Chemical mass closure and source-specific composition of atmospheric particles

It has been known for decades that particles can cause adverse health effects as they are deposited within the respiratory system. Atmospheric aerosol particles influence climate by scattering solar radiation but aerosol particles act also as the nuclei around which cloud droplets form. The principal objectives of this thesis were to investigate the chemical composition and the sources of fine particles in different environments (traffic, urban background, remote) as well as during some specific air pollution situations. Quantifying the climate and health effects of atmospheric aerosols is not possible without detailed information of the aerosol chemical composition. Aerosol measurements were carried out at nine sites in six countries (Finland, Germany, Czech, Netherlands, Greece and Italy). Several different instruments were used in order to measure both the particulate matter (PM) mass and its chemical composition. In the off-line measurements the samples were collected first on a substrate or filter and gravimetric and chemical analysis were conducted in the laboratory. In the on-line measurements the sampling and analysis were either a combined procedure or performed successively within the same instrument. Results from the impactor samples were analyzed by the statistical methods. This thesis comprises also a work where a method for the determination carbonaceous matter size distribution by using a multistage impactor was developed. It was found that the chemistry of PM has usually strong spatial, temporal and size-dependent variability. In the Finnish sites most of the fine PM consisted of organic matter. However, in Greece sulfate dominated the fine PM and in Italy nitrate made the largest contribution to the fine PM. Regarding the size-dependent chemical composition, organic components were likely to be enriched in smaller particles than inorganic ions. Data analysis showed that organic carbon (OC) had four major sources in Helsinki. Secondary production was the major source in Helsinki during spring, summer and fall, whereas in winter biomass combustion dominated OC. The significant impact of biomass combustion on OC concentrations was also observed in the measurements performed in Central Europe. In this thesis aerosol samples were collected mainly by the conventional filter and impactor methods which suffered from the long integration time. However, by filter and impactor measurements chemical mass closure was achieved accurately, and a simple filter sampling was found to be useful in order to explain the sources of PM on the seasonal basis. The online instruments gave additional information related to the temporal variations of the sources and the atmospheric mixing conditions.

Chemical and source characterisation of size-segregated urban air particulate matter

Recent epidemiological studies have shown a consistent association of the mass concentration of urban air thoracic (PM10) and fine (PM2.5) particles with mortality and morbidity among cardiorespiratory patients. However, the chemical characteristics of different particulate size ranges and the biological mechanisms responsible for these adverse health effects are not well known. The principal aims of this thesis were to validate a high volume cascade impactor (HVCI) for the collection of particulate matter for physicochemical and toxicological studies, and to make an in-depth chemical and source characterisation of samples collected during different pollution situations. The particulate samples were collected with the HVCI, virtual impactors and a Berner low pressure impactor in six European cities: Helsinki, Duisburg, Prague, Amsterdam, Barcelona and Athens. The samples were analysed for particle mass, common ions, total and water-soluble elements as well as elemental and organic carbon. Laboratory calibration and field comparisons indicated that the HVCI can provide a unique large capacity, high efficiency sampling of size-segregated aerosol particles. The cutoff sizes of the recommended HVCI configuration were 2.4, 0.9 and 0.2 μm. The HVCI mass concentrations were in a good agreement with the reference methods, but the chemical composition of especially the fine particulate samples showed some differences. This implies that the chemical characterization of the exposure variable in toxicological studies needs to be done from the same HVCI samples as used in cell and animal studies. The data from parallel, low volume reference samplers provide valuable additional information for chemical mass closure and source assessment. The major components of PM2.5 in the virtual impactor samples were carbonaceous compounds, secondary inorganic ions and sea salt, whereas those of coarse particles (PM2.5-10) were soil-derived compounds, carbonaceous compounds, sea salt and nitrate. The major and minor components together accounted for 77-106% and 77-96% of the gravimetrically-measured masses of fine and coarse particles, respectively. Relatively large differences between sampling campaigns were observed in the organic carbon content of the PM2.5 samples as well as the mineral composition of the PM2.5-10 samples. A source assessment based on chemical tracers suggested clear differences in the dominant sources (e.g. traffic, residential heating with solid fuels, metal industry plants, regional or long-range transport) between the sampling campaigns. In summary, the field campaigns exhibited different profiles with regard to particulate sources, size distribution and chemical composition, thus, providing a highly useful setup for toxicological studies on the size-segregated HVCI samples.

