Orientador: Maria Aparecida Azevedo Pereira da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-22T10:21:59Z (GMT). No. of bitstreams: 1 Biasoto_AlineCamaraoTelles_D.pdf: 2961321 bytes, checksum: 2144f2646383ead14df3703953f1a70a (MD5) Previous issue date: 2013 / Resumo: O suco concentrado de caju apresenta grande potencial de mercado, mas tem sua receptividade prejudicada em decorrência da perda, por evaporação ou degradação, de compostos voláteis importantes para o aroma e sabor da bebida. Os objetivos desta pesquisa foram: conhecer a dinâmica da perda e formação de voláteis durante a concentração do suco de caju por evaporação, avaliar o impacto dessas alterações sobre o perfil sensorial da bebida ao longo do processo de concentração, e identificar a importância odorífera dos voláteis perdidos e formados. Suco fresco de caju (clone CCP76) foi concentrado de 10,3°Brix a 42,1°Brix em evaporador piloto tipo termo-sifão, operando em sistema fechado, com vácuo de 700mmHg e com vapor a 110oC. Ao longo do processo de concentração cinco amostras de suco foram recolhidas. Seus teores de sólidos solúveis foram de 11,8°Brix, 14,9°Brix, 20,2°Brix, 29,6°Brix e 42,1°Brix. Os voláteis do suco fresco e das cinco amostras de suco concentrado foram extraídos por método de enriquecimento dos vapores do headspace em armadilha contendo polímero poroso (Porapak®), procedendo-se duas horas de captura sob vácuo de 70mmHg, e eluição dos voláteis capturados em acetona. Os voláteis foram identificados por cromatografia gasosa-espectrometria de massas (CG-EM) e quantificados por padronização externa, utilizando-se 12 padrões de diferentes classes químicas. A importância odorífera dos voláteis presentes nos isolados do suco fresco e do suco concentrado a 42,1°Brix foi avaliada pela técnica de cromatografia gasosa-olfatometria (CG-O) Osme. O perfil sensorial do suco fresco e das cinco amostras de suco concentrado foi gerado pela técnica de Análise Descritiva Quantitativa (ADQ®). Os dados sensoriais foram analisados por ANOVA, Tukey (p=0,05) e Análise de Componentes Principais (ACP). Modelos preditivos gerados para avaliar a dinâmica da perda e formação de ésteres, terpenos, álcoois, aldeídos, cetonas e hidrocarbonetos ao longo da concentração do suco de caju, indicaram que logo na primeira etapa de concentração, quando o suco foi concentrado até 11,8°Brix, foram perdidos aproximadamente 95% dos terpenos, 85% dos ácidos e cerca de 50% das cetonas e aldeídos. Já na segunda etapa do processamento, quando a bebida foi concentrada até 14,9°Brix, foram perdidos mais de 90% dos ésteres inicialmente presente no suco fresco, 85% dos álcoois e 90% dos hidrocarbonetos. Quando o suco atingiu 20,2°Brix, o conteúdo de álcoois e principalmente de hidrocarbonetos passou a aumentar, sugerindo uma possível formação de voláteis dessas classes químicas nas etapas finais de concentração do suco. Alterações significativas no perfil sensorial ocorreram a partir da concentração do suco acima de 20,2°Brix, com destaque para o aumento na intensidade de aroma e sabor cozido, aroma e sabor passado, aroma e gosto doce e redução de aroma e sabor de caju fresco. A análise CG-olfatometrica e correlações entre os dados instrumentais e sensoriais identificaram os seguintes voláteis como marcadores potenciais da intensidade de aroma e sabor de caju fresco na bebida: isovalerato de metila, 2-metil-butanoato de etila, butanoato de etila, isovalerato de etila, hexanoato de etila, butanoato de metila, 2-metil-butanoato de metila e 2-metilene-butanoato de etila. Por sua vez, os voláteis pentanal, tolueno, salicilato de homomentila, psi-cumeno e acetato de 1-metil-hexila correlacionaram-se positivamente com intensidade dos aromas e sabores de cozido e passado no suco de caju. De um modo geral, a perda de ésteres e terpenos ao longo da concentração do suco, associada ao aumento dos níveis de hidrocarbonetos promoveu alterações drásticas no perfil sensorial do suco concentrado. Uma adequada recuperação dos terpenos e ésteres evaporados no inicio do processo de concentração, seguida da sua reincorporação ao suco processado seria uma solução para a melhoria da qualidade sensorial do suco concentrado por evaporação / Abstract: Concentrated cashew apple juice shows considerable market potential, but its acceptability is affected by the loss of volatile compounds of importance to the aroma and flavor of the beverage, due to evaporation or degradation. The objectives of this research were: understand the dynamics of the loss and formation of volatiles during the concentration of cashew apple juice by evaporative concentration, evaluate the impact of these alterations on the sensory profile of the beverage throughout the concentration process, and identify the odiferous importance of the lost and formed volatiles. Fresh cashew-apple juice (clone CCP76) at 10.3ºBrix were concentrated to 42.1ºBrix in a pilot thermo-syphon type evaporator operating in a closed system with 700mmHg of vacuum and steam at 110ºC. Five juice samples were taken throughout the concentration process and were found to contain the following soluble solids contents: 11.8°Brix, 14.9°Brix, 20.2°Brix, 29.6°Brix and 42.1°Brix. The volatiles of the fresh juice and of the five concentrated samples were extracted from the headspaces for two hours using a vapor enrichment method with a trap containing the porous polymer Porapak® under a vacuum of 70mmHg, followed by elution of the trapped volatiles into acetone. The volatiles were identified by gas chromatography-mass spectrometry (GC-MS) and quantified by external standardization using 12 standards of different chemical classes. The odoriferous importance of the volatiles present in the isolates from the fresh juice and from that concentrated to 42.1ºBrix were evaluated by the Osme gas chromatography-olfactometry (GC-O) technique. The sensory profiles of the fresh juice and of the five samples of concentrated juice were generated by Quantitative Descriptive Analysis (QDA®). The sensory data were analyzed by ANOVA, Tukey (p=0.05) and by the Principle Component Analysis (PCA). Predictive models generated to evaluate the dynamic of the loss and formation of esters, terpenes, alcohols, aldehydes, ketones and hydrocarbons during concentration of the cashew-apple juice indicated that in the first step of concentration, when the juice was concentrated to 11.8ºBrix, approximately 95% of the terpenes were lost, 85% of the acids, about 50% of the ketones and aldehydes. In the second processing step when the beverage was concentrated to 14.9ºBrix, more than 90% of the esters initially present in the fresh juice were lost, more than 90% of the hydrocarbons and 85% of the alcohols. When the juice reached 20.2ºBrix, the content of alcohols and principally that of hydrocarbons starting increasing again, suggesting the formation of volatiles from these chemical classes in the final juice concentration steps. Significant changes in the sensory profile occurred when the juice was concentrated to 20.2ºBrix or above, highlighting increases in the cooked flavor and aroma, overripe flavor and aroma and sweet flavors and aromas, with reductions in the fresh cashew apple flavor and aroma. The GC-olfactometry analysis plus correlations between the instrumental and sensory data identified the following volatiles as potential markers of the intensity of fresh cashew apple flavor and aroma in the beverage: methyl isovalerate, ethyl 2-methyl butanoate, ethyl butanoate, ethyl isovalerate, ethyl hexanoate, methyl butanoate, methyl 2-methyl butanoate and ethyl 2-methylene- butanoate. On the other hand, the volatiles pentanal, toluene, homomenthyl salicylate, psi-cumene and 1-methyl-hexyl acetate correlated positively with the intensities of the cooked and overripe aromas and flavors of cashew apple juice. In general it can be conclude that the loss of esters and terpenes during concentration of the juice, associated with the increase in hydrocarbons resulted in drastic changes in the sensory profile of the concentrated juice. One possible solution for improvement of the sensory quality of the concentrated juice could be an adequate recovery of the terpenes and esters evaporated off at the start of the concentration process by evaporation, followed by their reincorporation into the processed juice / Doutorado / Consumo e Qualidade de Alimentos / Doutora em Alimentos e Nutrição

