This thesis named "Analysis of natural organic dyes and pigments by mass spectrometry" investigates the identification of selected natural organic dyes and pigments by qualitative Laser Desorption/Ionisation - Time of Flight Mass Spectrometry analysis (LDI-TOF MS). The advantage of LDI-TOF MS method is its quick and reliable identification of low molecular weight material without preparatory chemical or time-consuming modification of samples. This method can be used for the analysis of works of art or for verifying their authenticity thanks to requiring only a little amount of sample. The LDI-TOF MS was tested on 19 organic dyes and pigments (e.g. alizarin, apigenin, baicalein, flavone, xanthone, tannic acid), four exemplarily prepared lakes (alizarin, purpurin, chrysin a quercetin lakes) and lakes mixed with organic binding media. The method was also successfully applied to two samples of blue color that were taken from Josef Čapek's painting called 'Procházka' (The Walk), that was dating back to 1936.

O trabalho apresenta o desenvolvimento de células solares fotoeletroquímicas baseadas na sensibilização de n-TiO2 por corantes sintéticos e naturais. Abrange as etapas envolvidas na sua obtenção, desde a preparação dos compostos sensibilizadores, filmes semicondutores e meio eletrolítico, até a montagem e medidas de eficiência, com a otimização dos diversos componentes do sistema, num arranjo do tipo sanduíche. O fotoanodo consiste num filme de TiO2 nanocristalino sensibilizado pelo corante num substrato condutor. O contraeletrodo é composto de um substrato condutor recoberto com camada transparente de platina. Entre os eletrodos é disposta a camada de eletrólito, geralmente solução de l2/Lil em acetonitrila. A espessura do filme de semicondutor é controlada com os métodos empregados na deposição de sua dispersão. A transparência final depende ainda do método de preparação das dispersões. Utilizando as espécies cis-[(dcbH2)2RuLL\')2+, dcbH2 = 4,4\'-(CO2H)2-2,2\'bipiridina e L/L\' = cianopiridina, quinolina e H2O, como sensibilizador, obteve-se conversão eficiente de luz visível em eletricidade com valores de IPCE de até 50 % entre 400 e 550 nm. Os processos de transferência e recombinação de elétron na interface sensibilizador/semicondutor foram investigados por experimentos com técnicas resolvidas no tempo empregando sensibilizadores ancorados aos filmes transparentes de TiO2. O trabalho envolveu ainda incorporações técnicas para aumentar a eficiência da célula, como filamentos metálicos protegidos e a combinação de unidades independentes numa associação modular, que são objetos de patentes depositadas. / This work presents the development on photoelectrochemical solar cells based on sensitization of n-TiO2 by synthetic and natural dyes. It comprises several steps involved in the fabrication and assembling of the cells in a sandwich-type design. Preparation of sensitizers, semiconductor films and electrolyte media, as well as efficiency measurements and optimization of several components are presented. The photoanode consists of a dye-sensitized nanocrystalline n-TiO2 film onto a conductive substrate. The counterelectrode is a conductive substrate covered with a thin, transparent platinum layer. The electrolyte layer, usually l2/Lil in acetonitrile, is placed between the electrodes. The deposition process of the semiconductor dispersion onto the substrates regulates the resulting thickness of the film. The final transparency is also controlled by the procedure employed in the preparation of the semiconductor dispersion. The species cis-[(dcbH2)2RuLL\']2+, dcbH2 = 4,4\'-(CO2H)2-2,2\'-bipyridine and L/L\' = 4-cyanopyridine, quinoline and H2O, were employed as sensitizers resulting in IPCE (Incident Monochromatic Photon to Current Conversion Efficiency) values as high as 50 % from 400 to 550 nm. Electron transfer and recombination processes across the semiconductor/sensitizer interface were investigated with time-resolved experiments employing transparent films of n-TiO2 sensitized by the anchored species. Other approaches aiming improvements in efficiencies and the preparation of photoelectrochemical solar cells for different applications or through environmentally friendly processes are discussed. The use of protected metallic filaments and the modular arrangement of single cells are issues of patents.

