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Household and road dust as indicators of airborne particulate matter elemental composition
Klemen Teran, 2020, doktorska disertacija

Opis: Household dust (HD) and road dust (RD) are widespread and easily accessible urban sediments, which are influenced by deposition of airborne particulate matter (PM). Since airborne PM is considered to be one of the most important pollutants in urban areas, with significant adverse effects on human health, a better understanding of its elemental composition and dispersion mechanisms is needed. The present study examines whether the HD and RD elemental composition can be used as a quick alternative method for the determination of corresponding PM elemental composition over a selected area. In summer 2016, HD, RD, and topsoil samples were collected from 249 sampling locations distributed across rural, urban, and industrial areas in Slovenia. The collected samples were sieved for particle diameters below 63 μm and analysed for 53 elements with ICP-MS after aqua regia digestion. SEM/EDS analyses were applied for the determination of characteristic particles at the microlevel. Finally, the elemental composition of HD and RD was compared with the PM10 elemental composition obtained from National Network for Ambient Air Quality Monitoring governed by Slovenian Environmental Agency (ARSO) to determine any potential connection between them. The results show that HD and RD are considerably enriched with a large set of elements compared to the topsoil. Correlations and factor analyses show that spatial distribution of factor scores in RD revealed strong regional trends, connected with soil resuspension (Al, Ce, Ga, K, La, Li, P, Rb, Sc and Y) or with anthropogenic sources such as traffic (Ag, Bi, Cu, Sb and Sn), steel mill emissions (Cr, Mo, Mn, Ni and W) and construction material decomposition (Ca and Sr). In contrast, HD elemental composition was highly variable between sampling locations. Variability was probably caused by indoor sources, such as smoking (Ce and La), biomass combustion (K, P and Rb), construction material decomposition (Ca and Sr) and residents’ professional occupation: dental care employees (Ag, Au, Pd) and employees in the metal-processing industry (Cr, Mo, Ni). Among deposited particles in RD, urbanization processes, such as fossil fuel combustion and traffic emissions, including brake pad abrasion and tyre wear, contributed the largest share of particles with anomalous elemental composition. Brake pad abrasion, for instance, contributed Ba-, Cu-, Sn-, and Zn-enriched irregular, angular and tabular particles, while tyre wear produced elongated rubber particles with traces of Ba, Cu, and Zn. RD from urban areas showed significantly higher elemental levels of Ag, Bi, Ca, Cd, Cr, Cu, Hg, Fe, Mo, Nb, Pb, Pt, Sb, Sn, Sr, Ti, Zn, and W in comparison to the rural environment, indicating the strong impact of urbanization on RD elemental composition. Another important anthropogenic source of deposited particles in RD were steel mills. Strong anomalies of Cr, Mo and Ni were detected in their vicinity. Their elemental levels decreased with distancing from the plan location, reaching urban background levels between 15 and 20 km from the mills. SEM/EDS analyses identified enrichments of Cr, Mn, Mo, Ni, V, and W in spherical particles and particles with partially melted surfaces, which were found only in the proximity of steel mills, indicating their influence of the PM deposition. Comparison of RD and the corresponding PM10 elemental composition showed that the RD fraction with particle diameters below 63 μm reflects PM10 elemental composition for the last 30 to 90 days for Cr, Cu, Mo and Zn and can be used as a predictor for PM10 elemental levels. This is not true for HD, as indoor particle sources prevail over the deposition of ambient PM10.
Ključne besede: household dust, road dust, particulate matter, PM10, pollution, Slovenia, steel mills, topsoil, traffic, urbanization
Objavljeno: 02.12.2020; Ogledov: 332; Prenosov: 32
.pdf Polno besedilo (16,34 MB)