An efficient two step procedure has been developed using CI GC/MS for analyzing amphetamines and related compounds. The first step allows the analysis of underivatized amphetamines with the necessary sensitivity and specificity to give spectral identification, including differentiation between methamphetamine and phentermine. The second step involves preparing a chiral derivative of the extract to identify d and 1-isomeric composition.

During paper manufacturing, coating and adhesives are added to paper and cardboard to improve quality and durability. When the paper is later recycled or becoming new paper, the coatings may pollute the water used in the recycling process. Thus, it is important to know in which fraction these coatings finish during the process. In this study, laboratory made samples that mimic the repulping and paper making process is used. The different fractions of the processes were analyzed for a clay as well as a polymer coating. Metal content from clay coating is analyzed using inductively coupled plasma-mass spectrometry and microwave plasma-atomic emission spectrometry. For analyzing polymer coating, gas chromatography-mass spectrometry was used. From the result of the analysis the Reject sample, which was collected with a bigger mesh sieve in a repulping system, contained the highest amount of both clay and polymer coating. The other sample fractions from the repulping process and paper making process, did not contain as high mass content of either clay nor polymer coating.

The diploma thesis is focused on the study of chemical reaction products in prebiotic atmospheres. The theoretical part deals with the main theories of composing the atmosphere of the early Earth, hypotheses of the origin of life and genetic code in the form of RNA, the atmosphere of the moon Titan and the basic characteristics of the gliding arc discharge, and the analytical techniques used in the diploma thesis. In the experimental part, study of products was carried out by experimental atmospheric simulations in a special stainless steel reactor in various mixtures of gases N2, CH4, CO2 and O2. The electrical discharge for atmospheric simulation was generated by an electrode configuration for the gliding arc discharge and glow discharge. Detection and identification of chemical reaction products was performed by Gas Chromatography with Mass Spectrometry (GC-MS) and Flame Ionization Detector (GC-FID), Testo 350 M/XL and Proton Transfer Reaction Mass Spectrometry (PTR-MS). A theoretical kinetic model was created to predict and confirm the detected products. During the experiments, the dependence of the product intensity on changes in the composition of the gaseous mixture and the applied value of the electric current was also observed.

This master's thesis deals with the analysis of biochar extracts by separation methods. All analyzed biochar was produced from waterworks sludge by microwave pyrolysis. The aim of the thesis is the optimization of the sample preparation method and its analysis in a laboratory environment. With the ever-growing world population, the problem of a sustainable economy in both agriculture and waste management is becoming increasingly urgent. This fact has led most countries to consider promoting the so-called Circular Economy. The use of sewage sludge as a feedstock for biochar production is perfectly in line with this strategy. So far, however, the short term and the long term benefits and risks of using biochar have not been sufficiently described. Potentially hazardous organic substances were extracted from the biochar extracts by three techniques: liquid-liquid extraction, solid-phase extraction, and solid- phase micro-extraction. The obtained samples were analyzed using the GS-MS/TOF method. The individual methods were compared. Several biochar samples from WWTP Brno and WWTP Drahovice were selected and analyzed to verify the suitability of the selected sample analysis method.

Biochar is created during the pyrolysis of organic biomass. Once added into the soil, it can improve its features. Biochars made from sewage sludge have various compositions. It is because of the vast difference between entrance materials. Organic pollutants can be absorbed into its surface during the cooling proces sof pyrolysis. If released into the enviroment, these compounds can cause inhibition of plant growth, get into food chains and adversely affect living organisms. Organic pollutans are determined most often by GC/MS after organic solvent extraction.

The main goal of this thesis was to study plasma generated by surface discharge and its application in volatile organic compound destruction. Introduction of this thesis deals with the issue of volatile organic compound. The term of volatile organic compound was defined and explained. Summary of the most important sources of volatile organic compound emissions and possible technics for their elimination was presented. This thesis drew attention on negative aspects of volatile organic compounds on human organism and on the whole environment. The problems of surface discharge and its possible application in various branches are known only few years therefore construction of plasma reactor itself was the first independent step of this work. The plasma reactor was consisted of electrode, which was created from the series of metal stripes each other separated by dielectric barrier. On the surface of the electrode, discharge was regulated and distributed. For the reason of technical limits experiment time was limited up to one minute. The experimental part describes reactor for surface discharge and other parts of apparatus in which degradation volatile organic compound was carried out. Nitrogen was used as carrier gas and it was mixed with air before entering into the reactor. Samples of compounds after degradation process were taken from reactor for the subsequent analysis. Analysis of the products proceeded in a gas chromatogram linked to mass spectrometer. The decomposition products were adsorbed in the SPME filaments or in sorption tubes. The decomposition products were analysed also through the mean of Testo 350 M/XL. This apparatus provided the information on the concentration of small molecules such as CO, H2, NO, NO2 and CxHy Hexane, cyclohexane and xylene were used as VOC examples. Analysis of GC-MS showed decomposition products of hexane, cyclohexane and xylene. The decomposition products were especially various alcohols, ketones, aldehydes and benzene compounds. The apparatus Testo 350 M/XL was unable to detect any CxHy, only large quantity of NO2. This thesis was further focused on possible factors which could have an influence on degradation of compounds, for example input power or different flow of oxygen. It was found that increasing power declined the removal efficiency. The maximum removal efficiency was 87 % for degradation of hexane at the lowest input power. Next part of this thesis was focused on diagnostics of plasma generated in the surface discharge form. The optical emission spectroscopy has been chosen as the best method for plasma characterisation. By this method, various important discharge parameters can be determined, e.g. vibration and rotation temperature. The obtained numeric value of rotation temperature was 840±80 K and vibration temperature was 1880±140 K. The obtained results may be used as a fundament for further study of VOC decomposition in surface discharge.

