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The objectives of this research programme were to examine the influence of manufacturing and processing parameters on the environmental stability of aqueous acrylic based latices and to also extend the programme to an assessment of the behaviour of various stabiliser types suitable to such materials through either end-group modification or direct in-situ addition. During the research programme a number of physical and chemical techniques were assessed to routinely characterise and monitor the photochemical and thermal degradation of acrylic latices. These were based on emulsion polymerised formulations of methyl methacrylate and butyl acrylate. In the first instance, acrylic latices based on different formulations were chosen as homopolymers and copolymers. Here the nature of impurities and oxidation products generated during various stages of their manufacture have to be characterised and inter-related to their influence on subsequent environmental degradation. This involved the use of reflectance FT-IR spectroscopy to show functional group changes together with colourimetric U.V. analysis to determine photochemical generation of hydroperoxides. The early chemical changes and their subsequent influence on the physical and chemical properties of the latices during the later stages of environmental degradation were found to exhibit a close inter-relationship. In this regard the formation and the manufacturing temperatures and periods were crucial. Thermal methods of analysis were also used to characterise differences in the properties of the latices before and during thermal and photochemical oxidation. The nature of the residual persulphate initiator and the compositions of the latices in terms of end group modification were important parameters. De-esterification and hydroperoxide formation were found to be important processes during latex degradation while the use of low levels of co-monomer addition. such as methacrylic acicL to the emulsion reaction gave latices with improved light stability. Subsequent aspects of the research programme involved a detailed investigation into the behaviour and performance of various stabiliser types and formulations. Thus, while coreactive hindered piperidine stabilisers was found to be effective, the incorporation of simple terminal dialkyl acrylamide/methacrylaroide groups were also found to be effective. The efficiency of dialkylamide groups operating through a sacrificial mechanism is discussed. The influence of these processing operations on subsequent stabiliser activity provides valuable information on the mode of action of these stabilisers in such complex media. Further work involved a study into the effect of fluorinated methacrylates used in emulsion polymerised formulations. Here, the presence of residual starting materials in the monomer was found to have a detrimental effect in terms of photostability. Subsequent analysis of acrylic resins, based on solution polymerised formulations of methyl methacrylate and fluorinated methacrylates, was undertaken. The influence of reactive stabiliser types on these resins was important and to improve stabiliser perfonnance, synergistic stabiliser formulations were studied. This project will provide important fundamental information on the behaviour of active chromophores produced during the manufacturing process and hopefully resuh in the development of monitoring methodologies to establish paint quality.

"The simultaneous degradation of five organic contaminants: 1,4 dioxane, n-nitrosodimethylamine, tris-2-chloroethyl phosphate, gemfibrozil, and 17β estradiol, was investigated using a 1 L batch water-jacketed UV photoreactor utilizing titanium dioxide (TiO2) nanoparticles (Degussa P-25) as a photocatalyst. The primary objectives of this research were: (1) to experimentally assess the feasibility of heterogeneous photocatalysis as a promising alternative for the degradation of organic compounds in water; and (2) to model the chemical reactions by the application of two different approaches based on adsorption – surface reactions (Langmuir–Hinshelwood) and its simplification to a first order rate reaction. These objectives were motivated by the lack of information regarding simultaneous degradation of organic compounds in different categories as found in real aqueous matrices, and generation of specific intermediates that could eventually represent a potential risk to the environment. Contaminants were chosen based on their occurrence in water sources, their representativeness of individual sub-categories, and their importance as part of the CCL3 as potential contaminants to be regulated. Contaminant degradation was evaluated over time, and the TiO2 concentration and solution pH were varied under constant UV irradiation, oxygen delivery rate, mixing gradient, and temperature. 

 Specific accomplishments of this study were: (1) reaction kinetics data were obtained from the UV/TiO2 experiments and showed the potential that this UV/TiO2 process has for effectively removing different types of organic compounds from water; (2) a good fit was obtained between photocatalytic reaction kinetics models and the contaminant data using pseudo first-order and Langmuir-Hinshelwood (L-H) models; (3) results of the analytical methods developed in this study were validated by measurements performed by a certified laboratory; (4) the reaction kinetic parameters obtained in this study were normalized to electrical energy per order, reactor volume and surface area of the photocatalyst in order to provide rate constants with wider applicability for scale-up to more complex systems; and (5) degradation intermediates from the oxidation process and from interaction among compounds were identified and possible pathways for their formation suggested. This research has provided a better understanding of the photocatalytic process for the removal of organic contaminants from complex aqueous matrices."

