53 resultados para Secondary Organic Aerosols

em Helda - Digital Repository of University of Helsinki


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Volatile organic compounds (VOCs) have a great influence on tropospheric chemistry; they affect ozone formation and they or their reaction products are able to take part in secondary organic aerosol formation; some of the VOCs are themselves toxic. Knowing the concentrations and sources of different reactive volatile organic compounds is essential for the development of ozone control strategies and for studies of secondary organic aerosol formation. The objective of this work was to study volatile organic compounds in urban air, develop and validate determination methods for them, characterize their concentrations and estimate the contributions of different VOC sources. Of the different compound groups detected in the urban air of Helsinki, alkanes were found to have the highest concentrations, but when the concentrations were scaled against the reactivity with hydroxyl radicals (OH), aromatic hydrocarbons and alkenes were found to have the greatest effect on local chemistry. Comparisons with rural sites showed that concentrations at Utö and Hyytiälä were generally lower than those in Helsinki, especially for the alkenes and aromatic hydrocarbons, but concentrations of halogenated hydrocarbons at Utö and carbonyls at Hyytiälä were at the same level as in Helsinki. Most halogenated hydrocarbons do not have any significant sources in Helsinki, and carbonyls are formed in the atmosphere in the reactions of other VOCs, and are therefore also produced in other than urban areas. At Hyytiälä carbonyls were found to have an important role in the local chemistry. The contribution of carbonyls as an OH sink was higher than that of the monoterpenes and aromatic hydrocarbons. Based on the emission profile and concentration measurements, the contributions of different sources were estimated at urban (Helsinki) and residential (Järvenpää) sites using a chemical mass balance (CMB) receptor model. It was shown that it is possible to apply CMB in the case of a large number of different compounds with different properties. According to the CMB analysis, the major sources for these VOCs in Helsinki were traffic and distant sources. At the residential site in Järvenpää, the contribution due to traffic was minor, while distant sources, liquid gasoline and wood combustion made higher contributions. It was also shown that wood combustion can be an important source at some locations of VOCs usually considered as traffic-related compounds (e.g., benzene).

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Volatile organic compounds (VOCs) affect atmospheric chemistry and thereafter also participate in the climate change in many ways. The long-lived greenhouse gases and tropospheric ozone are the most important radiative forcing components warming the climate, while aerosols are the most important cooling component. VOCs can have warming effects on the climate: they participate in tropospheric ozone formation and compete for oxidants with the greenhouse gases thus, for example, lengthening the atmospheric lifetime of methane. Some VOCs, on the other hand, cool the atmosphere by taking part in the formation of aerosol particles. Some VOCs, in addition, have direct health effects, such as carcinogenic benzene. VOCs are emitted into the atmosphere in various processes. Primary emissions of VOC include biogenic emissions from vegetation, biomass burning and human activities. VOCs are also produced in secondary emissions from the reactions of other organic compounds. Globally, forests are the largest source of VOC entering the atmosphere. This thesis focuses on the measurement results of emissions and concentrations of VOCs in one of the largest vegetation zones in the world, the boreal zone. An automated sampling system was designed and built for continuous VOC concentration and emission measurements with a proton transfer reaction - mass spectrometer (PTR-MS). The system measured one hour at a time in three-hourly cycles: 1) ambient volume mixing-ratios of VOCs in the Scots-pine-dominated boreal forest, 2) VOC fluxes above the canopy, and 3) VOC emissions from Scots pine shoots. In addition to the online PTR-MS measurements, we determined the composition and seasonality of the VOC emissions from a Siberian larch with adsorbent samples and GC-MS analysis. The VOC emissions from Siberian larch were reported for the fist time in the literature. The VOC emissions were 90% monoterpenes (mainly sabinene) and the rest sesquiterpenes (mainly a-farnesene). The normalized monoterpene emission potentials were highest in late summer, rising again in late autumn. The normalized sesquiterpene emission potentials were also highest in late summer, but decreased towards the autumn. The emissions of mono- and sesquiterpenes from the deciduous Siberian larch, as well as the emissions of monoterpenes measured from the evergreen Scots pine, were well described by the temperature-dependent algorithm. In the Scots-pine-dominated forest, canopy-scale emissions of monoterpenes and oxygenated VOCs (OVOCs) were of the same magnitude. Methanol and acetone were the most abundant OVOCs emitted from the forest and also in the ambient air. Annually, methanol and mixing ratios were of the order of 1 ppbv. The monoterpene and sum of isoprene 2-methyl-3-buten-2-ol (MBO) volume mixing-ratios were an order of magnitude lower. The majority of the monoterpene and methanol emissions from the Scots-pinedominated forest were explained by emissions from Scots pine shoots. The VOCs were divided into three classes based on the dynamics of the summer-time concentrations: 1) reactive compounds with local biological, anthropogenic or chemical sources (methanol, acetone, butanol and hexanal), 2) compounds whose emissions are only temperaturedependent (monoterpenes), 3) long-lived compounds (benzene, acetaldehyde). Biogenic VOC (methanol, acetone, isoprene MBO and monoterpene) volume mixing-ratios had clear diurnal patterns during summer. The ambient mixing ratios of other VOCs did not show this behaviour. During winter we did not observe systematical diurnal cycles for any of the VOCs. Different sources, removal processes and turbulent mixing explained the dynamics of the measured mixing-ratios qualitatively. However, quantitative understanding will require longterm emission measurements of the OVOCs and the use of comprehensive chemistry models. Keywords: Hydrocarbons, VOC, fluxes, volume mixing-ratio, boreal forest

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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.