As indústrias têxteis desempenham um importante papel na economia nacional e mundial. Entretanto, do ponto de vista ambiental, suas atividades são consideradas como potencialmente poluidoras e utilizadoras de recursos naturais. Os corantes azo reativos são os principais corantes utilizados no setor para o tingimento do algodão no Brasil e no mundo. Devido à sua baixa fixação à fibra e a variações no processo de produção, cerca de 30 % da concentração inicial utilizada nos banhos de tingimento são perdidos e vão compor o efluente final. Esses compostos apresentam uma baixa biodegradabilidade e elevada solubilidade em água e, por isso, não são completamente removidos pelos processos biológicos convencionais. Os corantes quando descartados sem tratamento adequado no corpo dágua receptor podem causar modificações estéticas, alterar a fotossíntese e a solubilidade dos gases, além de serem tóxicos e genotóxicos para a biota. Os principais objetivos do trabalho foram avaliar a toxicidade e genotoxicidade de dois diferentes corantes azo reativos (Remazol Preto B RPB e Remazol Alaranjado 3R R3AR) e a eficiência de redução da cor e toxicidade após o uso da radiação com feixe de elétrons. Também foi analisada a toxicidade dos corantes em diferentes formas químicas, que podem ser encontradas nos efluentes. Os ensaios de toxicidade aguda realizados com Vibrio fischeri, Daphnia similis e Biomphalaria glabrata evidenciaram diferentes padrões de resposta para os corantes. Os dois corantes em suas formas químicas foram levemente tóxicos para Vibrio fischeri, com exceção da forma vinilsulfona do corante RPB que foi tóxico (CE(I)5015min = 6,23 mg L-1). Nos ensaios com Daphnia similis, o corante RPB foi levemente tóxico na sua forma original, sulfatoetilsulfona (CE(I)5048h = 91,25 mg L-1) e não apresentou toxicidade nas demais formas químicas. Entretanto, o corante RA3R foi tóxico para o dafnídeo, sendo muito tóxico na forma vinilsulfona (CE(I)5048h = 0,54 mg L-1). Não foi observada toxicidade nos ensaios com o organismo Biomphalaria glabrata. A toxicidade crônica foi avaliada com o organismo Ceriodaphnia dubia e o corante RPB apresentou valores de CENO e CEO iguais a 12,5 e 25 mg L-1, respectivamente, para a forma sulfatoetilsulfona. Após a hidrólise do corante (vinilsulfona e hidroxietilsulfona) foi observado um aumento os valores obtidos de CENO e CEO. Não foi verificado efeito crônico para o corante R3AR e suas formas químicas. O teste do cometa adaptado para o caramujo Biomphalaria glabrata foi utilizado para avaliar a genotoxicidade dos corantes. O corante RPB apresentou genotoxicidade nas concentrações mais elevadas (1 e 2 g L-1), com valores de dano quantitativo de 117 e 112 e o R3AR não foi genotóxico. O uso da radiação com feixes de elétrons demonstrou eficácia na remoção da cor dos corantes. Com a dose de 10 kGy foi possível uma redução de 97,64 % para RPB e de 96,8 % para R3AR. Após irradiação do corante RPB com a dose de 10 kGy foi evidenciada uma redução de 59,52 % da toxicidade aguda avaliada com Vibrio fischeri. Nas demais doses não houve redução significativa, assim como na avaliação com Daphnia similis, onde os valores de CE(I)5048h obtidos foram menores que o corante não irradiado. O corante R3AR apresentou diminuição da toxicidade mais acentuada após a radiação quando comparado com o RPB, com reduções de 82,95 % (V. fischeri) e 71,26 % (D. similis) com 10 kGy. / The textile industries play an important role in national and global economy. But, their activities are considered potentially polluting. The use of large volumes of water and the production of colored wastewater with high organic matter are among the main issues raised, especially during the stage of dyeing and washing of the textile process. The reactive azo dyes are the main colors used in the industry for dyeing of cotton in Brazil and worldwide. Because of its low setting and variations in the fiber production process, about 30% of the initial concentration used in the dyeing baths are lost and will compose the final effluent. These compounds have a low biodegradability, are highly soluble in water and therefore are not completely removed by conventional biological