Olena Pliekhova, doktorska disertacija

Opis: This work entitled «Zr/Cu-TiO2 catalysts for photocatalytic water treatment» tackles a problem of tons of dyes discharged everyday mainly from textile industries. This is a huge concern because of dyes persistence, toxicity and potential to the bioaccumulation in living organisms. Here, a small contribution to overall problem is presented. The research work consists of three main parts: Theoretical background, Experimental and Results and discussion. In the Theoretical background chapter the overall problem is identified and discussed. The main water treatment techniques are presented briefly with their advantages and drawbacks. Photocatalysis assisted with TiO2 is shown as an alternative additional technique with its own pros and cons. Further, a cursory overview of TiO2 modification techniques is made and advantages in using copper and zirconium oxides for TiO2 modification are presented. The reason and possible positive effect of using of two oxides simultaneously for TiO2 modification is indicated. Additionally, a positive impact of solar light for overall rate of dyes degradation assisted with TiO2 is discussed. Within the framework of photosensitization effect, the problem of using dyes for assessment of photocatalytic properties of materials under the visible light is touched on. Photothermal methods as possible beneficial techniques for this purpose are proposed. In the Experimental chapter, all experimental techniques used in current research work with the technical details specific for the research work are presented. There are methods of materials preparation, photocatalytic tests under different conditions and varying model pollutants, and physico-chemical characterization techniques. The Results and discussion chapter is divided by three subchapters. Each chapter is dedicated to one hypothesis, which was checked and confirmed or disproved. The first hypothesis is about beneficial loading of copper and zirconium oxides to TiO2. After numerous experiments held, it was concluded that the pair of copper and zirconium oxides is beneficial for simultaneous application on TiO2 surface to promote its performance. The second subchapter is about zirconium distribution and its impact on the activity of studied materials towards the antraquinone dye Reactive Blue 19. Different techniques such as XRD, TEM, EXAFS and many others were used in order to characterize the materials and to understand the details of the processes taking place. The existence of upper limit of copper oxide loading for its beneficial effect on TiO2 performance was demonstrated. It was observed that zirconium species loading leads to improvement in performance of materials with higher copper loading, which otherwise lowers activity of TiO2 – this is in case when copper only above its optimal level is present. It was concluded that zirconium oxide containing species occupy rutile surface sites in mixed phase TiO2 and this way beneficially influence the material performance towards the dye removal. The third subchapter is about the visible light TiO2 assisted dye degradation. It is well known that photosensitization mechanism of dye degradation appears under the visible and as a consequence under the solar light irradiation. This leads to the overall enhancement of dyes degradation, which is positive and may be used as a benefit for faster pollutant destruction. However, this fact leads to mishmash in the determination of real photocatalytic activity of materials towards the dye. It was hypothesized that the impact of photosensitization mechanism on the overall material performance against Reactive blue 19 dye (RB19) descends with the dye concentration lowering. Thermal lens spectrometry (TLS) which is sensitive to chemicals at low concentrations was used for hypothesis evaluation. To summarize the research work achievements, the conclusions of the thesis are given at the end.
Ključne besede: titanium dioxide, photocatalysis, zirconium/copper, surface modification, water treatment, dyes
Objavljeno: 03.12.2019; Ogledov: 1106; Prenosov: 38
.pdf Polno besedilo (3,18 MB)

The detection and study of biologically active compounds in environmental processes and samples
Mojca Žorž Furlan, doktorska disertacija