Optimum geometry for uniform deposits on a rotating substrate from a point source

The application of an algorithm shows that maximum uniformity of film thickness on a rotating substrate is achieved for a normalized source-to-substrate distance ratio, h/r =1.183.

On uniformity of film thickness on rotating substrates having a large source-to-substrate height

Abstract is not available.

A note on the application of a radiation condition for a source in a rotating stratified fluid

The motion due to an oscillatory point source in a rotating stratified fluid has been studied by Sarma & Naidu (1972) by using threefold Fourier transforms. The solution obtained by them in the hyperbolic case is wrong since they did not make use of any radiation condition, which is always necessary to get the correct solution. Whenever the motion is created by a source, the condition of radiation is that the sources must remain sources, not sinks of energy and no energy may be radiated from infinity into the prescribed singularities of the field. The purpose of the present note is to explain how Lighthill's (1960) radiation condition can be applied in the hyperbolic case to pick the correct solution. Further, the solution thus obtained is reiterated by an alternative procedure using Sommerfeld's (1964) radiation condition.

Isotopic records of terrestrial ice age environments in mammoth bioapatite

Palaeoenvironments of the latter half of the Weichselian ice age and the transition to the Holocene, from ca. 52 to 4 ka, were investigated using isotopic analysis of oxygen, carbon and strontium in mammal skeletal apatite. The study material consisted predominantly of subfossil bones and teeth of the woolly mammoth (Mammuthus primigenius Blumenbach), collected from Europe and Wrangel Island, northeastern Siberia. All samples have been radiocarbon dated, and their ages range from >52 ka to 4 ka. Altogether, 100 specimens were sampled for the isotopic work. In Europe, the studies focused on the glacial palaeoclimate and habitat palaeoecology. To minimise the influence of possible diagenetic effects, the palaeoclimatological and ecological reconstructions were based on the enamel samples only. The results of the oxygen isotope analysis of mammoth enamel phosphate from Finland and adjacent nortwestern Russia, Estonia, Latvia, Lithuania, Poland, Denmark and Sweden provide the first estimate of oxygen isotope values in glacial precipitation in northern Europe. The glacial precipitation oxygen isotope values range from ca. -9.2±1.5 in western Denmark to -15.3 in Kirillov, northwestern Russia. These values are 0.6-4.1 lower than those in present-day precipitation, with the largest changes recorded in the currently marine influenced southern Sweden and the Baltic region. The new enamel-derived oxygen isotope data from this study, combined with oxygen isotope records from earlier investigations on mammoth tooth enamel and palaeogroundwaters, facilitate a reconstruction of the spatial patterns of the oxygen isotope values of precipitation and palaeotemperatures over much of Europe. The reconstructed geographic pattern of oxygen isotope levels in precipitation during 52-24 ka reflects the progressive isotopic depletion of air masses moving northeast, consistent with a westerly source of moisture for the entire region, and a circulation pattern similar to that of the present-day. The application of regionally varied δ/T-slopes, estimated from palaeogroundwater data and modern spatial correlations, yield reasonable estimates of glacial surface temperatures in Europe and imply 2-9°C lower long-term mean annual surface temperatures during the glacial period. The isotopic composition of carbon in the enamel samples indicates a pure C3 diet for the European mammoths, in agreement with previous investigations of mammoth ecology. A faint geographical gradient in the carbon isotope values of enamel is discernible, with more negative values in the northeast. The spatial trend is consistent with the climatic implications of the enamel oxygen isotope data, but may also suggest regional differences in habitat openness. The palaeogeographical changes caused by the eustatic rise of global sea level at the end of the Weichselian ice age was investigated on Wrangel Island, using the strontium isotope (Sr-87/Sr-86) ratios in the skeletal apatite of the local mammoth fauna. The diagenetic evaluations suggest good preservation of the original Sr isotope ratios, even in the bone specimens included in the study material. To estimate present-day environmental Sr isotope values on Wrangel Island, bioapatite samples from modern reindeer and muskoxen, as well as surface waters from rivers and ice wedges were analysed. A significant shift towards more radiogenic bioapatite Sr isotope ratios, from 0.71218 ± 0.00103 to 0.71491 ± 0.00138, marks the beginning of the Holocene. This implies a change in the migration patterns of the mammals, ultimately reflecting the inundation of the mainland connection and isolation of the population. The bioapatite Sr isotope data supports published coastline reconstructions placing the time of separation from the mainland to ca. 10-10.5 ka ago. The shift towards more radiogenic Sr isotope values in mid-Holocene subfossil remains after 8 ka ago reflects the rapid rise of the sea level from 10 to 8 ka, resulting in a considerable reduction of the accessible range area on the early Wrangel Island.