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Aerosols impact the planet and our daily lives through various effects, perhaps most notably those related to their climatic and health-related consequences. While there are several primary particle sources, secondary new particle formation from precursor vapors is also known to be a frequent, global phenomenon. Nevertheless, the formation mechanism of new particles, as well as the vapors participating in the process, remain a mystery. This thesis consists of studies on new particle formation specifically from the point of view of numerical modeling. A dependence of formation rate of 3 nm particles on the sulphuric acid concentration to the power of 1-2 has been observed. This suggests nucleation mechanism to be of first or second order with respect to the sulphuric acid concentration, in other words the mechanisms based on activation or kinetic collision of clusters. However, model studies have had difficulties in replicating the small exponents observed in nature. The work done in this thesis indicates that the exponents may be lowered by the participation of a co-condensing (and potentially nucleating) low-volatility organic vapor, or by increasing the assumed size of the critical clusters. On the other hand, the presented new and more accurate method for determining the exponent indicates high diurnal variability. Additionally, these studies included several semi-empirical nucleation rate parameterizations as well as a detailed investigation of the analysis used to determine the apparent particle formation rate. Due to their high proportion of the earth's surface area, oceans could potentially prove to be climatically significant sources of secondary particles. In the lack of marine observation data, new particle formation events in a coastal region were parameterized and studied. Since the formation mechanism is believed to be similar, the new parameterization was applied in a marine scenario. The work showed that marine CCN production is feasible in the presence of additional vapors contributing to particle growth. Finally, a new method to estimate concentrations of condensing organics was developed. The algorithm utilizes a Markov chain Monte Carlo method to determine the required combination of vapor concentrations by comparing a measured particle size distribution with one from an aerosol dynamics process model. The evaluation indicated excellent agreement against model data, and initial results with field data appear sound as well.

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The Earth s climate is a highly dynamic and complex system in which atmospheric aerosols have been increasingly recognized to play a key role. Aerosol particles affect the climate through a multitude of processes, directly by absorbing and reflecting radiation and indirectly by changing the properties of clouds. Because of the complexity, quantification of the effects of aerosols continues to be a highly uncertain science. Better understanding of the effects of aerosols requires more information on aerosol chemistry. Before the determination of aerosol chemical composition by the various available analytical techniques, aerosol particles must be reliably sampled and prepared. Indeed, sampling is one of the most challenging steps in aerosol studies, since all available sampling techniques harbor drawbacks. In this study, novel methodologies were developed for sampling and determination of the chemical composition of atmospheric aerosols. In the particle-into-liquid sampler (PILS), aerosol particles grow in saturated water vapor with further impaction and dissolution in liquid water. Once in water, the aerosol sample can then be transported and analyzed by various off-line or on-line techniques. In this study, PILS was modified and the sampling procedure was optimized to obtain less altered aerosol samples with good time resolution. A combination of denuders with different coatings was tested to adsorb gas phase compounds before PILS. Mixtures of water with alcohols were introduced to increase the solubility of aerosols. Minimum sampling time required was determined by collecting samples off-line every hour and proceeding with liquid-liquid extraction (LLE) and analysis by gas chromatography-mass spectrometry (GC-MS). The laboriousness of LLE followed by GC-MS analysis next prompted an evaluation of solid-phase extraction (SPE) for the extraction of aldehydes and acids in aerosol samples. These two compound groups are thought to be key for aerosol growth. Octadecylsilica, hydrophilic-lipophilic balance (HLB), and mixed phase anion exchange (MAX) were tested as extraction materials. MAX proved to be efficient for acids, but no tested material offered sufficient adsorption for aldehydes. Thus, PILS samples were extracted only with MAX to guarantee good results for