Cyanobacterial blooms and their toxins are a major water quality and potential health risk around the world. This thesis developed an analytical method for microcystin congeners in sediments in order to examine their fate in lakes and establish the history of toxin-producing cyanobacteria in relation to environmental change using lake sediments. A novel method for both intra- and extracellular microcystins in lake sediments was developed, consisting of accelerated solvent extraction, hydrophilic-lipophilic balance solid phase extraction and multiple reaction monitoring-based HPLC-MS/MS quantitation. The method achieved comparable recoveries of intra- and extracellular cyanotoxins based on nine microcystins and nodularin (marine analogue). The analytical method was validated using surficial and deeper sediments from seven lakes of diverse geography and trophic state. To study the fate of microcystins, a multi-year, whole lake study of Microcystis blooms was conducted to obtain both in situ and in vitro half-life estimates of microcystin-LA (MC-LA), an understudied, but increasingly reported microcystin. MC-LA appeared to undergo slower rates of decomposition and persist longer than the more frequently studied MC-LR. Experimentally, high light intensity increased in vitro decomposition of dissolved MC-LA while high temperature enhanced decomposition in the particulate phase. Sediment deposition measurements and estimates of sediment-pore water distribution coefficients, sediment accumulation rates, and diffusive fluxes indicated that microcystin congeners differ in their fate. Notably, MC-LA preferentially distributed into pore water and remobilized (by diffusion) from sediments and into overlying water while MC-RR adsorbed more strongly to sediment particles. Finally, the sediment record of an eutrophic lake of major recreational importance was examined to identify possible drivers of toxigenic cyanobacteria and determine if the perceived increase in toxigenic cyanobacteria could be corroborated. Microcystins were detected to the bottom of the core (early 1800s), indicating that toxigenic cyanobacteria were present prior to the first permanent settlements. Microcystins were significantly correlated with changes in diatom-inferred nutrients (DI-TP and DI-TKN) within the sediment core as well as with specific algal pigments. Sediment microcystins in the upper layers also significantly correlated with a 20-year monitoring record for water column microcystins suggesting that sediment microcystins can be used as a proxy for past surface water conditions.

Submitted by Biblioteca Central (biblioteca@unicap.br) on 2018-07-18T15:02:02Z No. of bitstreams: 2 laura_truan_oliveira.pdf: 9994700 bytes, checksum: 7ffacf25cb42eb47ae93409cdbdf0fc0 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-07-18T15:02:02Z (GMT). No. of bitstreams: 2 laura_truan_oliveira.pdf: 9994700 bytes, checksum: 7ffacf25cb42eb47ae93409cdbdf0fc0 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-07-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES# / #2075167498588264571# / #600 / Microorganisms have a high potential in the production of several essential metabolites for various industrial sectors. Among these metabolites are the pigments and biosurfactants that are important molecules used in the food, textile, cosmetic and pharmaceutical industries. In this context, this study was carried out to identify the species of Penicillium sp. Isolated from the soil of the caatinga of Pernambuco, besides producing, isolating and characterizing the pigment and biosurfactant produced. Penicillium sp. isolated were identified by morphological and molecular analyzes (PCR), while pigment and biosurfactant production was performed using medium containing different concentrations of whey and barley according to the Delineation central composite (CCD) 22. Pigment extraction was performed from biomass, purification by thin layer chromatography (TLC) and column chromatography, pigment was preliminarily identified by high performance liquid chromatography (HPLC). While the biosurfactant was extracted from the metabolic liquid and proved the extracellular production by the surface tension. The results obtained from the classic identification for Aspergilloides indicate that the fungus belongs to the genus and species Penicillium sclerotiorum. This fungus was able to produce high yield of biomass (15.4g/L) and pink pigment (2.23 g/L) in the medium consisting of 8% whey and 6% barley in condition four of the planning. In this medium, the data showed high carbon content (42.56%) and nitrogen (6.28%), resulting in a C / N ratio of 15: 1. The pigment had a pink band with a value of Rf = 0.961, retention time of 2.828 at 247 nm and inhibitory activity for gram-negative bacteria (Staphylococcus aureus and