Biological control of bellyache bush (Jatropha gossypiifolia) in Australia: South America as a possible source of natural enemies

Bellyache bush (Jatropha gossypiifolia, Euphorbiaceae), a deciduous shrub introduced as an ornamental from tropical America, is a major and expanding weed of rangelands and riparian zones in northern Australia. Biological control is the most economically viable and long-term management solution for this weed. Surveys for potential biological control agents for J gossypiifolia in Mexico,Central America and the Caribbean resulted in release of the seed-feeding jewel bug Agonosoma trilineatum (Hemiptera: Scutelleridae), which failed to establish, and prioritisation of a leaf-rust Phakopsora arthuriana (Puccineales: Phakopsoraceae) for host-specificity testing, which is ongoing. With poor prospects for new agents from Mexico and Central America and the Caribbean, the search for candidate agents on J gossypiifolia shifted to localities south of the equator. Surveys were conducted on the purple-leaf form of J gossypiifolia, Jatropha excisa, Jatropha clavuligera and Jatropha curcas in Peru, Bolivia and Paraguay in 2012 and 2013. A total of 11 insect species, one mite species and the leaf-rust (P. arthuriana) were observed. These include a yet to be described leafmining moth (Stomphastis sp.) (Lepidoptera: Gracillaridae), a shoot and leaf-galling midge Prodiplosis longifila, and leaf-feeding midge Prodiplosis sp. near longifila (both Diptera:Cecidomyiidae) and an unidentified leaf-feeding moth larva (Lepidoptera: Notodontidae). The leafminer is widespread and damaging and has a field host range restricted to the genus Jatropha in Peru and Bolivia, holds the greatest promise as a biological control agent in Australia. Phakopsora arthuriana was recorded for the first time ever from Bolivia and Peru. Further exploration will be conducted in Peru and Bolivia during the wet season to confirm the field host range of collected agents,and to look for more new agents. Promising agents with field host-range restricted to Jatropha spp. will be imported into a quarantine facility in Australia for host-specificity testing.

Separation of 35S-Labeled thionucleosides of Escherichia coli and Pseudomonas aeruginosa transfer RNAs on a phosphocellulose column

35S-Labeled thionucleosides prepared from Escherichia coli and Pseudomonas aeruginosa tRNAs were chromatographed separately on a phosphocellulose column with a linear salt gradient of 0.005–0.1 M ammonium formate (pH 3.9). The thionucleosides of E. coli tRNA were quantitatively separated into four peaks which were identified using authentic samples as 4-thiouridine (78 %), 2-methylthio-N6-isopentenyladenosine (8 %), 2-thiocytidine (2.5 %) and 5-methylaminomethyl-2-thiouridine (11.5 %). In the case of P. aeruginosa tRNA four radioactive thionucleoside peaks were also observed. One major difference was the almost complete absence of 2-methylthio-N6-isopentenyladenosine and the presence of a new peak of radioactivity in the nucleosides of P. aeruginosa. The relative proportions of the various thionucleosides were found to be different in E. coli and P. aeruginosa tRNAs.