organic acids determined by liquid chromatography-mass spectrometry (HPLC-MS). On-line coupling of SPE with HPLC-MS is relatively easy, and here on-line coupling of PILS with HPLC-MS through the SPE trap produced some interesting data on relevant acids in atmospheric aerosol samples. A completely different approach to aerosol sampling, namely, differential mobility analyzer (DMA)-assisted filter sampling, was employed in this study to provide information about the size dependent chemical composition of aerosols and understanding of the processes driving aerosol growth from nano-size clusters to climatically relevant particles (>40 nm). The DMA was set to sample particles with diameters of 50, 40, and 30 nm and aerosols were collected on teflon or quartz fiber filters. To clarify the gas-phase contribution, zero gas-phase samples were collected by switching off the DMA every other 15 minutes. Gas-phase compounds were adsorbed equally well on both types of filter, and were found to contribute significantly to the total compound mass. Gas-phase adsorption is especially significant during the collection of nanometer-size aerosols and needs always to be taken into account. Other aims of this study were to determine the oxidation products of β-caryophyllene (the major sesquiterpene in boreal forest) in aerosol particles. Since reference compounds are needed for verification of the accuracy of analytical measurements, three oxidation products of β-caryophyllene were synthesized: β-caryophyllene aldehyde, β-nocaryophyllene aldehyde, and β-caryophyllinic acid. All three were identified for the first time in ambient aerosol samples, at relatively high concentrations, and their contribution to the aerosol mass (and probably growth) was concluded to be significant. Methodological and instrumental developments presented in this work enable fuller understanding of the processes behind biogenic aerosol formation and provide new tools for more precise determination of biosphere-atmosphere interactions.

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Dioxins are organic toxicants that are known to impair tooth development, especially dental hard tissue formation. The most toxic dioxin congener is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Further, clinical studies suggest that maternal smoking during pregnancy can affect child s tooth development. One of the main components of tobacco smoke is the group of non-halogenated polycyclic aromatic hydrocarbons (PAHs), a representative of which is 7,12-dimethylbenz[a]anthracene (DMBA). Tributyltin (TBT), an organic tin compound, has been shown to impair bone mineralization in experimental animals. In addition to exposure to organic toxicants, a well-established cause for enamel hypomineralization is excess fluoride intake. The principal aim of this thesis project was to examine in vitro if, in addition to dioxins, other organic environmental toxicants, like PAHs and organic tin compounds, have adverse effects on tooth development, specifically on formation and mineralization of the major dental hard tissues, the dentin and the enamel. The second aim was to investigate in vitro if fluoride could intensify the manifestation of the detrimental developmental dental effects elicited by TCDD. The study was conducted by culturing mandibular first and second molar tooth germs of E18 NMRI mouse embryos in a Trowell-type organ culture and exposing them to DMBA, TBT, and sodium fluoride (NaF) and/or TCDD at various concentrations during the secretory and mineralization stages of development. Specific methods used were HE-staining for studying cell and tissue morphology, BrdU-staining for cell proliferation, TUNEL-staining for apoptosis, and QPCR, in situ hybridization and immunohistochemistry for the expressions of selected genes associated with mineralization. This thesis work showed that DMBA, TBT, TCDD and NaF interfere with dentin and enamel formation of embryonic mouse tooth in vitro, and that fluoride can potentiate the harmful effect of TCDD. The results suggested that adverse effects of TBT involve altered expression of genes associated with mineralization, and that DMBA and TBT as well as NaF and TCDD together primarily affect dentin mineralization. Since amelogenesis does not start until mineralization of dentin begins, impaired enamel matrix secretion could be a secondary effect. Dioxins, PAHs and organotins are all liposoluble and can be transferred to the infant by breast-feeding. Since doses are usually very low, developmental toxicity on most of the organs is difficult to indentify clinically. However, tooth may act as an indicator of exposure, since the major dental hard tissues, the dentin and the enamel, are not replaced once they have been formed. Thus, disturbed dental hard tissue formation raises the question of more extensive developmental toxicity.

