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.

Novel polymeric flame retardant plasticizers for poly(vinyl chloride)

Polyphosphate esters have been used as polymeric flame retardant plasticizers in poly(vinyl chloride); thermal and flammability studies were carried out to evaluate their efficiencies as fire retardants. A comparison is also made on the fire retardancy of the conventional simple phosphates with that of the polyphosphates as novel fire retardant plasticizers for PVC.

Palladium(II) chloride complexes of bis(pyrazolyl)cyclotriphosphazenes

Reactions of the bis(3,5-dimethylpyrazolyl)cyclotriphosphazene derivatives gem-N3P3(MeNCH(2)CH(2)O)(2)(dmp)(2) (1) and nongeminal cis-N3P3(OPh)(4)(dmp)(2) (2) with PdCl2 afford complexes of the type [PdCl2.(L)] (L = 1 or 2). In these complexes, the phosphazenes act as bidentate NN-donor ligands with the two pyrazolyl pyridinic nitrogen atoms bonded to the metal, thus forming a six- and an eight-membered chelate ring, respectively. The structures of 2 and [PdCl2.(2)] (4) have been confirmed by single-crystal X-ray diffraction. Crystal data for 2: a = 16.759(2) Angstrom, b = 10.788(3) Angstrom, c = 19.635(9) Angstrom, beta = 101.61(3)degrees, P2(1/c), Z = 4, R = 0.038 for 4688 reflections with F > 5 sigma(F). Crystal data for 4: a = 9.701(3) Angstrom, b = 24.853(4) Angstrom, c = 15.794(4) Angstrom, beta = 101.46(2)degrees, P2(1/n), Z = 4, R = 0.030 for 5416 reflections with F > 5 sigma(F).

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.

Correlation of seasonal changes in sperm output with endocrinological changes in the adult male bonnet monkey, Macaca radiata

We have examined the monthly variations in sperm output and attempted to correlate the profiles of endocrine hormones secreted with the sperm counts throughout the ,year in the adult male bonnet monkey. As previously reported, there was a distinct spurt in sperm output beginning September through December months. A concomitant increase in serum testosterone and prolactin concentrations were also noted during September through November (mid and post-monsoon season). Although there was a marked increase in gonadotropin releasing hormone stimulated testosterone secretion, the peak testosterone concentrations post gonadotropin releasing hormone injection did not vary significantly (P>0.05) throughout the year. Basal serum follicle stimulating hormone concentrations did not vary significantly (P>0.05) during April to June months compared to September-November months. Serum inhibin concentration remained unaltered throughout the year, except in the month of March. The results of this study provide evidence for annual rhythms in prolactin and testosterone secretion and a distinct seasonality in the sperm output of the adult male bonnet monkey, but the pituitary responsiveness to exogenous gonadotropin releasing hormone remains unaltered throughout the year. Because of the existence of seasonality as noted in the present study, future studies which utilize the adult male bonnet monkey as an experimental model need to take into consideration the seasonal effects on reproductive function in this species.

A Non-contact measurement technique to measure micro surface stress and obtain deformation profiles of the order of 1nm in Micro-cantilever based structures by single image Optical Diffraction method

A new method based on analysis of a single diffraction pattern is proposed to measure deflections in micro-cantilever (MC) based sensor probes, achieving typical deflection resolutions of 1nm and surface stress changes of 50 mu N/m. The proposed method employs a double MC structure where the deflection of one of the micro-cantilevers relative to the other due to surface stress changes results in a linear shift of intensity maxima of the Fraunhofer diffraction pattern of the transilluminated MC. Measurement of such shifts in the intensity maxima of a particular order along the length of the structure can be done to an accuracy of 0.01mm leading to the proposed sensitivity of deflection measurement in a typical microcantilever. This method can overcome the fundamental measurement sensitivity limit set by diffraction and pointing stability of laser beam in the widely used Optical Beam Deflection method (OBDM).