processes. In addition, other processes do not promote degradation but the tranference to solid environment. The dyes discarded without treatment in the water body can cause aesthetic modifications, alter photosynthesis and gas solubility, as well as being toxic and genotoxic. The main objectives of this study were to evaluate the toxicity and genotoxicity of two reactive azo dyes (Remazol Black B - RPB and Remazol Orange 3R R3AR) and the percentage of color and toxicity reduction after the use of electron beam radiation. The acute toxicity assays performed with Vibrio fischeri, Daphnia similis and Biomphalaria glabrata showed different response patterns for dyes. The different chemical forms of dyes were slightly toxic to Vibrio fischeri and only the RPB dye (vinylsulphone) was toxic (EC5015min = 6,23 mg L-1). In tests with Daphnia similis, the dye RPB was slightly toxic in its patern form, sulphatoethylsulphone, (CE5048h = 91,25 mg L-1) and showed no toxicity in other chemical forms. However, the RA3R dye was toxic to the dafnids and the vinylsulphone form very toxic (EC5048h = 0,54 mg L-1). No toxicity was observed in Biomphalaria glabrata assays. Chronic toxicity was assessed with the organism Ceriodaphnia dubia and the NOEC and OEC values of RPB dye (sulphatoethylsulphone) were 12.5 and 25 mg L-1, respectively. After hydrolysis of the dye (vinylsulphone and hydroxyethylsulphone) was shown to increase the values obtained from the NOEC ans OEC. There was no chronic effect for the R3AR dye and its chemical forms to C. dubia. The comet assay adapted to hemocytes of Biomphalaria glabrata was used to assess the genotoxicity of the dyes. The RPB dye was genotoxic at highest concentrations (1 and 2 g L-1), with quantitative values of DNA damage equal to 117 and 112 and the R3AR dye was not genotoxic. The use of radiation with electron beams have proven effective in removing the color dyes. With a dose of 10 kGy a reduction of 97.64% and 96.8% for R3AR and RPB, respectively, was achievied. Possibly, the color removal was mainly due to the interaction of reactive species such as hydroxyl radicals generated in the radiolysis of water after the radiation beam of electrons. After radiation of the RPB dye a dose of 10 kGy reduced 59.52 % of the acute toxicity measured with Vibrio fischeri. For the other doses there was no significant reduction, as well as with Daphnia similis, where the values of EC5048h obtained were smaller than the non-irradiated dye. The R3AR dye showed better decreased toxicity after radiation when compared with the RPB, with reductions of 82.95% (V. fischeri) and 71.26% (D. similis) with 10 kGy.

Submitted by Cátia Araújo (catia.araujo@unipampa.edu.br) on 2017-01-25T11:56:40Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Aplicação de biomassa vegetal como material adsorvente de corantes sintéticos em meio aquoso.pdf: 1420791 bytes, checksum: f4b861d3708be64b1349e48cab1b1bd9 (MD5) / Approved for entry into archive by Cátia Araújo (catia.araujo@unipampa.edu.br) on 2017-01-25T11:57:53Z (GMT) No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Aplicação de biomassa vegetal como material adsorvente de corantes sintéticos em meio aquoso.pdf: 1420791 bytes, checksum: f4b861d3708be64b1349e48cab1b1bd9 (MD5) / Made available in DSpace on 2017-01-25T11:57:53Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Aplicação de biomassa vegetal como material adsorvente de corantes sintéticos em meio aquoso.pdf: 1420791 bytes, checksum: f4b861d3708be64b1349e48cab1b1bd9 (MD5) Previous issue date: 2013-08-23 / O presente estudo descreve a preparação, caracterização e aplicação de novos adsorventes naturais, biomassa da casca da romã (BCR) e a biomassa da semente de caqui (BSC) na remoção dos corantes sintéticos Cristal Violeta (CV) e Azul de Toluidina (AT) em solução aquosa. As habilidades dos novos adsorventes foram estudadas através do procedimento de adsorção em batelada a temperatura de 25 ºC. Os adsorventes foram caracterizados por Espectroscopia vibracional na região do infravermelho com transformada de Fourier (FTIR), Termogravimetria (TGA), Microscopia eletrônica de varredura (MEV) e Isotermas de adsorção-dessorção de nitrogênio