Klebsiella pneumoniae) and Candida glabrata yeast. Still, the maximum biosurfactant production occurred in the medium consisting of 4% whey and 2% barley with a reduction in surface tension from 70 to 27 mN/m. Emulsion index of 68% using engine burned oil, dispersion index of 33.15 cm2 and reduced viscosity from 279.6 to 48.5 cP. Penicillium sclerotiorum demonstrated the ability to produce pigment and biosurfactants from an economic environment consisting of whey and barley, thus presenting a viable alternative for the substitution of synthetic dyes and chemical surfactants meeting the essential requirements for sustainability. / Os micro-organismos apresentam elevado potencial na produção de diversos metabolitos essenciais para diferentes setores industriais. Dentre estes metabolitos estão os pigmentos e biossurfactantes que são importantes biomoléculas utilizadas na indústria alimentícia, têxtil, cosmética e farmacêutica. Neste contexto este estudo foi realizado com objetivo de identificar a espécie de Penicillium sp. isolado do solo da Caatinga de Pernambuco, além de produzir, isolar e caracterizar o pigmento e biossurfactante produzidos. O Penicillium sp. isolado foi identificado por análises morfológicas e molecular (PCR), enquanto a produção do pigmento e biossurfactante foi realizada utilizando meio contendo diferentes concentrações de soro de leite e cevada de acordo com o planejamento Delineamento Composto Central (DCC) de 22. A extração do pigmento foi realizada a partir da biomassa, a purificação através de cromatografia de camada delgada (CCD) e cromatografia em coluna, pigmento foi preliminarmente identificado por cromatografia líquida de alta eficiência (CLAE). Enquanto o biossurfactante foi extraído a partir do liquido metabólico e comprovado a produção extracelular pela tensão superficial. Os resultados obtidos a partir da identificação clássica para Aspergilloides indicam o fungo como pertencente ao gênero e espécie Penicillium sclerotiorum. Este fungo foi capaz de produzir elevado rendimento de biomassa (15,4g/L) e pigmento rosa (2,23 g/L) no meio constituído de 8% de soro de leite e 6% de cevada na condição quatro do planejamento. Neste meio, os resultados demonstraram elevado teor de carbono (42,56%) e nitrogênio (6,28%), resultando na razão de C/N de 15:1. O pigmento apresentou banda de coloração rosa intenso com valor de Rf=0,961, tempo de retenção de 2,828 a 247 nm e atividade inibitória para as bactérias (Staphylococcus aureus e Klebsiella pneumoniae) e na levedura Candida glabrata. Por outro lado a máxima produção de biossurfactante ocorreu no meio constituído por 4% de soro de leite e 2% de cevada com redução da tensão superficial de 70 para 27 mN/m. Um índice de emulsificação de 68% utilizando óleo queimado de motor, índice de dispersão de 33,15 cm2 e viscosidade reduzida de 279,6 para 48,5 cP. Penicillium sclerotiorum demonstrou habilidade de produzir pigmento e biossurfactantes a partir de meio econômico constituído de soro de leite e cevada, apresentando desta forma, uma alternativa viável para substituição dos corantes sintéticos e surfactantes químicos atendendo aos requisitos essenciais para sustentabilidade.

Este trabalho envolve o estudo sobre os níveis de pigmentos fotossintéticos, carotenóides e clorofilas, presentes nas algas marinhas Tetraselmis gracilis e Gracilaria tenuistipitata, em condições de senescência celular e estresse antropogênico (poluição metálica). Em razão do papel fundamental dos carotenóides na organização de membranas tilacóides, o papel estrutural de carotenos e do extrato metanólico de T. gracilis em bicamadas lipídicas também foi avaliado. Para estes estudos foram realizados o cultivo, coleta e construção das curvas de crescimento das algas, obtenção dos cromatogramas típicos, identificação de alguns pigmentos fotossintéticos através de padrões, análise dos extratos brutos em diferentes fases de crescimento e respectiva quantificação. Foram realizados bioensaios de toxicidade dos metais Cd, Cu, Hg e Pb e foram estimados os parâmetros toxicológicos CE15 e CE50 (concentração efetiva para a redução de 15 e 50%, respectivamente, do crescimento algal). Os modelos de estresse agudo e crônico foram construídos para cada metal e a quantificação dos pigmentos fotossintéticos foi realizada. Lipossomos foram confeccionados com a incorporação de carotenos e do extrato metanólico de T. gracilis na bicamada e foram realizadas medidas de espalhamento de luz, de calorimetria, do diâmetro hidrodinâmico e de fosfolípides. A cinética de liberação e de permeação de NO foi estudada através de medidas de fluorescência e de quimiluminescência. Também foi realizada a extração e pré-isolamento dos carotenóides presentes em T. gracilis. Os mecanismos de defesa contra espécies reativas de oxigênio foram diferentes em razão