Separation β-apocarotenals and related compounds by reversed-phase paper and thin-layer chromatography

Abstract is not available.

Measuring and tracking quality factors in Free and Open Source Software projects

Free and Open Source Software (FOSS) has gained increased interest in the computer software industry, but assessing its quality remains a challenge. FOSS development is frequently carried out by globally distributed development teams, and all stages of development are publicly visible. Several product and process-level quality factors can be measured using the public data. This thesis presents a theoretical background for software quality and metrics and their application in a FOSS environment. Information available from FOSS projects in three information spaces are presented, and a quality model suitable for use in a FOSS context is constructed. The model includes both process and product quality metrics, and takes into account the tools and working methods commonly used in FOSS projects. A subset of the constructed quality model is applied to three FOSS projects, highlighting both theoretical and practical concerns in implementing automatic metric collection and analysis. The experiment shows that useful quality information can be extracted from the vast amount of data available. In particular, projects vary in their growth rate, complexity, modularity and team structure.

Superhydrophobic fabrics for oil-water separation based on the metal organic charge transfer complex CuTCNAQ

This work reports on the fabrication of a superhydrophobic nylon textile based on the organic charge transfer complex CuTCNAQ (TCNAQ = 11,11,12,12-tetracyanoanthraquinodimethane). The nylon fabric that is metallized with copper undergoes a spontaneous chemical reaction with TCNAQ dissolved in acetonitrile to form nanorods of CuTCNAQ that are intertwined over the entire surface of the fabric. This creates the necessary micro and nanoscale roughness that is required for the Cassie-Baxter state thereby achieving a superhydrophobic/superoleophilic surface without the need for a fluorinated surface. The material is characterised with SEM, FT-IR and XPS spectroscopy and investigated for its ability to separate oil and water in two modes, namely under gravity and as an absorbent. It is found that the fabric can separate dichloromethane, olive oil and crude oil from water and in fact reduce the water content of the oil during the separation process. The fabric is reusable and tolerant to conditions such as seawater, hydrochloric acid and extensive time periods on the shelf. Given that CuTCNAQ is a copper based semiconductor may also open up the possibility of other applications in areas such as photocatalysis and antibacterial applications.

Näkövammaisten tietokoneavusteinen tiedon hankinta

The study examines various uses of computer technology in acquisition of information for visually impaired people. For this study 29 visually impaired persons took part in a survey about their experiences concerning acquisition of infomation and use of computers, especially with a screen magnification program, a speech synthesizer and a braille display. According to the responses, the evolution of computer technology offers an important possibility for visually impaired people to cope with everyday activities and interacting with the environment. Nevertheless, the functionality of assistive technology needs further development to become more usable and versatile. Since the challenges of independent observation of environment were emphasized in the survey, the study led into developing a portable text vision system called Tekstinäkö. Contrary to typical stand-alone applications, Tekstinäkö system was constructed by combining devices and programs that are readily available on consumer market. As the system operates, pictures are taken by a digital camera and instantly transmitted to a text recognition program in a laptop computer that talks out loud the text using a speech synthesizer. Visually impaired test users described that even unsure interpretations of the texts in the environment given by Tekstinäkö system are at least a welcome addition to complete perception of the environment. It became clear that even with a modest development work it is possible to bring new, useful and valuable methods to everyday life of disabled people. Unconventional production process of the system appeared to be efficient as well. Achieved results and the proposed working model offer one suggestion for giving enough attention to easily overlooked needs of the people with special abilities. ACM Computing Classification System (1998): K.4.2 Social Issues: Assistive technologies for persons with disabilities I.4.9 Image processing and computer vision: Applications Keywords: Visually impaired, computer-assisted, information, acquisition, assistive technology, computer, screen magnification program, speech synthesizer, braille display, survey, testing, text recognition, camera, text, perception, picture, environment, trasportation, guidance, independence, vision, disabled, blind, speech, synthesizer, braille, software engineering, programming, program, system, freeware, shareware, open source, Tekstinäkö, text vision, TopOCR, Autohotkey, computer engineering, computer science