usando os métodos BET e BJH. A técnica de FTIR mostrou a presença de grupos funcionais na superfície dos adsorventes como COOH, OH e C=O responsáveis pela adsorção dos corantes. As análises das micrografias eletrônicas mostraram a diferença nas morfologias estruturais dos adsorventes antes e depois do processo de adsorção. Parâmetros como pH da solução, tempo de contato e dosagem de adsorvente foram otimizados para as melhores condições de adsorção dos adsorventes. As isotermas de adsorção foram obtidas a 25 ºC os dados experimentais ajustados aos modelos de Langmuir, Freundlich, Sips e Redlich-Peterson. A cinética de adsorção foi estudada através dos modelos cinéticos de pseudo-primeira ordem, pseudo-segunda ordem e quimissorção de Elovich. Os resultados obtidos mostram a viabilidade da aplicação dos novos adsorventes na remoção de corantes sintéticos de meio aquoso. / The present study describes the preparation, characterization and application of new natural adsorbents, pomegranate bark biomass (BCR) and the biomass of the seed of persimmon (BSC) in the removal of synthetic dyes crystal violet (CV) and toluidine blue (AT) aqueous solution. The skills of new adsorbents were studied through the procedure in batch adsorption temperature of 25 ºC. The adsorbents were characterized by vibrational spectroscopy in the infrared Fourier transform spectroscopy (FTIR), thermogravimetry (TGA), Microscopy scanning electron (SEM) and adsorption-desorption isotherms of nitrogen using the BET and BJH methods. The technique FTIR showed the presence of functional groups on the surface of adsorbents such as COOH, OH and C = O responsible for adsorption of the dyes.The analysis of electron micrographs showed structural differences in the morphologies of the adsorbents before and after the adsorption process. Parameters as solution pH, contact time and adsorbent dosage were optimized for better adsorption of the adsorbents. The adsorption isotherms were obtained at 25 °C the experimental data fitted to Langmuir, Freiundlich, Sips and Redlich-Peterson. The adsorption kinetics was studied using kinetic models of pseudo-first order and pseudo-second order Elovich chemisorption. The results show the feasibility of applying the new adsorbents for the removal of synthetic dyes from the aqueous medium.

Este estudo in vitro avaliou o efeito da adição de rodamina B dissolvida em etanol nas concentrações de 0,02mg/mL e 0,10mg/mL, nas propriedades mecânicas dos sistemas adesivos não simplificados considerados padrão-ouro. 96 coroas de terceiros molares humanos hígidos foram seccionadas transversalmente no terço oclusal para remoção do esmalte e exposição da dentina. Os espécimes foram divididos de acordo com os sistemas adesivos Adper Scotchbond Multi-Purpose (MP) - convencional de três passos ou Clearfil SE Bond (SE) - autocondicionante de dois passos: MP-C e SE-C (MP e SE controles); MP-C1 e SE-C1 (MP e SE com rodamina B 0,02mg/mL); MP-C2 e SE-C2: (MP e SE com rodamina B 0,10mg/mL). Para o teste de RU, os espécimes (n=10) foram submetidos ao desgaste com lixas de granulação 320 e 600. A dentina foi tratada de acordo com as instruções de cada fabricante dos sistemas adesivos e restaurada com resina composta FiltekTM Z250. Após o armazenamento em saliva artificial (7dias/37oC), os espécimes foram seccionados para obtenção de palitos com 0,64 mm2 de área média e submetidos ao teste de microtração em máquina de teste universal a 0,5 mm/min, que foram analisados após 7 dias e 6 meses. O modo de fratura dos espécimes foi analisado com estereomicroscópio digital (x200) e classificado em: adesiva, coesiva em dentina, coesiva em resina e mista. Para o teste de MS, as coroas seccionadas (n=6) foram planificadas com lixa de granulação 600. A dentina foi tratada de acordo com as instruções de cada fabricante dos sistemas adesivos e os espécimes foram mantidos secos em estufa a 37oC durante 48 horas. O teste de MS foi realizado utilizando ponta Knoop (Microdurômetro Shimadzu HMV-2), a 10x e carga estática de 25gF por 10 segundos. Os resultados obtidos foram analisados por análise de variância (ANOVA-2 critérios) e teste de Bonferroni para comparações múltiplas (p<0,05). A análise de acordo com o tempo foi realizada com o teste de t-student. Os valores médios de RU e desvio padrão (MPa±dp; 7 dias / 6 meses) foram: MP-C (41,95±2,38 / 22,76±3,66); MP-C1 (28,02±5,12 / 17,93±5,70); MP-C2 (26,28±5,55 / 14,30±5,68); SE-C (46,07±1,43 / 19,07±6,75); SE-C1 (37,49±13,31 / 18,54±6,71); SE-C2 (34,16±7,71 / 17,89±4,87). No tempo de 7 dias, os fatores sistema adesivo e concentração de rodamina B foram significantes. Após 6 meses, apenas o fator concentração de rodamina B foi significante. A falha de fratura predominante em todos os grupos foi adesiva. Os valores de MS (KHN) e desvio padrão foram: MP-C (8,97±3,85); MP-C1 (7,33±0,99); MP-C2 (7,17±2,45); SE-C (4,71±4,42); SE-C1 (4,42±0,56); SE-C2 (3,27±0,30). Na comparação entre os sistemas adesivos, eles diferiram entre si na condição controle e de 0,10mg/mL. Para cada adesivo, não houve diferença entre as distintas condições de acordo com a adição de rodamina B. Em função dos resultados apresentados, a adição de rodamina B nos sistemas adesivos não simplificados MP e SE, nas concentrações de 0,02mg/mL e 0,10mg/mL, deve ser incorporada com cautela para que não influencie nas propriedades mecânicas do material. / This in vitro study evaluated the effect of addition of rhodamine B dissolved in ethanol in concentrations of 0.02mg/mL and 0.10mg/mL, the mechanical properties of non-simplified adhesive systems. 96 crowns of human third molars were transversely sectioned on the oclusal third to remove the enamel and exposure the dentin. The specimens were divided according to the adhesive systems Adper Scotchbond Multi-Purpose (MP) 3-step-etch-andrinse or Clearfil SE Bond (SE) 2-step-self-ecthing: MP-C and SE-C (MP and SE controls); MP-C1 and SE-C1 (MP and SE with 0.02mg/mL rhodamine B); MP-C2 and SE-C2: (MP and SE with 0.10mg/mL rhodamine B). For the &#x3BC;TBS test, the specimens (n=10) were ground with 320- to 600-grit silicon carbide paper. The dentin was treated according to the instructions of each manufacturer and restored with composite resin FiltekTM Z250. The specimens were stored in artificial saliva (7 days/37oC), and then sectioned to obtain sticks with an average of 0.64 mm2 area and submitted to &#x3BC;TBS test at a universal testing machine at 0.5 mm/min, which were analyzed immediately after 7 days and 6 months. The mode of fracture of the specimens was analyzed with digital stereomicroscope (x200) and classified as: adhesive, cohesive in dentine, cohesive in resin and mixed. For the SM test, the sectioned crowns (n=6) were flattened with 600-grit silicon carbide paper. The dentin was treated according to the manufacturers instructions for each adhesive system and the specimens were stored in dry condition at 37oC during 48 hours. The SM test was performed with Knoop indenter (Shimadzu HMV-2 hardness tester), at 10x and 25gF of load for 10 seconds. The results were analyzed by two-way analysis of variance tests and the Bonferroni test for multiple comparisons (p<0.05). The analysis regarding time was checked with t-student test. The mean &#x3BC;TBS and standard deviation (MPa±dp; 7 days / 6 months) were: MP-C (41.95±2.38 / 22.76±3.66); MP-C1 (28.02±5.12 / 17.93±5.70); MP-C2 (26.28±5.55 / 14.30±5.68); SE-C (46.07±1.43 / 19.07±6.75); SE-C1 (37.49±13.31 / 18.54±6.71); SE-C2 (34.16±7.71 / 17.89±4.87). In the immediate time, the adhesive system and rhodamine B concentration factors were significant. After 6 months, only the rhodamine B concentration was a significant factor. The predominant failure in all groups was adhesive. The values of SM and standard deviation were: MP-C (8.97±3.85); MP-C1 (7.33±0.99); MP-C2 (7.17±2.45); SE-C (4.71±4.42); SE-C1 (4.42±0.56); SE-C2 (3.27±0.30). In the comparison between the adhesive systems, they were significantly different for the conditions control and 0.10mg/mL. For each adhesive systems, there was no difference between the different conditions according to the addition of rhodamine B. Regarding the shown results, addition of rodhamine B in non-simplified adhesives MP and SE, in the concentrations of 0.02mg/mL e 0.10mg/mL must be carefully added to avoid implications to the mechanical properties of the materials.