das distintas variações observadas nos níveis de pigmentos para cada metal estudado e tipo de estresse. Também foi observado um aumento do nível de pigmentos em função do aumento do tempo de exposição correspondendo provavelmente a uma estratégia aclimatativa extremamente importante no papel de adaptação e sobrevivência de organismos fotossintéticos, o que torna este tipo de avaliação, principalmente dos níveis de carotenóides, uma ferramenta útil como parâmetro de avaliação de poluição ambiental, além do emprego da biomassa como ferramenta de biorremoção de metais. Em relação aos valores de CE50 observados, o valor encontrado para o Cu foi inferior ao padrão previsto na Resolução do CONAMA no 357. Portanto, efluentes contendo Cu em níveis permitidos poderão causar danos à biota marinha. Mais ainda, sugere-se que os limites recomendáveis para este metal deverão ser revistos e alterados para a preservação de ecossistemas aquáticos. A incorporação do extrato de T. gracilis ocasionou uma grande perturbação na estruturação da membrana, resultando na fluidificação da bicamada lipídica, independente da fase de crescimento. O β-caroteno e o licopeno interferem na estruturação de bicamadas lipídicas diminuindo o diâmetro hidrodinâmico das vesículas unilamelares grandes, efeito ainda não descrito na literatura, reduzindo o valor da temperatura na qual se inicia a transição de fase, alargando a faixa onde ocorre a transição, reduzindo os valores capacidade calorífica e da entalpia e, conseqüentemente, modificando a cooperatividade da transição. Somente o β-caroteno causou fluidificação do sistema lipídico e aumento da velocidade de permeação de NO através da membrana, sugerindo o provável papel do β-caroteno na modulação de propriedades físicas da membrana. / This work involves the study of the levels of photosynthetic pigments, carotenoids and chlorophylls, contained in the marine algae Tetraselmis gracilis and Gracilaria tenuistipitata, under conditions of cellular senescence and anthropogenic stress (metallic pollution). Due to the fundamental organizational role of carotenoids in thylakoid membranes, its structural features in lipid bilayers were evaluated. Also in this last mentioned study, it was employed the methanolic extract of T. gracilis. In order to perform these studies, the algae were cultivated and the growth curves determined. Also, the typical chromatograms were obtained, and some photosynthetic pigments were identified trough commercial standards, which were then analyzed and quantified in crude extracts of different growth phases. The toxicity of the metals Cd, Cu, Hg and Pb were determined trough bioassays, which led to the toxicological parameters EC15 and EC50 estimation (the effective concentration that causes 15 and 50% of reduction of the algal growth, respectively). For each metal, the acute and chronic stress models were built, and the photosynthetic pigments contents\' quantified. Liposomes were constructed with the incorporation of carotenes and of the T. gracilis\' methanolic extract in the bilayer, which were then submitted to light scattering, calorimetric, hydrodynamic radius and phospholipid assays. Fluorescence and chemiluminescence measurements were used to study the NO kinetics of liberation and permeation. Also, it was accomplished the extraction and pre-isolation of carotenes contained in T. gracilis. For each type of metal and stress occasioned, different levels of pigments were observed, a consequence of the different mechanisms employed against reactive oxygen species. At higher exposure periods, higher pigments\' contents were quantified, which probably corresponds to an algae acclimatative strategy. The EC50 value found for Cu is higher than the standard one previously stated in the CONAMA\'s nº 357 resolution. This means that effluents containing Cu, in levels allowed by the law, may cause damage to the marine biota. Moreover, it\'s suggested a reevaluation of the standard limiting value for this metal, in order to preserve aquatic ecosystems. A higher fluidity of the lipid bilayer, occasioned by a large perturbation of the membrane\'s structure, was accomplished by incorporating the extract of T. gracilis. This was observed independently of the cells\' growth phase. &$946;-carotene and licopene interfere in the lipid bilayer structure, lowering the hydrodynamic diameter of large unilamellar vesicles, an effect not previously reported in literature. This reduces the temperature were the phase transition initiates, broadens the transition gap, lowers the calorific capacity and enthalpy values, consequently, modifying the transition cooperation. Only β-carotene induces a higher fluidity of the lipid system and a faster NO permeation trough the membrane, which suggests that it may modify physical properties of the membrane.