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In order to evaluate the influence of ambient aerosol particles on cloud formation, climate and human health, detailed information about the concentration and composition of ambient aerosol particles is needed. The dura-tion of aerosol formation, growth and removal processes in the atmosphere range from minutes to hours, which highlights the need for high-time-resolution data in order to understand the underlying processes. This thesis focuses on characterization of ambient levels, size distributions and sources of water-soluble organic carbon (WSOC) in ambient aerosols. The results show that in the location of this study typically 50-60 % of organic carbon in fine particles is water-soluble. The amount of WSOC was observed to increase as aerosols age, likely due to further oxidation of organic compounds. In the boreal region the main sources of WSOC were biomass burning during the winter and secondary aerosol formation during the summer. WSOC was mainly attributed to a fine particle mode between 0.1 - 1 μm, although different size distributions were measured for different sources. The WSOC concentrations and size distributions had a clear seasonal variation. Another main focus of this thesis was to test and further develop the high-time-resolution methods for chemical characterization of ambient aerosol particles. The concentrations of the main chemical components (ions, OC, EC) of ambient aerosol particles were measured online during a year-long intensive measurement campaign conducted on the SMEAR III station in Southern Finland. The results were compared to the results of traditional filter collections in order to study sampling artifacts and limitations related to each method. To achieve better a time resolution for the WSOC and ion measurements, a particle-into-liquid sampler (PILS) was coupled with a total organic carbon analyzer (TOC) and two ion chromatographs (IC). The PILS-TOC-IC provided important data about diurnal variations and short-time plumes, which cannot be resolved from the filter samples. In summary, the measurements made for this thesis provide new information on the concentrations, size distribu-tions and sources of WSOC in ambient aerosol particles in the boreal region. The analytical and collection me-thods needed for the online characterization of aerosol chemical composition were further developed in order to provide more reliable high-time-resolution measurements.

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Tämän pro gradu -lopputyön aiheena on englannin kielen modaalisten apuverbien ns. ydinjoukko: will, would, can, could, shall, should, may, might ja must. Semantiikan kannalta nämä apuverbit ovat erityisen kompleksisia: niiden tulkinnassa on usein huomattavaa monivivahteisuutta, vaikka perinteiset kieliopit antavat ymmärtää niillä olevan kaksi tai kolme toisistaan selkeästi erillään olevaa merkitystä. Ne asettavatkin vieraan kielen oppimisympäristössä erityisiä haasteita. Viimeaikainen kehitys korpuslingvistiikan metodeissa on tuottanut entistä tarkempia kuvauksia siitä, miten modaalisia apuverbejä nykyenglannissa käytetään ja mihin suuntaan niiden kehitys on lyhyenkin ajan sisällä kulkenut. Tämän tutkielman tavoitteena on ollut verrata näiden uusien tutkimusten tuloksia siihen todellisuuteen, jonka englannin kielen lukiotasoinen oppimateriaali Suomessa opiskelijalle tarjoaa. Lähdin siitä, että opetussuunnitelman vaatima autenttisuus ja kommunikaativisuus kieltenopetuksessa tulisi näkyä tasapuolisena modaalisten apuverbien kohteluna. Alkuperäinen hypoteesini kuitenkin oli, että siinä miten modaalisuus ilmenee autenttisessa ympäristössä ja siinä miten se esitetään oppikirjoissa, on poikkeavuuksia. Lähestymistapani tähän tutkielmaan oli korpuslähtöinen. Valitsin kahdesta lukion kirjasarjasta ne