ethylthioxanthate complexes of some transition metals have been interpreted on the basis of normal coordinate treatments of the 1:1 molecular models. The band assignments are disscussed in comparison with those in closely related xanthate molecules.

Convex-transitive Banach spaces and their hyperplanes

The topic of this dissertation is the geometric and isometric theory of Banach spaces. This work is motivated by the known Banach-Mazur rotation problem, which asks whether each transitive separable Banach space is isometrically a Hilbert space. A Banach space X is said to be transitive if the isometry group of X acts transitively on the unit sphere of X. In fact, some weaker symmetry conditions than transitivity are studied in the dissertation. One such condition is an almost isometric version of transitivity. Another investigated condition is convex-transitivity, which requires that the closed convex hull of the orbit of any point of the unit sphere under the rotation group is the whole unit ball. Following the tradition developed around the rotation problem, some contemporary problems are studied. Namely, we attempt to characterize Hilbert spaces by using convex-transitivity together with the existence of a 1-dimensional bicontractive projection on the space, and some mild geometric assumptions. The convex-transitivity of some vector-valued function spaces is studied as well. The thesis also touches convex-transitivity of Banach lattices and resembling geometric cases.

Homogeneous model theory of metric structures

This thesis studies homogeneous classes of complete metric spaces. Over the past few decades model theory has been extended to cover a variety of nonelementary frameworks. Shelah introduced the abstact elementary classes (AEC) in the 1980s as a common framework for the study of nonelementary classes. Another direction of extension has been the development of model theory for metric structures. This thesis takes a step in the direction of combining these two by introducing an AEC-like setting for studying metric structures. To find balance between generality and the possibility to develop stability theoretic tools, we work in a homogeneous context, thus extending the usual compact approach. The homogeneous context enables the application of stability theoretic tools developed in discrete homogeneous model theory. Using these we prove categoricity transfer theorems for homogeneous metric structures with respect to isometric isomorphisms. We also show how generalized isomorphisms can be added to the class, giving a model theoretic approach to, e.g., Banach space isomorphisms or operator approximations. The novelty is the built-in treatment of these generalized isomorphisms making, e.g., stability up to perturbation the natural stability notion. With respect to these generalized isomorphisms we develop a notion of independence. It behaves well already for structures which are omega-stable up to perturbation and coincides with the one from classical homogeneous model theory over saturated enough models. We also introduce a notion of isolation and prove dominance for it.

Metal complexes of thiophene 2-thiocarboxamide. Proton and 13C NMR, IR and electronic spectral studies

The complexes of thiophene 2-thiocarboxamide (TTCA) with some metal chlorides and bromides [M = Ni(II), Zn(II), Cd(II), Hg(II) and Cu(I)] are described. Elemental analyses, magnetic susceptibilities and conductance studies, electronic, IR, proton and 13C magnetic resonance spectra are reported. The results suggest exclusive coordination of TTCA through the thiocarbonyl sulfur. The influence of the thiophene ring on the donor properties of the thioamide are discussed.

Statistical analysis of spectral data: A methodology for designing an intelligent monitoring system for the diabetic foot

Early detection of (pre-)signs of ulceration on a diabetic foot is valuable for clinical practice. Hyperspectral imaging is a promising technique for detection and classification of such (pre-)signs. However, the number of the spectral bands should be limited to avoid overfitting, which is critical for pixel classification with hyperspectral image data. The goal was to design a detector/classifier based on spectral imaging (SI) with a small number of optical bandpass filters. The performance and stability of the design were also investigated. The selection of the bandpass filters boils down to a feature selection problem. A dataset was built, containing reflectance spectra of 227 skin spots from 64 patients, measured with a spectrometer. Each skin spot was annotated manually by clinicians as "healthy" or a specific (pre-)sign of ulceration. Statistical analysis on the data set showed the number of required filters is between 3 and 7, depending on additional constraints on the filter set. The stability analysis revealed that shot noise was the most critical factor affecting the classification performance. It indicated that this impact could be avoided in future SI systems with a camera sensor whose saturation level is higher than 106, or by postimage processing.

Synthesis, spectral and electrochemical properties of donor/acceptor substituted fluoroarylporphyrins

Spectroscopic and electrochemical redox properties of a series of fluorinated porphyrins bearing donor-acceptor groups and their Zn(II) and Cu(II) derivatives are presented. The magnitude of the ring reduction potentials and charge transfer properties derived from spectral data depend on the nature and position of the substituent(s), (nitro/dimethylamino) and the central metal ions.

Spectral and thermal data on polystyrene peroxide

Poly(styrene peroxide) has been prepared and characterized. Nuclear magnetlc resonance (NMR) spectra Of the polymer show the shift Of aliphatic protons. Differential scanning calorimetric (DSC) and differential thermal analysis (DTA) results show anexothermic peak around 110 OC which is characteristic of peroxide decomposition.

Unitary Processes with Independent Increments and Representations of Hilbert Tensor Algebras

The aim of this article is to characterize unitary increment process by a quantum stochastic integral representation on symmetric Fock space. Under certain assumptions we have proved its unitary equivalence to a Hudson-Parthasarathy flow.

Spectral Tuning and Adaptation to Different Light Environments of Mysid Visual Pigments

In the present thesis, questions of spectral tuning, the relation of spectral and thermal properties of visual pigments, and evolutionary adaptation to different light environments were addressed using a group of small crustaceans of the genus Mysis as a model. The study was based on microspectrophotometric measurements of visual pigment absorbance spectra, electrophysiological measurements of spectral sensitivities of dark-adapted eyes, and sequencing of the opsin gene retrieved through PCR. The spectral properties were related to the spectral transmission of the respective light environments, as well as to the phylogentic histories of the species. The photoactivation energy (Ea) was estimated from temperature effects on spectral sensitivity in the long-wavelength range, and calculations were made for optimal quantum catch and optimal signal-to-noise ratio in the different light environments. The opsin amino acid sequences of spectrally characterized individuals were compared to find candidate residues for spectral tuning. The general purpose was to clarify to what extent and on what time scale adaptive evolution has driven the functional properties of (mysid) visual pigments towards optimal performance in different light environments. An ultimate goal was to find the molecular mechanisms underlying the spectral tuning and to understand the balance between evolutionary adaptation and molecular constraints. The totally consistent segregation of absorption maxima (λmax) into (shorter-wavelength) marine and (longer-wavelength) freshwater populations suggests that truly adaptive evolution is involved in tuning the visual pigment for optimal performance, driven by selection for high absolute visual sensitivity. On the other hand, the similarity in λmax and opsin sequence between several populations of freshwater M. relicta in spectrally different lakes highlights the limits to adaptation set by evolutionary history and time. A strong inverse correlation between Ea and λmax was found among all visual pigments studied in these respects, including those of M. relicta and 10 species of vertebrate pigments, and this was used to infer thermal noise. The conceptual signal-to-noise ratios thus calculated for pigments with different λmax in the Baltic Sea and Lake Pääjärvi light environments supported the notion that spectral adaptation works towards maximizing the signal-to-noise ratio rather than quantum catch as such. Judged by the shape of absorbance spectra, the visual pigments of all populations of M. relicta and M. salemaai used exclusively the A2 chromophore (3, 4-dehydroretinal). A comparison of amino acid substitutions between M. relicta and M. salemaai indicated that mysid shrimps have a small number of readily available tuning sites to shift between a shorter - and a longer -wavelength opsin. However, phylogenetic history seems to have prevented marine M. relicta from converting back to the (presumably) ancestral opsin form, and thus the more recent reinvention of marine spectral sensitivity has been accomplished by some other novel mechanism, yet to be found