Carotenoides são considerados substâncias bioativas e seu consumo tem sido associado à prevenção de doenças crônicas não transmissíveis. Os carotenoides com atividade pró-vitamínica atuam no combate à hipovitaminose A. O objetivo desta dissertação foi descrever a ingestão de carotenoides, destacando a contribuição do consumo fora do domicílio, de acordo com fatores socioeconômicos, demográficos e estado nutricional, além de identificar as principais fontes alimentares presentes na dieta da população brasileira. Utilizou-se como base de dados as informações integrantes do bloco de consumo alimentar pessoal, da Pesquisa de Orçamentos Familiares (POF 2008-2009), realizada pelo Instituto Brasileiro de Geografia e Estatística (IBGE), que envolveu 34.003 indivíduos com idade de 10 anos ou mais. Um banco de dados foi construído para viabilizar o cálculo das quantidades (médias) de carotenoides presentes na dieta dos participantes da amostra. Foram utilizadas principalmente informações contidas na base Nutrient Database for Standard Reference Release 23 - United States Department of Agriculture (USDA) e a Tabela Brasileira de Composição de Carotenoides em Alimentos. Foram elaboradas análises estatísticas descritivas envolvendo o cálculo de ingestão de carotenoides no domicílio e fora dele e as variáveis selecionadas. O consumo médio per capita foi de 4.117,0 µg/dia para carotenoides totais e 2.337,9 µg/dia para os pró-vitamínicos A. As maiores médias de ingestão de carotenoides (totais; pró-vitamínicos) foram identificadas entre os seguintes grupos: mulheres (4.245,8 µg/dia; 2.458,9 µg/dia), moradores do meio urbano (4.143,2 µg/dia; 2.364,20 µg/dia), habitantes da Região Sul (4.987,6 µg/dia; 2.948,9 µg/dia), idosos (4.694,3 µg/dia; 2.853,8 µg/dia), indivíduos com os maiores rendimentos (5.596,7 µg/dia; 3.236,6 µg/dia), com curso de pós-graduação completo (7.009,7 µg/dia; 4.143,5 µg/dia), de cor amarela (5.692,7 µg/dia; 3.436,9 µg/dia) e aqueles classificados com os maiores Índice de Massa Corporal - IMC (4.445,1 µg/dia; 2.535,0 µg/dia). Constatou-se que a contribuição fora do domicílio representou até ¼ da ingestão total de carotenoides. Observou-se que os indivíduos do sexo feminino, idade acima de 60 anos e obesos, embora ingerissem maiores quantidades destas substâncias, integraram os grupamentos que (em relação ao total) apresentaram menor participação na ingestão fora do domicílio. O crescimento da renda e da escolaridade foi fundamental para proporcionar níveis mais elevados de consumo. As principais fontes de carotenoides na dieta da população brasileira foram: salada, suco, alface, tomate, mamão, melancia, abóbora, batata-doce, cenoura, milho verde e ovo de galinha. Fora do domicílio prevaleceu a ingestão dos três primeiros alimentos/preparações. Os níveis de ingestão revelaram-se expressivamente inferiores aos preconizados como seguros. Medidas de incentivo ao consumo de frutas, verduras, legumes e seus derivados (fontes de carotenoides), sobretudo entre os jovens, são necessárias e prioritárias, especialmente com vistas à prevenção de doenças crônicas não transmissíveis e no combate à hipovitaminose A. / Carotenoids are considered bioactive substances and its consumption has been associated to prevention of chronic non communicable diseases. The carotenoids with pro-vitamin activity act against hypovitaminosis A. The aim of this dissertation was to report the carotenoids intake, highlighting the contribution of outof- home food consumption, accordingly with socioeconomic and demographical factors, nutritional status, also to identify the main food sources in the diet of Brazilian population. A secondary data from the 2008-2009 Household Budget Survey - POF - was used, published by the Brazilian Institute of Geography and Statistics (IBGE). The sample consisted of 34,003 study subjects (13,569 households), with at least 10 years-old. A database was built to allow the calculation of quantities (average) of carotenoids in the diet of study participants. Information was used primarily by the Nutrient Database for Standard Reference Release 23 - United States Department of Agriculture (USDA) and the Brazilian Table of Carotenoids Composition in Food. Descriptive statistical analysis was performed for calculation of carotenoid intake at home and out-of-home consumption. The average daily consumption per capita was 4,117.0 µg/day for total carotenoids and 2,337.9 µg/day