kirjat, joissa modaaliset apuverbit mainittiin eksplisiittisesti. Skannasin jokaisen neljästä eri kirjasta löytyvän (kokonaisen) tekstin ja rakensin näistä aineksista pienen korpuksen. Tästä korpuksesta hain korpusanalyyseihin tarkoitetulla ohjelmalla kaikki lauseet, joissa esiintyi modaalisia apuverbejä. Tämän jälkeen analysoin jokaisen modaalisen apuverbin semanttisesti lauseyhteydessään. Tämän analyysin tuloksena pystyin rakentamaan taulukoita ja vertailemaan tuloksia uusimpien tutkimusten tuloksiin. Tämän tutkielman perusteella poikkeavuuksia on olemassa. Yleisesti ottaen modaalisten apuverbien keskinäinen frekvenssi oli oikean suuntainen: mitään apuverbiä ei ollut käytetty merkittävästi enemmän tai vähemmän kuin mitä viimeaikaisen tutkimuksen valossa olisi suotavaa. Sen sijaan apuverbien semanttisessa jakaumassa oli paikoin suuriakin eroja siinä, mitkä merkitykset oppikirjoissa painottuivat ja mitkä taas nykyenglannissa vaikuttaisivat olevan frekvensseiltään suurempia. Erityisesti can ja must erottuivat joukosta siinä, että oppikirjojen tarjoama kuva niiden käytöstä on päinvastainen kuin mitä voisi odottaa: can-verbin käyttö painottui selvästi tarkoittamaan ’kykyä’ eikä ’mahdollisuutta’, joka nykytutkimuksen valossa on sen pääasiallinen käyttötapa. Toisaalta must tarkoitti aineistossa ylikorostuneesti ’pakkoa’, kun se useimmiten nykyään tarkoittaa yhtä usein ’johtopäätöstä’ kuin ’pakkoa’. Lisäksi ’lupaa’ pyydettiin aineistossa merkillisen harvoin. Tulosten perusteella esitän, että oppikirjojen tekijät yleisellä tasolla luopuisivat kielioppikirjojen luutuneista käsityksistä ja uskaltaisivat altistaa opiskelijat koko modaalisten apuverbien merkityskirjolle.

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Suomen koulutuspolitiikasta vastaavat viranomaiset ovat reagoineet kansainvälisten kommunikaatiotarpeiden asettamiin haasteisiin ja muuttaneet yhden lukion A-tasoisen vieraan kielen kurssin sisällön vastaamaan suullisen viestinnän tarpeita. Tutkimuksessa selvitetään, miten englannin puhestrategioita voi opettaa suomalaisille lukiolaisille ja mitä metodeja on käytettävissä puhestrategioiden oppimisen arvioimiseksi. Vastaan asettamiini kysymyksiin aikaisemman tutkimuskirjallisuuden ja englannin kielen lukio-opetuksesta keräämäni aineiston avulla. Keskeisiä elementtejä tutkielmassa ovat erityisesti pragmaattinen kompetenssi ja kolme yleisen tason puhestrategiaa (keskustelun aloittaminen, oman puheenvuoron säilyttäminen sekä keskustelun ylläpitäminen). Aineistossa on mukana 65 ensimmäisen vuosiluokan lukiolaista (luokka A ja B) Helsingistä ja Espoosta. Opetusmateriaalina on käytetty SCOTS korpusta; tarkemmin määriteltynä puhetiedosto nimeltä Conversation 20: Four secondary school girls in the North East. Tiedostossa esille tulleet, kolmeen puhestrategiaan liittyvät fraasit, sanat ja rakenteet havainnollistettiin opiskelijoille mm. AntConc - konkordanssiohjelman avulla. Opiskelijat tekivät myös kirjallisia ja suullisia harjoituksia, jotka liittyivät puhestrategioihin. Neljälle vapaaehtoiselle opiskelijalle suunnattu toinen suullinen tehtävätyyppi vapaamuotoisine keskusteluineen äänitettiin, transkriboitiin ja tuloksia arvioitiin mm. eurooppalaisen viitekehyksen avulla. Lisäksi B - luokka vastasi kyselylomakkeeseen, jossa kysyttiin heidän mielipiteitään esim. hyödyllisimmästä testioppitunnista sekä heidän osallistumishalukkuudestaan uudelle pitkän englannin kahdeksannelle syventävälle kurssille. Tutkimustulokset ovat kannustavia ja osoittavat, että puhestrategioita on mahdollista opettaa jo lukiotasolla. Vaikka tutkimuksessa käytetty lähestymistapa oli opiskelijoille osittain uusi, valtaosa heistä myönsi oppineensa uutta englannin kielen keskustelurakenteista. Lisäksi vapaaehtoisten opiskelijoiden äänitetyt ja transkriboidut keskustelut tarjoavat hyvän lähtökohdan mahdolliselle jatkotutkimukselle.