Opis: Environmental pollution in the 21th century still represents a global problem for human and animal health. Despite general awareness about released substances and their degradation products their fate and possibilities of removal are not well investigated. Even though the chemicals released are dispersed and diluted in water cycles, their poor biodegradability and/or strong accumulation can result in the intoxication of exposed organisms. Similarly, as a part of the environment, food can get contaminated by bioactive substances during different steps of preparation. Not only artificial compounds such as pesticides or pharmaceuticals, but also natural toxins enter the food chain and impact negatively on humans' and animals' health. In addition, the activity of some bacteria can influence the production of amines from amino acids after fermentation, to which the human body responds with several symptoms of intoxication. Several analytical methods for the determination of trace levels of broad range contaminants have been developed. Due to the largely robust, selective and sensitive features of the conventional (rearguard) techniques, they represent the first choice for analysing multiple organic compounds in frequently very complex matrices. However, screening (vanguard) methods are paving the way in the chemical analytics as a solution that provides simplicity and rapid analytical responses with binary (yes/no) answers. They require little or no sample treatment as well as more economically-efficient instrumentation. The combination of vanguard-rearguard analytical strategies hence offers a compromise between classical analytical figures of merit and productivity-related characteristics. In the first part of our research feasibility studies for the application of TLS and/or TLM in novel analytical methods for the determination of lipid-lowering drug atorvastatin and a mycotoxin ochratoxin A . The survey on atorvastatin performed spectrophotometrically has shown a decrease of ATV-sulpho-vanillin product at the wavelength of its maximum absorbance after dilution by organic solvent, which was investigated due to the possible increasing of the method sensitivity. As the predicted LODs that could be obtained by TLM (0.3 mg/L) could not reach the concentration of ATV usually present in the environment (ng/L-g/L) further experiments on this subject were therefore not justified. On the other hand, the ELISA assay for the determination of ochratoxin A was performed. In case of μFIA-TLM, the measurements were influenced by high background signal resulting in high LODs of TLM (470 pg/mL), which is known as a background limited technique. It was estimated that the LODs of standard ELISA assay could not be significantly improved, therefore no further research was conducted in this direction. In the second part of the dissertation, a sensitive rearguard system by coupling HPLC and TLS for the determination of biogenic amines in wine samples was developed. Putrescine, cadaverine, histamine and tyramine were separated and detected on a HPLC-TLS system after derivatization by dabsyl chloride. The method was optimized in terms of chromatographic conditions and in terms of TLS parameters. Also, the sensitivity of the newly developed method was evaluated by comparing the TLS detection with DAD detection in terms of LOD values, where TLS showed 3.6-fold improvement compared to DAD. Afterwards, the standard addition calibration was performed and evaluated for its recoveries (86−117%) in the determination of the four BAs. The applicability of the novel method was tested by the analysis of real white and red wine samples and by comparing the results to the standard HPLC-FL method and concentrations of BAs in wine samples were in good accordance. In addition, the dabsylated BAs showed better stability compared to the OPA derivatives as they have not lost the peak intensity after 17h of storage. In the third part, a vanguard system for detection of the overall biogenic amines concentration was developed by employing μFIA-TLM. Initially, NH4Cl standard solutions were applied in the indophenol reaction for batch mode, off-line μFIA-TLM and in an on-line indophenol formation for μFIA-TLM detection. By adding 50 % of EtOH to indophenol we obtained 9-fold improvement. In addition, indophenol showed good stability under TLM conditions. We optimized the microfluidic and TLM parameters in the off-line and on-line indophenol reaction. The addition of 5% ethanol to the reagent in the on-line reaction resulted in the 3-fold improvement of the signal-to-noise ratio. Further on, the overall reaction, including the enzymatic and the following indophenol reaction, was optimized by choosing the optimal buffer (pH=7, 0.5 M) and alkaline conditions (2M NaOH). The influence of interferences from amino compounds was also evaluated and discussed. The off-line and on-line μFIA-TLM were evaluated by their performance characteristics. The LOD for ammonia detection reached 2.3 μM and the applicability in ammonia detection in water samples was discussed. Similar LOD of 3.2 μM was obtained for the overall concentration of BAs and LOD of 3.8 μM for histamine, which is more than 4-folds lower value as the lowest suggested limits of intake for histamine in wine samples (2 mg/L; 18 μM). Finally, an immobilization procedure on magnetic nanoparticles was developed for the possible implementation of the selected enzyme in a miniaturized biosensor.
Ključne besede: thermal lens spectrometry, thermal lens microscopy, high performance liquid chromatography, microfluidics, biogenic amines, microbial transglutaminase, indophenol (Berthelot) reaction
Objavljeno: 04.06.2018; Ogledov: 1833; Prenosov: 157
.pdf Polno besedilo (2,90 MB)