for provitamin A carotenoids. The highest average intake of carotenoids (total; provitaminic) was found between the following groups: women (4,245.8 µg/day; 2,458.9 µg/day), urban dwellers (4,143.2 µg/day; 2,364.20 µg/day), South region population (4,987.6 µg/day; 2,948.9 µg/day), elderly people (4,694.3 µg/day; 2,853.8 µg/day), high-income individuals (5,596.7 µg/day; 3,236.6 µg/day), with full graduate degree (7,009.7 µg/day; 4,143.5 µg/day), yellow skinned person (5,692.7 µg/day; 3,436.9 µg/day) and those classified with highest Body Mass Index (BMI) (4,445.1 µg/day; 2,535.0 µg/day). The out-ofhome contribution found in this present study represented up to ¼ of the total intake of carotenoids. It was observed that individuals over 60 years, female and obese people, although ingested larger amount of these substances, belonged to the groups (in relation with total) which showed less interest in out-of-home eating. The increase in income and education was essential to provide higher levels of consumption. The main dietary carotenoids sources of Brazilian population were: salad, juice, lettuce, tomato, papaya, watermelon, pumpkin, sweet potato, carrot, corn and chicken egg. The consumption of first three food/preparation prevailed outside the home. The intake levels showed expressively lower than those recommended as safe. Policies to promote the consumption of fruits, vegetables and derived products (carotenoids sources) are necessary and priority, particularly among young people, especially aiming to prevent the risk of chronic diseases and combating hypovitaminosis A.

\'Piraroxa\' e \'Vanda\' são cultivares de alface cujos comportamentos pós-colheita ainda não foram caracterizados. Um dos diferenciais destas cultivares pode estar relacionado ao seu alto potencial antioxidante como resultado da ação de seus compostos fenólicos. A fim de avaliar os parâmetros pós-colheita e a viabilidade do uso destas cultivares como fontes de antioxidantes, o presente trabalho teve como objetivo investigar suas respostas fisiológicas e bioquímicas, comparando-as entre si em diferentes temperaturas de armazenamento e em épocas de colheita distintas. Tanto no verão quanto no inverno, as hortaliças foram armazenadas por 28 dias à 0ºC e 95-97%UR e por quatro dias em condição ambiente monitorada. Em todas as condições de armazenamento e períodos de colheita, não houve diferença entre as cultivares e tendências decrescentes foram observadas para a produção de etileno e as taxas respiratórias. O armazenamento refrigerado proporcionou acentuado declínio destas variáveis. Já em condição ambiente, na colheita de verão, a cv. Vanda apresentou produção superior de etileno e, na colheita de inverno, a cv. Piraroxa apresentou taxas respiratórias mais elevadas. Os parâmetros de coloração permaneceram constantes. As cultivares apresentaram tendências similares entre si, tanto para a perda de massa fresca quanto para o conteúdo de clorofila e carotenoides, e o armazenamento refrigerado e as altas umidades relativas mostraram-se eficazes para o controle da perda de massa. O conteúdo de antocianinas foi influenciado pela temperatura de armazenamento, mas não pela época de colheita, e não demonstrou estar diretamente relacionado ao potencial antioxidante da cv. Piraroxa. As características de qualidade representadas pela aparência das hortaliças foram preservadas, em armazenamento refrigerado, até o 28º dia e, em condição ambiente, até o primeiro e segundo dias. A atividade da polifenoloxidase (PPO) e o potencial antioxidante das hortaliças foram influenciados pela época de colheita, mas não pela temperatura de armazenamento. A cv. Vanda apresentou atividade da PPO superior na colheita de verão e a cv. Piraroxa apresentou potencial antioxidante superior em todas as condições de armazenamento e épocas de colheita. O teor de compostos fenólicos e a atividade sequestrante do radical livre DPPH apresentaram valores superiores na colheita de verão para ambas as cultivares, com tendências à constância de valores, enquanto o sistema-modelo ?