Effect of surface roughness on diffusion-limited charge transfer

A theory is developed for diffusion-limited charge transfer on a non-fractally rough electrode. The perturbation expressions are obtained for concentration, current density and measured diffusion-limited current for arbitrary one- and two-dimensional surface profiles. The random surface model is employed for a rough electrode\electrolyte interface. In this model the gross geometrical property of an electrochemically active rough surface - the surface structure factor-is related to the average electrode current, current density and concentration. Under short and long time regimes, various morphological features of the rough electrodes, i.e. excess area (related to roughness slope), curvature, correlation length, etc. are related to the (average) current transients. A two-point Pade approximant is used to develop an all time average current expression in terms of partial morphological features of the rough surface. The inverse problem of predicting the surface structure factor from the observed transients is also described. Finally, the effect of surface roughness is studied for specific surface statistics, namely a Gaussian correlation function. It is shown how the surface roughness enhances the overall diffusion-limited charge transfer current.

Reaction of normal and pseudo 2-formylbenzenesulfonyl chlorides with amines:experimental and theoretical studies on the structure of 2-formyl benzenesulfonamides in solid, solution and gas phases

The reaction of 2-formylbenzenesulfonyl chloride 1 and its pseudo isomer 2 with primary amines give either the corresponding sulfonamido Schiff bases or the corresponding 2-formylbenzenesulfonamide depending on the concentration of the amine used. The derivatives exist as an equilibrium mixture of the corresponding sulfonamide and 2-alkyl-3-hydroxy(or 3-aminoalkyl)-benzisothiazole-1,1-dioxide. Spectroscopic studies suggest that 2-formylbenzenesulfonamides exist as benzisothiazole-1,1-dioxides in the solid state, as a mixture of 2-formylbenzenesulfonamide and the corresponding benzisothiazole-1,1-dioxide in solution and as 2-formyl-benzenesulfonamides in the gas phase.

Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

The reaction of the amino spirocyclic cyclotriphosphazene N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with palladium chloride gives the stable chelate complex [PdCl2.2] (4). An X-ray crystallographic study reveals that one of the nitrogen atoms of the diaminoalkane moiety and an adjacent phosphazene ring nitrogen atom are bonded to the metal. An analogous reaction with the phosphazene N3P3(NMe2)4(NHCH2CH2NH) (1) gives initially a similar complex which undergoes facile hydrolysis to give the novel monometallic and bimetallic complexes [PdCl2.HN3P3(O)(NMe2)4(NHCH2CH2NH2)] (5) and [PdCl{N3P3(NMe2)4(NCH2CH2NH2)}]2(O) (6), which have been structurally characterized; in the former, an (oxophosphazadienyl)ethylenediamine is chelated to the metal whereas, in the latter, an oxobridged bis(cyclotriphosphazene) acts as a hexadentate nitrogen donor ligand in its dianionic form. Crystal data for 4 : a = 14.137(1) angstrom, b = 8.3332(5) angstrom, c = 19.205(2) angstrom, beta = 96.108(7)degrees, P2(1)/c, Z = 4, R = 0.027 with 3090 reflections (F > 5sigma(F)). Crystal data for 5 : a = 8.368(2) angstrom, b = 16.841(4) A, c = 16.092(5) angstrom, beta = 98.31(2)degrees, P2(1)/n, Z = 4, R = 0.049 with 3519 reflections (F > 5sigma(F)). Crystal data for 6 : a = 22.455(6) angstrom, b = 14.882(3) angstrom, c = 13.026(5) angstrom, 6 = 98.55(2)degrees, C2/c, Z = 4, R = 0.038 with 3023 reflections (F > 5sigma(F)).

Diurnal variation of atmospheric CO2 concentration and delta C-13 in an urban atmosphere during winter-role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO2 mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO2 mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30-07:30 IST) and afternoon time (16:00-18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12 degrees 58' N, 77 degrees 38' E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of similar to 7% the in CO2 mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO2 from morning samples showed a depletion in the carbon isotope ratio by similar to 2 parts per thousand compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) ``polluted air'' (PA) with isotopically enriched ``free atmospheric air'' (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.