The lethal effect of ultraviolet (UV) light on microorganisms is well known and many studies have been undertaken into the effects of UV induced damage. Most of this work has been experimental; by comparison relatively little theoretical work has been undertaken to analyse the kinetics of the UV inactivation process, or to develop quantitative methodologies to support the experimental work. This paper presents a new and simple model for quantifying the photolysis rate. A theoretical study is also presented in this paper which quantifies photolysis rates for E. coli O26 and E. coli O157:H7. This study uses experimental data collected by Tosa and Hirata, and reveals the photolysis rate for E. coil O26 during the UV irradiation process to be 4.69 x 10(-3) m2 J(-1). By comparison, E. coli O157:H7 is much more susceptible to UV induced damage than E. coli O26, having a photolysis constant of only 2.09 x 10(-3) m2 J(-1).

The selectivity mechanism of the UV-light activated metal oxide semiconductor (MOS) gas sensors was studied. A reaction model based on two competing redox processes was presented to solve the selectivity problem. A concept named dynamic equilibrium of adsorbed oxygen concentration was brought about in this model and two reaction responses were discussed: (1) when most of the MOS surface is adsorbed with oxygen, the resistance of the MOS gas sensor will decrease upon the injection of reducing agents (RAs); (2) when most of the MOS surface is not adsorbed with oxygen, the resistance of the MOS gas sensor will increase upon the injection of RAs. Finally, experiments were conducted on ZnO MOS gas sensors to prove the proposed hypothesis of the reaction mechanism. / Thesis / Master of Applied Science (MASc)

The benefits of low UV dose treatment of horticultural produce – also known as hormetic treatment - have been attested to in numerous studies conducted over the last 15 years. However, commercial growers have not adopted the concept of hormesis. With increasingly stringent controls on the use of fungicides and other chemical agents the time has come to examine how hormetic treatment might be applied in the horticulture sector. The objectives of this work were firstly, to confirm UV-induced hormetic effects applied postharvest for a number of different types of produce, namely, tomatoes, broccoli, strawberries and mangoes. Secondly, to evaluate the use of rollers to ensure full surface treatment of produce, and thirdly to evaluate the possibility of treating produce preharvest. In order to investigate surface UV dose distributions, a polystyrene sphere (Diameter 70 mm) was used to simulate fruits such as tomatoes, apples, peaches etc., that have an approximately spherical form. Biodosimetry based on spores of Bacillus subtilis was employed to experimentally determine UV doses and to compare the results obtained with theoretical predictions. Good agreement was obtained and the modelling approach was extended to other types of produce. This showed the amenability of mechanical rollers to ensure full surface treatment of produce. Postharvest treatment of produce was carried using conventional low intensity UV sources principally emitting at 254 nm and also a commercially available high energy pulsed UV source. Treatment using the conventional UV source was carried out on mechanical rollers within a UV cabinet designed for this work at a fixed distance from the source and at an intensity of 1000 μW/cm2. A 5 minute conventional UV treatment of tomatoes was approximately comparable to fruit given a 3-pulsed treatment using the pulsed source (507 J/pulse of polychromatic light). The colour and texture of both groups of fruit were significantly maintained as compared with controls. The treated tomatoes also showed a significant increase in the ascorbic acid levels during storage. Similarly, a 15 minute conventional UV treatment of broccoli heads was comparable to heads given a 10-pulsed treatment using the pulsed source. Where both treatments gave rise to a statistically significant retention of green colour of treated broccoli. In addition, mangoes given a 10 minute conventional UV treatment were comparable to fruit given a 20-pulsed treatment using the pulsed source with both treatments leading to maintenance of texture as compared to control fruit. This confirmed the UV-hormetic effects. The effects of conventional and pulsed treatments are compared and discussed. Preharvest treatment of tomatoes and strawberries was carried out in commercial glasshouses. Doses of either 3 or 8 kJ/m2 were delivered to the fruits using a treatment device designed for the work, which delivered a combined intensity of 2000 μW/cm2 from two low pressure UV sources. The treated tomatoes showed a delay in development of colour as measured on the vine and after picking. Picked tomatoes were inoculated with P. digitatum and C. gloeosporioides and the results obtained showed a significant inhibition of the development of the fungi in the treated fruit during the storage period. These results suggest that the beneficial response shown by the preharvest treatment is not a localised one but a systematically induced resistance observable throughout the treated plant. This was shown by monitoring tomato fruits on treated plants which themselves where not directly exposed to the UV light. The two doses elicited different responses in the treated strawberries, with the 8 kJ/m2 dose causing the fruit to redden significantly faster than the 3 kJ/m2 treated fruits and controls. This could have significant nutritional benefit as the red colour of strawberries has been correlated with anthocyanin levels. On the other hand, treatment at the lower UV dose led to a lag in colour development. The amenability of the equipment utilised for commercial application is discussed.