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This academic work begins with a compact presentation of the general background to the study, which also includes an autobiography for the interest in this research. The presentation provides readers who know little of the topic of this research and of the structure of the educational system as well as of the value given to education in Nigeria. It further concentrates on the dynamic interplay of the effect of academic and professional qualification and teachers' job effectiveness in secondary schools in Nigeria in particular, and in Africa in general. The aim of this study is to produce a systematic analysis and rich theoretical and empirical description of teachers' teaching competencies. The theoretical part comprises a comprehensive literature review that focuses on research conducted in the areas of academic and professional qualification and teachers' job effectiveness, teaching competencies, and the role of teacher education with particular emphasis on school effectiveness and improvement. This research benefits greatly from the functionalist conception of education, which is built upon two emphases: the application of the scientific method to the objective social world, and the use of an analogy between the individual 'organism' and 'society'. To this end, it offers us an opportunity to define terms systematically and to view problems as always being interrelated with other components of society. The empirical part involves describing and interpreting what educational objectives can be achieved with the help of teachers' teaching competencies in close connection to educational planning, teacher training and development, and achieving them without waste. The data used in this study were collected between 2002 and 2003 from teachers, principals, supervisors of education from the Ministry of Education and Post Primary Schools Board in the Rivers State of Nigeria (N=300). The data were collected from interviews, documents, observation, and questionnaires and were analyzed using both qualitative and quantitative methods to strengthen the validity of the findings. The data collected were analyzed to answer the specific research questions and hypotheses posited in this study. The data analysis involved the use of multiple statistical procedures: Percentages Mean Point Value, T-test of Significance, One-Way Analysis of Variance (ANOVA), and Cross Tabulation. The results obtained from the data analysis show that teachers require professional knowledge and professional teaching skills, as well as a broad base of general knowledge (e.g., morality, service, cultural capital, institutional survey). Above all, in order to carry out instructional processes effectively, teachers should be both academically and professionally trained. This study revealed that teachers are not however expected to have an extraordinary memory, but rather looked upon as persons capable of thinking in the right direction. This study may provide a solution to the problem of teacher education and school effectiveness in Nigeria. For this reason, I offer this treatise to anyone seriously committed in improving schools in developing countries in general and in Nigeria in particular to improve the lives of all its citizens. In particular, I write this to encourage educational planners, education policy makers, curriculum developers, principals, teachers, and students of education interested in empirical information and methods to conceptualize the issue this study has raised and to provide them with useful suggestions to help them improve secondary schooling in Nigeria. Though, multiple audiences exist for any text. For this reason, I trust that the academic community will find this piece of work a useful addition to the existing literature on school effectiveness and school improvement. Through integrating concepts from a number of disciplines, I aim to describe as holistic a representation as space could allow of the components of school effectiveness and quality improvement. A new perspective on teachers' professional competencies, which not only take into consideration the unique characteristics of the variables used in this study, but also recommend their environmental and cultural derivation. In addition, researchers should focus their attention on the ways in which both professional and non-professional teachers construct and apply their methodological competencies, such as their grouping procedures and behaviors to the schooling of students. Keywords: Professional Training, Academic Training, Professionally Qualified, Academically Qualified, Professional Qualification, Academic Qualification, Job Effectiveness, Job Efficiency, Educational Planning, Teacher Training and Development, Nigeria.