-caroteno/ácido linoleico demonstrou tendências crescentes, com elevações significativas a partir do segundo dia de armazenamento em condição ambiente e a partir do 21º dia de armazenamento refrigerado. Os parâmetros fisiológicos analisados evidenciaram grande similaridade em relação ao comportamento pós-colheita das duas cultivares e a durabilidade e manutenção das características qualitativas das hortaliças durante o armazenamento refrigerado foi extremamente satisfatória. Em contrapartida, o armazenamento, tanto em condição ambiente monitorada quanto em refrigeração, não demonstrou constituir-se como técnica válida para a maximização do potencial antioxidante das hortaliças, embora a alface constitua fonte dietética importante de antioxidantes. / \'Piraroxa\' and \'Vanda\' are lettuce cultivars whose postharvest behavior has not yet been characterized. One of the differentials of these cultivars may be related to its high antioxidant potential as a result of its phenolic compounds action. In order to evaluate the postharvest parameters and feasibility of using these cultivars as sources of antioxidants, this study aimed to investigate their physiological and biochemical responses, comparing them to each other at different storage temperatures and at different harvest times. Vegetables were stored for 28 days at 0ºC and 95-97%RH and for four days at ambient monitored condition regardless of summer or winter seasons. In all storage conditions and harvest periods there was no difference between cultivars and decreasing trends were observed for ethylene production and respiratory rates. Cold storage provided dramatic decline of these variables. At ambient condition, however, cv. Vanda showed higher production of ethylene in the summer harvest and cv. Piraroxa had higher respiratory rates in the winter harvest. Color parameters remained constant. Cultivars showed similar trends among one another for both weight loss and the content of chlorophyll and carotenoids. Also, cold storage and high relative humidity were effective for the control of weight loss. Anthocyanins content was influenced by storage temperature, not by the harvest season, and did not show to be directly related to the antioxidant potential of cv. Piraroxa. Vegetables quality appeared to be preserved on cold storage until day 28, and at ambient condition until the first and second days. Polyphenol oxidase (PPO) activity and antioxidant potential of vegetables were influenced by harvest time, but not by the storage temperature. \'Vanda\' showed higher PPO activity in the summer harvest and \'Piraroxa\' showed higher antioxidant potential in all storage conditions and harvest times. Phenolic content and free radical scavenging activity of DPPH showed higher values in summer harvest for both cultivars, with constant value tendencies, while the model system ?-carotene/linoleic acid showed increasing trends, with significant increases in the second day of storage at ambient condition and after 21 days of refrigerated storage. The physiological parameters analyzed showed great similarity to postharvest behavior of the two cultivars, and the durability and maintenance of vegetables quality during refrigerated storage were extremely satisfactory. In contrast, both ambient and refrigerated monitored storages did not show as valid techniques for maximizing the antioxidant potential of vegetables, although lettuce constitutes an important source of dietary antioxidants.

Breeding of coniferous trees in the Czech Republic is undergoing an important development during last decades, especially thanks to molecular-genetic methods, which refine and simplify mapping of tree genotypes and the selection of superior genotypes. Recently, in the Czech Republic superior genotypes are selected based on forestry parameters (tree height, trunk diameter, and timber quality) what does not always correlate with the ability of a tree to resist abiotic and biotic stresses. Recently, there is an effort to include in the breeding also physiological parameters and select superior genotypes using nonspecific stress indicators, which are able to correspond better to tree fitness than the forestry growth parameters. The present thesis deals with genotypes of Scots pine (Pinus sylvestris L.) growing in seed orchards Doubrava and Silov in the Pilsen region in the Czech Republic. Seed orchards are tree plantations, which serve as a reserve of the genetically valuable reproduction material, they are parts of breeding programs. Pine needles were collected in July 2015 and analyzed for non-specific stress indicators - photosynthetic pigments, phenolics, lignin, cellulose and proline contents and leaf reflectance and fast chlorophyll fluorescence measurements. First objective of the present thesis...