<p>For produced biogas to be usable as vehicle fuel it has to be upgraded to a higher energy content. This is accomplished by elevation of the methane concentration through removal of carbon dioxide. Absorption with water wash is the most common upgrading method used in Sweden today. The upgrading technique is based on the fact that carbon dioxide is more soluble in water than methane. Upgrading plants that utilises this method have problems with microbial growth in the system. This growth eventually leads to a stop in operation due to the gradually drop in upgrading capacity.</p><p>The aim of this thesis were to evaluate the possibility to through some kind of water treatment maintain an acceptable level of growth or altogether prevent it in order to maintain an acceptable process capacity and thereby avoid the need to clean. Through collection of literature the implementation possibilities were evaluated with regard to efficiency, economic sustainability and if there would be a release of any harmful substances.</p><p>In order to prevent the microbial growth in the columns the treatment should either focus on removing microorganisms or limit the accessible nutrients. For the single pass system it is concluded that the treatment should reduce the biofilm formation and be employed in an intermittent way. Among the evaluated treatments focusing on the reduction of microorganisms the addition of peracetic acid seems to be the most promising one. For the regenerating system the treatment method could focus on either one. As for the single pass system peracetic acid could be added to reduce the amount of microorganism. To reduce the amount of organic matter an advanced oxidation process could be deployed with the advantage that it also could remove the microorganisms.</p> / <p>För att kunna använda den producerade biogasen som fordonsgas måste dess energiinnehåll höjas. Detta åstadkoms genom avskiljning av koldioxid så att metankoncentrationen ökar. Den vanligaste förekommande uppgraderingstekniken i Sveriges är absorption med vatten, som bygger på att koldioxid är mer lösligt än metan i vatten under tryck. Uppgraderingsanläggningarna har mikrobiell tillväxt på fyllkropparna i absorptionskolonnen, vilket ofrånkommligen orsakar en lägre uppgraderingskapacitet och slutligen är ett stopp i produktionen nödvändig för kunna tvätta fyllkropparna. Anläggningarna som recirkulerar processvattnet kan även ha tillväxt i kolonnen, där den lösta koldioxiden tas bort.</p><p>Syftet med detta arbete var att genom en litteraturstudie undersöka om det vore möjligt att undvika eller åtminstone hålla tillväxten under en acceptabel nivå genom någon typ av vattenrening. De olika reningsmetoderna utvärderades med avseende på möjlighet att implementeras i det befintliga uppgraderings systemet, effektivitet, möjliga utsläpp och ekonomisk hållbarhet.</p><p>För att begränsa tillväxt i kolonnerna ska vattenreningen antingen fokusera på att ta bort mikroorganismer eller begränsa tillgången på näringsämnen för bakterierna som når kolonnerna via biogasen, luften som används för att ta bort koldioxiden från vattnet, eller via vattnet. För uppgraderingsanläggningar där processvattnet bara passerar kolonnen en gång rekommenderas en reningsmetod som fokuserar på reducera bildandet av biofilmen. Av de utvärderade metoderna ter sig perättiksyra som det bästa alternativet. För system med recirkulerande processvatten skulle reningsmetoden fokusera på antingen reduktion av mikroorganismer, organiskt material eller både och. Som för anläggningar med icke-cirkulerande vatten verkar perättiksyra vara det bästa alternativet för reduktion av mikroorganismer. En avancerad oxidationsprocess skulle kunna användas för att reducera mängden mikroorganismer och organiskt material.</p>