Diploma thesis deals with gliding arc discharge in non-equilibrium plasma, its properties and usage for dissociation of volatile organic compounds. Plasma techniques create a perspective alternative to classical methods such as adsorption, biofilters, thermal processes, freezing and condensation. The method used for analysis of dissociation products is described in the theoretical part as well. Method is gas chromatography and it is combined with mass spectroscopy. The experimental part contains the overall description of GlidArc reactor where volatile organic compounds were dissociated. The volatile organic compound is brought into the reactor from the reservoir by carrier gas (nitrogen); synthetic air was used as working gas. The reactor is connected to the device for sampling. This device has several openings for sampling by SPME fibre method, sorption tubes method and a special opening for probe entry from the device Testo 350 M/XL, which enables instant analysis of low-molecular compounds. GC-MS was used for determination of high-molecular products of dissociation. Products sorbed on SPME fibres were analysed directly, compounds sorbed by active carbon were extracted by carbon disulphide. Samples obtained using SPME fibres were analysed. The major products of the dissociaton were found due to this analysis, those major products are in the case of hexane: pentanal, 4 methyl-3-pentanal, 2-butoxy-ethanol, pentane a 2-hexene. Major products detected when dissociating cyclohexane were: l,3-dimethyl-butane, propanal, cyklohexanone, 5-hexenal a 2-pentyn-1-ol. Major products of xylene dissociation were methyl-benzene, benzaldehyde, 4-methyl-benzaldehyde, 1-nitroethyl-benzene a benzenmethanol. After analysis obtained using sorption tubes showed that mainly the dissociated compound was sorbed, but the products of the dissociation were presented in too low concentration for an adequate analysis. For that reason the sorption tubes were used only for quantitative determination of the compounds depending on the power supply. The dependence of the dissociation of the compounds on the power supply was observed using SPME fibres which were used for quantitative determination. The Results obtained by both obtained techniques were almost in accordance. Speaking of low-molecular compounds, dissociation of all compounds gave the same products, i.e. carbon dioxide, hydrogen, nitrogen oxide, nitrogen dioxide and water. The results show that the dissociation of VOC gives - besides many potentially dangerous dissociation products - significant amounts of nitrogen oxides which is harmful to the environment. Hence it is necessary to be concerned with problems studied in the future mainly with respect to limitation of NOx generation. It will be possible to optimalize the conditions of the VOC dissociation on the basis of future kinetic analysis.

Synthetic musk compounds (MUSK) or synthetic fragrances are organic substances commonly used as fragrant constituents of perfumes, detergents, cosmetics and personal care products. These compounds are discharged after use via domestic wastewater and sewage treatment plants to the aquatic environment. The result is accumulation in the environment and occurrence in a food chain especially of aquatic and marine ecosystems. Synthetic musk compounds are also found in surface water, fish tissues and also in body fluid (blood, urine, milk) and tissues of human body. Quantitative detection and studying properties of these compounds is an important activity because we have low knowledge about their fate in the environment (persistence, bioaccumulation) and toxicity. This diploma thesis is focused on three commonly used synthetic fragrances – tonalide, musk ketone and musk xylene. The base of this study was to perform a method optimisation for the determination of selected compounds in water and water biota (fish). The aim was determination of selected musk compounds in real samples (water, fish) and evaluation of the results. Pressurized solvent extraction (PSE) for fish samples and solid phase microextraction (SPME) for water samples were used for isolation of analytes from samples. The identification and quantification of analytes was carried out by high resolution gas chromatography – mass spectrometry.

The peppermint (Mentha piperita), the salvia (Salvia officinalis), the lemon balm (Melissa oficinalis), the camomile (Matricaria chamomilla) and the valerian (Valeriana officinalis) are herbs with healing effects. Their ethanol extracts are used for food fortification or in a cosmetic industry. Substances contained in herbal extracts were analyzed in this thesis. The extracts were prepared by maceration. Next, they were analyzed by using a gas chromatography and a mass spectrometry. The aim of this thesis was an optimalization of the method used for the analysis of sensorially active substances. Then, herbal extracts were analyzed and concentration of sensorially active substances was determined.