Aspectos ligados à saúde humana e ao meio ambiente têm ampliado o interesse da sociedade pelo uso de corantes naturais. Nesse contexto, inclui-se o retorno ao uso de corantes provenientes de matérias-primas de base florestal. Uma fonte potencial encontra-se na operação industrial de tratamento da madeira de Eucalyptus grandis por vapor. Usualmente, o resíduo líquido gerado ao final do processo é descartado, porém, por possuir cor, seu potencial como um corante natural para fibras têxteis foi aqui investigado. Especificamente, o resíduo foi aplicado em tecidos de algodão, lã e nylon, considerando-se o processo de tingimento por esgotamento. Foram estudados os efeitos da concentração do corante, forma de aplicação, in natura e em pó, tempo, temperatura, pH do banho de tingimento, e adição de sais metálicos no tingimento. Foi avaliada a solidez da cor dos tecidos tingidos quanto à luz, lavagem doméstica e fricção. O estudo contemplou as avaliação das características físico-química do resíduo, nos quesitos pH, cor, cromatografia de camada delgada e teores de sólidos totais e taninos condensados. Os resultados indicaram o resíduo líquido apresentando cor marrom, pH ácido, teor médio de sólidos totais e taninos condensados, respectivamente, de 2,2% e 0,93%. Os resultados das análises de cromatografia de camada delgada sugeriram a presença do ácido tânico na composição do resíduo. Em relação aos resultados de solidez de cor, verificou-se uma boa resistência dos tecidos tingidos à lavagem doméstica e uma solidez de cor à luz típica dos corantes naturais. Observou-se ainda uma boa solidez à fricção, com destaque para o excelente índice de fricção a seco nas malhas de algodão. O resíduo líquido revelou-se como um corante natural, com potencial de aceitação pela indústria têxtil, visando o tingimento de algodão, lã e nylon. / Natural dyes are gaining interest due to their expected low risk to human health and the environment. A source of natural dye was found in industrial operation of steaming Eucalyptus grandis wood. The liquid waste generated at the end of the process has been discarded. Due to this fact and the intensity of the color of the product, it was emerged the idea of this study, considering natural dye for textile fabrics. The waste was used for dyeing cotton, nylon and wool by exhaustion dyeing process. The effects of the dye concentration, the application in liquid and powder form, time, temperature, pH of the dyeing bath and the addition of metal salts in the bath were evaluated. The physic-chemical characteristics of the waste as pH, color, thin layer chromatography, and total solids and condensed tannins were also investigated. The resulting dyed fabrics were evaluated for color fastness to light, domestic washing and rubbing. The waste showed brown color, acidic pH, average total solids content of 2.2% and content of condensed tannins of 0.93%. The results from thin layer chromatography of the residue suggested the presence of tannic acid in its composition. Regarding the color fastness, it was found a very good result considering domestic washfastness, with lightfastness typical of natural dyes. The rubbing fastness was good, especially for cotton, which presented excellent grades. It was possible to consider the liquid residue as product potentially destined to the textile industry, regarding the natural dyeing of cotton, nylon and wool.