For produced biogas to be usable as vehicle fuel it has to be upgraded to a higher energy content. This is accomplished by elevation of the methane concentration through removal of carbon dioxide. Absorption with water wash is the most common upgrading method used in Sweden today. The upgrading technique is based on the fact that carbon dioxide is more soluble in water than methane. Upgrading plants that utilises this method have problems with microbial growth in the system. This growth eventually leads to a stop in operation due to the gradually drop in upgrading capacity. The aim of this thesis were to evaluate the possibility to through some kind of water treatment maintain an acceptable level of growth or altogether prevent it in order to maintain an acceptable process capacity and thereby avoid the need to clean. Through collection of literature the implementation possibilities were evaluated with regard to efficiency, economic sustainability and if there would be a release of any harmful substances. In order to prevent the microbial growth in the columns the treatment should either focus on removing microorganisms or limit the accessible nutrients. For the single pass system it is concluded that the treatment should reduce the biofilm formation and be employed in an intermittent way. Among the evaluated treatments focusing on the reduction of microorganisms the addition of peracetic acid seems to be the most promising one. For the regenerating system the treatment method could focus on either one. As for the single pass system peracetic acid could be added to reduce the amount of microorganism. To reduce the amount of organic matter an advanced oxidation process could be deployed with the advantage that it also could remove the microorganisms. / För att kunna använda den producerade biogasen som fordonsgas måste dess energiinnehåll höjas. Detta åstadkoms genom avskiljning av koldioxid så att metankoncentrationen ökar. Den vanligaste förekommande uppgraderingstekniken i Sveriges är absorption med vatten, som bygger på att koldioxid är mer lösligt än metan i vatten under tryck. Uppgraderingsanläggningarna har mikrobiell tillväxt på fyllkropparna i absorptionskolonnen, vilket ofrånkommligen orsakar en lägre uppgraderingskapacitet och slutligen är ett stopp i produktionen nödvändig för kunna tvätta fyllkropparna. Anläggningarna som recirkulerar processvattnet kan även ha tillväxt i kolonnen, där den lösta koldioxiden tas bort. Syftet med detta arbete var att genom en litteraturstudie undersöka om det vore möjligt att undvika eller åtminstone hålla tillväxten under en acceptabel nivå genom någon typ av vattenrening. De olika reningsmetoderna utvärderades med avseende på möjlighet att implementeras i det befintliga uppgraderings systemet, effektivitet, möjliga utsläpp och ekonomisk hållbarhet. För att begränsa tillväxt i kolonnerna ska vattenreningen antingen fokusera på att ta bort mikroorganismer eller begränsa tillgången på näringsämnen för bakterierna som når kolonnerna via biogasen, luften som används för att ta bort koldioxiden från vattnet, eller via vattnet. För uppgraderingsanläggningar där processvattnet bara passerar kolonnen en gång rekommenderas en reningsmetod som fokuserar på reducera bildandet av biofilmen. Av de utvärderade metoderna ter sig perättiksyra som det bästa alternativet. För system med recirkulerande processvatten skulle reningsmetoden fokusera på antingen reduktion av mikroorganismer, organiskt material eller både och. Som för anläggningar med icke-cirkulerande vatten verkar perättiksyra vara det bästa alternativet för reduktion av mikroorganismer. En avancerad oxidationsprocess skulle kunna användas för att reducera mängden mikroorganismer och organiskt material.

Yes / This article describes the synthesis and application of lanthanide-based luminophores for visualisation under short wavelength ultraviolet (UV) activation (typically 254 nm). Luminophores are chemical compounds which re-emit light of longer wavelength than typical fluorescence and phosphorescence, following photoexcitation, because of efficient energy transfer from the ligands to the lanthanide ion emission levels. The luminophores described in this article are all derived from europium and terbium metal complexes and cover the complete colour gamut. Selection of appropriate ligands allows for water solubility or water insolubility (if required pigment or disperse “dye” applications). Similar to dyeing or printing processes, the anionic complexes can be applied to polyamide fibres or to cellulosic fibres, whereas dispersions of the non-ionic complexes are suitable for polyester or cellulose acetate fibre application. The water-soluble derivatives are also suitable for ink-jet printing and the water-insoluble derivatives are suitable for lithographic or intaglio paper printing. The novel complexes are excited by radiation below 300 nm and thus cannot be activated by sunlight (the earth's atmosphere prevents light below about 300 nm reaching the surface). Accordingly, the photo-stability of the dyed materials and prints obtained is excellent. These materials could be used in security marking applications, for example bank-notes and passports, where they could replace the current fluorophores that are rendered visible under near UV light (typically 365 nm) illumination but exhibit relatively poor photo-stability. The development of an RGB (red, green and blue) colour palette for inkjet printing based on these innovative luminophores will significantly support the design of digitally printed security features. / The research was part funded by Inovink Ltd and theWorshipful Company of Clothworkers of the City of London.

Cutaneous lupus erythematosus (CLE) represents a complex autoimmune disease with a broad phenotypic spectrum ranging from acute to chronic destructive cutaneous lesions. Patients with CLE exhibit high photosensitivity and ultraviolet (UV) irradiation can lead to systemic flares in systemic lupus erythematosus. However, the exact mechanisms how UV irradiation enhances cutaneous inflammation in lupus are not fully understood. Recently, new molecular mechanisms of UV-driven immune responses in CLE were identified, offering potential therapeutic approaches. Especially the induction of type I interferons, central cytokines in lupus pathogenesis which are released by various skin cells, have become the focus of current research. In this review, we describe current pathogenic concepts of photosensitivity in lupus erythematosus, including UV-driven activation of intracellular nucleic acid sensors, cellular cytokine production and immune cell activation. Furthermore, we discuss activated pathways contributing to enhanced apoptosis as well as intracellular translocation of autoantigens thereby promoting CLE upon UV light exposure.