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Aims: The aims of this study were 1) to identify and describe health economic studies that have used quality-adjusted life years (QALYs) based on actual measurements of patients' health-related quality of life (HRQoL); 2) to test the feasibility of routine collection of health-related quality of life (HRQoL) data as an indicator of effectiveness of secondary health care; and 3) to establish and compare the cost-utility of three large-volume surgical procedures in a real-world setting in the Helsinki University Central Hospital, a large referral hospital providing secondary and tertiary health-care services for a population of approximately 1.4 million. Patients and methods: So as to identify studies that have used QALYs as an outcome measure, a systematic search of the literature was performed using the Medline, Embase, CINAHL, SCI and Cochrane Library electronic databases. Initial screening of the identified articles involved two reviewers independently reading the abstracts; the full-text articles were also evaluated independently by two reviewers, with a third reviewer used in cases where the two reviewers could not agree a consensus on which articles should be included. The feasibility of routinely evaluating the cost-effectiveness of secondary health care was tested by setting up a system for collecting HRQoL data on approximately 4 900 patients' HRQoL before and after operative treatments performed in the hospital. The HRQoL data used as an indicator of treatment effectiveness was combined with diagnostic and financial indicators routinely collected in the hospital. To compare the cost-effectiveness of three surgical interventions, 712 patients admitted for routine operative treatment completed the 15D HRQoL questionnaire before and also 3-12 months after the operation. QALYs were calculated using the obtained utility data and expected remaining life years of the patients. Direct hospital costs were obtained from the clinical patient administration database of the hospital and a cost-utility analysis was performed from the perspective of the provider of secondary health care services. Main results: The systematic review (Study I) showed that although QALYs gained are considered an important measure of the effectiveness of health care, the number of studies in which QALYs are based on actual measurements of patients' HRQoL is still fairly limited. Of the reviewed full-text articles, only 70 reported QALYs based on actual before after measurements using a valid HRQoL instrument. Collection of simple cost-effectiveness data in secondary health care is feasible and could easily be expanded and performed on a routine basis (Study II). It allows meaningful comparisons between various treatments and provides a means for allocating limited health care resources. The cost per QALY gained was 2 770 for cervical operations and 1 740 for lumbar operations. In cases where surgery was delayed the cost per QALY was doubled (Study III). The cost per QALY ranges between subgroups in cataract surgery (Study IV). The cost per QALY gained was 5 130 for patients having both eyes operated on and 8 210 for patients with only one eye operated on during the 6-month follow-up. In patients whose first eye had been operated on previous to the study period, the mean HRQoL deteriorated after surgery, thus precluding the establishment of the cost per QALY. In arthroplasty patients (Study V) the mean cost per QALY gained in a one-year period was 6 710 for primary hip replacement, 52 270 for revision hip replacement, and 14 000 for primary knee replacement. Conclusions: Although the importance of cost-utility analyses has during recent years been stressed, there are only a limited number of studies in which the evaluation is based on patients own assessment of the treatment effectiveness. Most of the cost-effectiveness and cost-utility analyses are based on modeling that employs expert opinion regarding the outcome of treatment, not on patient-derived assessments. Routine collection of effectiveness information from patients entering treatment in secondary health care turned out to be easy enough and did not, for instance, require additional personnel on the wards in which the study was executed. The mean patient response rate was more than 70 %, suggesting that patients were happy to participate and appreciated the fact that the hospital showed an interest in their well-being even after the actual treatment episode had ended. Spinal surgery leads to a statistically significant and clinically important improvement in HRQoL. The cost per QALY gained was reasonable, at less than half of that observed for instance for hip replacement surgery. However, prolonged waiting for an operation approximately doubled the cost per QALY gained from the surgical intervention. The mean utility gain following routine cataract surgery in a real world setting was relatively small and confined mostly to patients who had had both eyes operated on. The cost of cataract surgery per QALY gained was higher than previously reported and was associated with considerable degree of uncertainty. Hip and knee replacement both improve HRQoL. The cost per QALY gained from knee replacement is two-fold compared to hip replacement. Cost-utility results from the three studied specialties showed that there is great variation in the cost-utility of surgical interventions performed in a real-world setting even when only common, widely accepted interventions are considered. However, the cost per QALY of all the studied interventions, except for revision hip arthroplasty, was well below 50 000, this figure being sometimes cited in the literature as a threshold level for the cost-effectiveness of an intervention. Based on the present study it may be concluded that routine evaluation of the cost-utility of secondary health care is feasible and produces information essential for a rational and balanced allocation of scarce health care resources.

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The temperature sensitivity of decomposition of different soil organic matter (SOM) fractions was studied with laboratory incubations using 13C and 14C isotopes to differentiate between SOM of different age. The quality of SOM and the functionality and composition of microbial communities in soils formed under different climatic conditions were also studied. Transferring of organic layers from a colder to a warmer climate was used to assess how changing climate, litter input and soil biology will affect soil respiration and its temperature sensitivity. Together, these studies gave a consistent picture on how warming climate will affect the decomposition of different SOM fractions in Finnish forest soils: the most labile C was least temperature sensitive, indicating that it is utilized irrespective of temperature. The decomposition of intermediate C, with mean residence times from some years to decades, was found to be highly temperature sensitive. Even older, centennially cycling C was again less temperature sensitive, indicating that different stabilizing mechanisms were limiting its decomposition even at higher temperatures. Because the highly temperature sensitive, decadally cycling C, forms a major part of SOM stock in the organic layers of the studied forest soils, these results mean that these soils could lose more carbon during the coming years and decades than estimated earlier. SOM decomposition in boreal forest soils is likely to increase more in response to climate warming, compared to temperate or tropical soils, also because the Q10 is temperature dependent. In the northern soils the warming will occur at a lower temperature range, where Q10 is higher, and a similar increase in temperature causes a higher relative increase in respiration rates. The Q10 at low temperatures was found to be inversely related to SOM quality. At higher temperatures respiration was increasingly limited by low substrate availability.