Poezija Franceta Prešerna v srednješolskih učbenikih in njena recepcija
Zoran Božič, 2010, doktorska disertacija

Opis: Disertacija obravnava dva problemska sklopa: poezijo Franceta Prešerna v srednješolskih učbenikih za pouk književnosti od leta 1850 do leta 2010 ter recepcijo Prešernovih pesmi skozi čas in v sodobnosti. V prvem problemskem sklopu razkriva dejavnike in postopke šolske kanonizacije Prešerna ter razvoj didaktizacije beril v smeri učne knjige za samostojno delo z besedilom. V drugem problemskem sklopu raziskuje posebnosti pri razumevanju, doživljanju in vrednotenju Prešernovih pesmi ter načine za njihovo čimbolj učinkovito šolsko predstavitev. Glede na to, da se je kanonizacija Prešerna začela že za časa njegovega življenja, je bil seveda vseh 160 let kanonski avtor, vendar pa kljub nenehnemu označevanju Prešerna za "največjega slovenskega pesnika" po številu besedilnih enot v berilih ni bil vedno prvi avtor, pač pa so ga večkrat prehitevali mlajši književniki, ki so bolj ustrezali trenutnim afinitetam sestavljavcev srednješolskih beril. Predvsem v drugi polovici 19. stoletja in tudi kasneje je bil zaradi negativnega odnosa šolskih oblasti do ljubezenske poezije izbor Prešernovih pesmi praviloma manj primeren (na nižji stopnji je bil največkrat objavljen sonet Memento mori, na višji stopnji pa cikel Soneti nesreče), nekatere ljubezenske pesmi pa so celo cenzurirali. Od druge polovice 19. stoletja do danes se je razvijal didaktični instrumentarij srednješolskih beril (najprej so začeli dodajati stvarne opombe, kasneje pa še vprašanja in naloge za dejavno razčlembo leposlovnega besedila), vendar so še zlasti v obdobju po drugi svetovni vojni nekateri sestavi beril didaktično pomenili izrazito nazadovanje. Od sedemdesetih let dalje berila vključujejo tako literarnovedne vsebine kot vprašanja in naloge, sodobna berila pa se praviloma (izjema je npr. antološki sestav Krakar 2003) razvijajo v smeri vezanega berila z relativno majhno ponudbo leposlovnih besedil. Zgodovinski pregled je pokazal, da so imeli težave z razumevanjem Prešernovih pesmi že njegovi sodobniki, kasneje pa tudi izobraženci, celo poznavalci Prešerna. Empirični preizkusi med slovenskimi srednješolci potrjujejo visoko recepcijsko zahtevnost Prešernove poezije. Nekatere osrednje Prešernove pesmi (npr. Krst pri Savici) zahtevajo izjemno gostoto dodanih opomb, zato je najustreznejše didaktično sredstvo za boljše razumevanje in doživljanje oblikovno in slogovno zahtevne klasične poezije dodana prozifikacija, kar so v celoti potrdili tudi rezultati pedagoškega eksperimenta.
Ključne besede: poezija, Prešeren, didaktika, recepcija, kanonizacija, srednja šola, berilo, kanonizacija, prozifikacija, pedagoški eksperiment
Objavljeno: 12.05.2016; Ogledov: 2884; Prenosov: 85
.pdf Polno besedilo (10,63 MB)

On non-simultaneous phases
Franc Marušič, 2005, doktorska disertacija

Ključne besede: jezikoslovje, slovenščina, skladnja, teorija faz, minimalizem, rekonstrukcija, dvig kvantifikatorjev, elektronski vir
Objavljeno: 15.10.2013; Ogledov: 3494; Prenosov: 9
.pdf Polno besedilo (1,25 MB)

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