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As permanent tattoos are becoming more popular and common, an increased number of allergic reactions to tattoos is reported. The purpose of this project was to analyze tattoo inks for hazardous substances, and whether they comply to current Swedish and European legislative requirements. The tattoo inks were qualitatively analyzed for pigments, and quantitatively analyzed for metals. A total of 73 tattoo inks were collected from various sources such as a tattoo ink supplier, online retailers, and provided directly from tattoo artists. The labels of each tattoo ink bottle were inspected to investigate their compliance with the Council of Europe and the Swedish Medical Products Agency. Matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-ToF-MS) was used to qualitatively analyze 20 selected tattoo inks for different pigments. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantitatively analyze trace metals in 70 of the samples. A large majority (90%) of the tested samples violated the requirements and criteria in the European resolution ResAP 2008(1), such as information on name and address of the manufacturer, minimum date of durability, sterility, batch number, and storage. Patch and allergy testing were incorrectly recommended for many samples in a way that is not accepted by dermatologists. In a worst-case scenario, this testing could be a sensitizing step. Also, it can not prevent future allergic reactions from occurring or provide any juridical insurance. Only one brand, World Famous, fulfilled the requirements for labeling for six of the seven samples (one sample failed due to a faulty declared pigment). The brands Tang Dragon and Dynamic did not fulfill any of the requirements listed in ResAP 2008(1). The list of ingredients was incorrect for all samples from Tang Dragon (bought prior to 2019 online). Also, six of the other 50 samples from different brands (World Famous, Intenze, Fusion Tattoo Ink, Eternal Ink, Solid Ink) declared at least one pigment incorrectly in their ingredients list. 25% of the declared and theoretically detectable pigments were detected by means of MALDI-ToF-MS, whereas the other pigments were either absent or below the limit of detection. Future analyses should include an MS/MS analysis. Polyethylene glycol (PEG) was identified qualatively in 15 of the 20 samples analyzed with MALDI-ToF-MS but was not listed in any of the ingredients lists. ICP-QQQ-MS is a very sensitive technique and could both detect and verify the presence of all metal-containing pigments, as well as the level of impurities. Copper was clearly more present in green and blue colors, regardless of the brand. The metal content was evidently dependent on the brand for arsenic, aluminum, bismuth, chromium, nickel, zinc, and strontium. Elevated levels of barium and strontium (partially very high levels: up to 727 mg/kg barium and up to 8.06 g/kg strontium) were found in several samples. High amounts of aluminum (4 to 11,0 g/kg) and titanium (as judged from white precipitates and ingredients lists) were present in most samples. Nickel (0.1 to 41 mg/kg) and chromium (0.1 to 139 mg/kg) were also present in the samples. Some other impurities were also present (arsenic – 3.8 mg/kg, mercury – 1.6 mg/kg, and lead – 5.4 mg/kg for one sample, respectively). Known sensitizing pigments were declared and partially confirmed by MALDI-ToF-MS in 17 of 53 samples of the brands Radiant Colour, Eternal Ink, Fusion Tattoo Ink, and Kuro Sumi. Four samples (from Intenze, Eternal Ink, and Kuro Sumi) also declared pigments listed as non-suitable substance according to the European Commission regulation on cosmetic products from 2009.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multiinstrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed. / Egyptian Ministry of Higher Educations

Iridescence is the property that makes colors vary by angle of observation. Technology has made it possible to print with ink that has this anisotropic property. The ink that is used contains microparticles and therefore only specific printing methods can be used, for example screen printing. This comes with new demands on halftones, due to its procedure; dots cannot be too small, and keeping structures should be prioritized. To minimize costs and time, prints should be simulated before sending an order. In this thesis, different methods to halftone for screen printing with iridescent ink are developed. Three existing methods are compared to methods that are developed for this specific cause. The result is presented as a 2D-mask and as an interactive 3D-simulation, using data measured from real ink. Also, properties of iridescence are analyzed to separate it from diffuse colors. An OpenGL simulation tool was developed for simulating halftones on 3D-models. The ink reflectance spectra are represented by polynomials that take as input the wavelength and observation angle. Given an observation angle, a spectrum can be found, which can be converted to RGB and set as the output color in the fragment shader. The program uses an RGB-mask which is the combined masks of the halftone. This is loaded as a texture which indicates what polynomial to use. There is no perfect method that works for all types of images. Images that contain colors similar to the inks benefit from morphological halftoning (enhanced structures) for iridescent areas, or foreground, and hatching (an angle dependant grid pattern) for diffuse areas, or background. Other images, that contain mixed colors as cyan, yellow or magenta, benefit froma hue separation error diffusion, where masks are created by thresholding the hue where the mixed colors are error diffused.The actual prints confirmed the hypothesis that tone reproduction can be of lower priority while structure and depth preservance should be highly prioritized. Iridescent colors can be separated from diffuse colors by thresholding the saturation combined with value, or the lightness of the Lab-representation