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With respect to resource management and environmental impact, organic farming offers rationales for agricultural sustainability. However, agronomic productivity is usually higher with conventional farming. This work aimed at investigating two factors of major importance for the agronomic productivity of organic crop husbandry, nitrogen (N) supply through symbiotic N fixation (SNF) and weed occurrence. Perennial red clover-grass leys and spring cereal crops subjected to regular agricultural practices were studied on 34 organic farms located in the southern and the north-western coastal regions of Finland. Herbage growth, clover content as a proportion of the ley and extent of SNF in perennial leys, and the occurrence of weed species and weed-crop competition in spring cereal stands were related to climate conditions, soil properties, and management measures. The herbage accumulated from the first and the second cut of one- and two-year-old leys averaged 7.5 t DM ha-1 (SD ± 1.7 t DM ha-1); the clover content averaged 43.9% (SD ± 18.8%). Along with the clover content, herbage production decreased with ley age. Radiation use efficiency (RUE) correlated positively with clover proportion but despite low clover contents, three-year-old leys were still productive with regard to RUE. SNF in the accumulated annual growth of one- and two-year-old leys averaged 247.5 kg N ha-1 yr-1 (SD ± 114.4 kg N ha-1 yr-1). It was supposed that if red clover-grass leys constituted 40% of the rotation, then the mean N supply by SNF would be able to sustain two or three succeeding cereal crops (green manure and forage ley, respectively), yielding 3.0 to 4.0 t grain ha-1. Being a function of clover biomass, the SNF increased from the first to the second cut and thereafter declined with ley age. Coefficients of variation of clover contents (and SNF) between and within fields were around 50%, which was about twice as high as those of herbage production. The lower were the clover contents, the higher were the within-field variations of clover as a proportion of the ley. Low clover contents in one-year-old leys and increasing variability with ley age suggested that red clover growth was limited by poor establishment and poor overwintering. The proportions of clover in leys were lower and their variability was higher in the northwest than in the south. Soil properties, primarily texture and structure, had a major impact on clover proportion and herbage production, which largely explained regional differences in ley growth. Within-field variability of soil properties can be amended through site-specific measures, including drainage, liming, and applications of organic manures and mineral fertilizers. Overwintering and the persistence of leys can be improved by the choice of winter-hardy varieties, careful establishment and the appropriate harvest regime. Mean grain yields of spring cereal crops amounted to 3.2 t ha-1 in the south and 3.6 t ha-1 in the northwest. At 570 and 565 m-2 for the south and northwest respectively, mean weed densities did not differ between the regions, whereas the respective mean weed biomass of 697 and 1594 kg dry weight ha-1, respectively did differ. Weed abundance varied remarkably between single fields. The number of weed species was higher in the south than in the northwest. For example, Fumaria officinalis and Lamium spp. were found only in the south. Frequencies and abundances of Lapsana communis, Myosotis arvensis, Polygonum aviculare, Tripleurospermum inodorum, and Vicia spp. were higher in the south, whereas those of Elymus repens, Persicaria spp. and Spergula arvensis were higher in the northwest. The number of years since conversion to organic farming, i.e. long-term management, was one of the variables that explained the abundance of single weed species. E. repens was the weed species whose biomass increased most with the duration of organic farming. Another significant variable was crop biomass, which was affected by short-term management. The presence of different weed species was related to the duration of organic farming and to low crop yield. This finding demonstrated that it was not the organic farming regime per se, which resulted in high weed infestation and low yielding crops, but failures in the understanding and the management of organic farming systems. Successful weed control relies on farm- and field-specific long- and short-term management approaches. The agronomic productivity of ley and spring cereal crops managed by full-time farmers with an interest in organic farming was on the same level as of the mean for conventional farming. Given the many options for further improvements of the agronomic performance of organic arable systems, organic farming offers foundations for the development of sustainable agriculture. The main threat to the sustainability of farming in Finland, both conventional and organic, is the spatial separation of crop production and animal husbandry by region, along with the simplification of associated crop rotations.