I investigated two unique processes developed throughout this body of work. The first technique is the cracking and lifting of an electroformed layer from a core vessel form. The second process, that I named “crunch-raising”, is used to form vessels. General data is gathered through research of traditional metalsmithing processes. Using an individualized approach, new data is gathered through extensive experimentation to develop a knowledge base because specific reference information does not currently exist. I find that an electroformed layer can be lifted from a core form with extreme torch heat to reveal the underlining vessel. I also find that the “crunch-raising” technique leaves a rippled texture in the surface of a vessel as it is being formed. I conclude that the project is successful. It is quite significant in that it has given me a personal vocabulary to define my current work.

This study traces the adaptation of the traditional gathering practices of Anglo/Celtic women to the landscape of Colonial Australia, thus developing a context for contemporary land-based art practices. Traditional gathering practices became one of the important forces that influenced and shaped the work of many women artists in post colonial Australia. Interacting with the landscape on a personal level helped contextualize women's gathering role into a contemporary theme, which linked past knowledge to present day voices. The author's art work is an interpretation of this traditional gathering practice. By relating herbal knowledge to present day concerns, she is able to extend the knowledge of past generations of women gatherers into present day images. The art work is also a diary of experiments, that are concerned with preserving the dye making recipes that have been handed down for generations. These botanical experiments have enabled the author to re-present herbal knowledge that took hundreds of years to glean, and to extend the use of the dyes obtained to create the art works. / Master of Arts (Hons) (Creative Arts)

This study presents findings on the effect of domestic laundry detergents on the fastness to light of selected fibre reactive dyes applied to cotton. The study was carried out to elucidate the reasons for the accelerated colour loss of cotton garments washed under Australian domestic laundering conditions. Cotton fabric dyed with commonly used reactive dyes were laundered with water only, several domestic detergents and a laboratory formulated neutral detergent, and then exposed to light for two hours in the wet state. Quantities of detergent used were in accordance with the manufacturers recommendations. Exposures were repeated fifteen times equivalent to 30 hours exposure. Colour loss and colour difference were measured after 5, 10 and 15 wash cycles and 10, 20 and 30 hours exposure. When the fabric was exposed wet the colour faded more rapidly than when exposed dry to light. Detergents increased the colour loss even when the fabric was not exposed to light. The presence of an oxidizing bleach (sodium perborate) in the detergent increased colour loss during washing and wet exposure to light. Ultraviolet radiation from the light source, heat, moisture, alkali and oxidising bleach during exposure resulted in hydrolysis of the dye-fibre bond causing dye desorption during washing and rinsing. Water alone increased the fading of the dyes most likely due to presence of dissolved oxygen held within the fibre. The combination of ultraviolet radiation and oxidizing bleaches altered the chemistry of the dye and hence its shade. This was particularly evident on the black dye and one of the navy blue dyes.

Rain fall-runoff response in temperate humid headwater catchments is mainly controlled by hydrolo gical processes at the hillslope scale. Applied tracer experiments with fluore scent dye and salt tracers are well known tools in groundwater studies at the large scale and vadose zone studies at the plot scale, where they provide a means to characterise subsurface flow. We extend this approach to the hillslope scale to investigate saturated and unsaturated flow path s concertedly at a forested hill slope in the Austrian Alps. Dye staining experiments at the plot scale revealed that crack s and soil pipe s function as preferential flow path s in the fine-textured soils of the study area, and these preferenti al flow structures were active in fast subsurface transport of tracers at the hillslope scale. Breakthrough curves obtained under steady flow conditions could be fitted well to a one-dimensional convection-dispersion model. Under natural rain fall a positive correlation of tracer concentrations to the transient flows was observed. The results of this study demon strate qualitative and quantitative effects of preferential flow feature s on subsurface stormflow in a temperate humid headwater catchment. It turn s out that / at the hill slope scale, the interaction s of structures and processes are intrinsically complex, which implies that attempts to model such a hillslope satisfactorily require detailed investigation s of effective structures and parameters at the scale of interest.