Novel Approaches to the Sampling of Atmospheric Aerosols and Determination of Chemical Composition

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.

Why Don't Students Talk? Causes of Foreign Language Communication Apprehension in English Classes: A Comparison of High Apprehensive and Low Apprehensive Upper Secondary Students.

OBJECTIVES. Oral foreign language skills are an integral part of one's social, academic and professional competence. This can be problematic for those suffering from foreign language communication apprehension (CA), or a fear of speaking a foreign language. CA manifests itself, for example, through feelings of anxiety and tension, physical arousal and avoidance of foreign language communication situations. According to scholars, foreign language CA may impede the language learning process significantly and have detrimental effects on one's language learning, academic achievement and career prospects. Drawing on upper secondary students' subjective experiences of communication situations in English as a foreign language, this study seeks, first, to describe, analyze and interpret why upper secondary students experience English language communication apprehension in English as a foreign language (EFL) classes. Second, this study seeks to analyse what the most anxiety-arousing oral production tasks in EFL classes are, and which features of different oral production tasks arouse English language communication apprehension and why. The ultimate objectives of the present study are to raise teachers' awareness of foreign language CA and its features, manifestations and impacts in foreign language classes as well as to suggest possible ways to minimize the anxiety-arousing features in foreign language classes. METHODS. The data was collected in two phases by means of six-part Likert-type questionnaires and theme interviews, and analysed using both quantitative and qualitative methods. The questionnaire data was collected in spring 2008. The respondents were 122 first-year upper secondary students, 68 % of whom were girls and 31 % of whom were boys. The data was analysed by statistical methods using SPSS software. The theme interviews were conducted in spring 2009. The interviewees were 11 second-year upper secondary students aged 17 to 19, who were chosen by purposeful selection on the basis of their English language CA level measured in the questionnaires. Six interviewees were classified as high apprehensives and five as low apprehensives according to their score in the foreign language CA scale in the questionnaires. The interview data was coded and thematized using the technique of content analysis. The analysis and interpretation of the data drew on a comparison of the self-reports of the highly apprehensive and low apprehensive upper secondary students. RESULTS. The causes of English language CA in EFL classes as reported by the students were both internal and external in nature. The most notable causes were a low self-assessed English proficiency, a concern over errors, a concern over evaluation, and a concern over the impression made on others. Other causes related to a high English language CA were a lack of authentic oral practise in EFL classes, discouraging teachers and negative experiences of learning English, unrealistic internal demands for oral English performance, high external demands and expectations for oral English performance, the conversation partner's higher English proficiency, and the audience's large size and unfamiliarity. The most anxiety-arousing oral production tasks in EFL classes were presentations or speeches with or without notes in front of the class, acting in front of the class, pair debates with the class as audience, expressing thoughts and ideas to the class, presentations or speeches without notes while seated, group debates with the class as audience, and answering to the teacher's questions involuntarily. The main features affecting the anxiety-arousing potential of an oral production task were a high degree of attention, a large audience, a high degree of evaluation, little time for preparation, little linguistic support, and a long duration.

Chemical Characterization of Urban Background Aerosol Using Online And Filter Methods

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.

Promoting the European Union : Attitudinal stance adjectives in three genres of EU communication to the public

Målet för Pro Gradu-avhandlingen är att undersöka hur Europeiska unionen (EU) marknadsförs genom användningen av värderande adjektiv i tre genrer av skriftlig kommunikation från EU till medlemsstaternas medborgare. Undersökningen är inriktad på tre forskningsfrågor: hur marknadsföringen av EU syns i användningen av värderande adjektiv i de tre genrerna, vilka de centrala skillnaderna mellan de tre genrerna är gällande användningen av värderande adjektiv, samt på vilket sätt texterna uppfyller sitt kommunikativa syfte, nämligen att informera allmänheten om EU:s verksamhet och marknadsföra EU som en giltig och handlingskraftig union. Den teoretiska ramen för undersökningen grundar sig på genreanalys, kommunikationsteori och teorier om hur författarens värdering (stance) syns i texter. Skillnaden mellan genre, texttyp och register diskuteras, och teoridelen redogör även för begreppet diskurssamfund, dvs. den grupp personer som i ett yrkesmässigt eller institutionellt sammanhang producerar och använder sig av en genre enligt dess kommunikativa konventioner. Materialet behandlas även utgående från Egon Werlichs indelning av texttyper i deskriptiva, narrativa, expositära, argumentativa och instruktiva texter. Materialet består av tre delar som representerar var sin genre: informationsbroschyrer, pressmeddelanden och den Allmänna rapporten om Europeiska unionens verksamhet, som utges av EU varje år. Storleken på varje del av materialet varierar mellan 20 000 - 30 000 ord. Materialet har valts på basis av de teman texterna behandlar, och kriterierna för urvalet är bl.a. att texterna behandlar ämnen som har anknytning till medborgarnas vardag, att de är riktade till allmänheten, och att de finns tillgängliga på Internet. Undersökningen är genomförd som en kvalitativ genreanalys. Materialet analyseras först utgående från kontexten och det samhälleliga sammanhanget enligt Vijay K. Bhatias metodik för analys av obekanta genrer. Det kommunikativa syftet, författaren och den tilltänkta läsarkretsen, dvs. målgruppen för kommunikationen, fastställs. Värderande adjektiv som uttrycker författarens hållning har plockats ur texten manuellt och med hjälp av konkordansprogrammet AntConc, och placerats i 16 kategorier enligt de värden de uttrycker. Varje genre analyseras sedan språkligt med utgångspunkt i adjektivlistorna, varefter resultaten jämförs med varandra. Undersökningen visar att pressmeddelandena innehåller det största antalet värderande adjektiv, medan informationsbroschyrerna innehåller det minsta antalet värderande adjektiv. Den Allmänna rapporten om Europeiska unionens verksamhet innehåller delar med tätt förekommande värderande adjektiv, i synnerhet i stycken som behandlar mer kontroversiella ämnen. I alla tre genrer sammanfaller ett högt antal värderande adjektiv med argumentativ text, och argumentativ text förekommer främst då ämnet som diskuteras rör sig på en mer abstrakt nivå, t.ex. om EU:s värderingar och grundläggande principer, eller då texten behandlar sådan politik som delar allmänhetens uppfattning. För EU utgör alla tre genrer viktiga kanaler för kommunikationen till medlemsstaternas medborgare, och EU kan genom sitt informationsmaterial och sina officiella publikationer informera om, förklara och marknadsföra sin verksamhet på ett sätt som avser att upprätthålla och förbättra EU:s image. Utarbetandet av lämpliga texter är ändå krävande på grund av den heterogena målgruppen, och det är en utmaning i sig att få fram rätt budskap bland det stora utbudet information som finns tillgängligt på Internet.