Evaluation of uranium incorporation from contaminated areas using teeth as bioindicators - a case study

The Southwest region of the Bahia state in Brazil hosts the largest uranium reserve of the country (100 kton in uranium, only), plus the cities of Caetite, Lagoa Real and Igapora. In this work, aim was at the investigation of uranium burdens on residents of these cities by using teeth as bioindicators, as a contribution for possible radiation protection measures. Thus, a total of 41 human teeth were collected, plus 50 from an allegedly uranium free area (the control region). Concentrations of uranium in teeth from residents of 5- to 87-y old were determined by means of a high-resolution inductively coupled plasma mass spectrometer (ICP-MS). The highest uranium concentration in teeth was measured from samples belonging to residents of Caetite (median equal to 16 ppb). Assuming that the uranium concentrations in teeth and bones are similar within 10-20% (for children and young adults), it concluded that uranium body levels in residents of Caetite are at least one order of magnitude higher than the worldwide average. This finding led to conclude that daily ingestion of uranium, from food and water, is equally high.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Evolution of ethyl carbamate during Madeira wine ageing by GC-MS: a new methodology

Recently, ethyl carbamate (EC) was reclassified by the International Agency for Research on Cancer (IARC) as "probably carcinogenic to humans" and occurs mainly in fermented beverages. Nowadays many countries have set limit values for EC in alcoholic beverages. In this sense and taking into account the low concentrations found in alcoholic beverages, the scientific community has shown interest for the development of new analytical methods, whereby its simplification plays an important role in the EC control and prevention. Firstly, a simple, rapid and sensitive methodology was developed for the EC quantification in fortified wines by microextraction by packed sorbent (MEPS) with gas chromatography coupled with a mass spectrometer detector (GC-MS). This method showed good linearity (R2 = 0.999) and sensitivity (LOD = 1.5 μg/L). The accuracy of the method was assessed by means of repeatability and reproducibility (RSD < 7%). Moreover, a good recovery has been demonstrated (97 – 106%) as well as its applicability (16 fortified wines). Thus, the developed methodology has proven to be an excellent approach for routine quantification of EC in fortified wines. The EC evolution was also evaluated during a year and half of Madeira wine ageing submitted to two traditional ageing methods, estufagem and canteiro, in order to evaluate the formation kinetic. The results revealed that estufagem process increased the formation kinetic and promoted a linear increase of the EC concentration (R2 ≥ 0.977), proportionally to the ageing time (4 months). However, when the wines are firstly submitted to estufagem and then undergo canteiro ageing, the EC values remain almost constant during the following 14 months. The results suggest that estufagem does not seem to be the critical factor in the EC formation, but instead the amount of precursors in the medium.

Comparative study of the whisky aroma profile based on headspace solid phase microextraction using different fibre coatings

A dynamic headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to ion trap mass spectrometry (GC–ITMS) method was developed and applied for the qualitative determination of the volatile compounds present in commercial whisky samples which alcoholic content was previously adjusted to 13% (v/v). Headspace SPME experimental conditions, such as fibre coating, extraction temperature and extraction time, were optimized in order to improve the extraction process. Five different SPME fibres were used in this study, namely, poly(dimethylsiloxane)(PDMS),poly(acrylate)(PA),Carboxen-poly(dimethylsiloxane)(CAR/PDMS),Carbowax-divinylbenzene(CW/DVB)and Carboxen-poly(dimethylsiloxane)-divinylbenzene (CAR/PDMS/DVB). The best results were obtained using a 75 m CAR/PDMS fibre during headspace extraction at 40◦C with stirring at 750rpm for 60min, after saturating the samples with salt. The optimised methodology was then appliedtoinvestigatethevolatilecompositionprofileofthreeScotchwhiskysamples—BlackLabel,BallantinesandHighlandClan.Approximately seventy volatile compounds were identified in the these samples, pertaining at several chemical groups, mainly fatty acids ethyl esters, higher alcohols, fatty acids, carbonyl compounds, monoterpenols, C13 norisoprenoids and some volatile phenols. The ethyl esters form an essential group of aroma components in whisky, to which they confer a pleasant aroma, with “fruity” odours. Qualitatively, the isoamyl acetate, with “banana” aroma,wasthemostinteresting.Quantitatively,significantcomponentsareethylestersofcaprilic,capricandlauricacids.Thehighestconcentration of fatty acids, were observed for caprilic and capric acids. From the higher alcohols the fusel oils (3-methylbutan-1-ol and 2.phenyletanol) are the most important ones.

Volatile flavour constituent patterns of terras madeirenses red wines extracted by dynamic headspace solid‐phase microextraction

A suitable analytical procedure based on static headspace solid-phase microextraction (SPME) followed by thermal desorption gas chromatography–ion trap mass spectrometry detection (GC–ITDMS), was developed and applied for the qualitative and semi-quantitative analysis of volatile components of Portuguese Terras Madeirenses red wines. The headspace SPME method was optimised in terms of fibre coating, extraction time, and extraction temperature. The performance of three commercially available SPME fibres, viz. 100 lm polydimethylsiloxane; 85 lm polyacrylate, PA; and 50/30 lm divinylbenzene/carboxen on polydimethylsiloxane, was evaluated and compared. The highest amounts extracted, in terms of the maximum signal recorded for the total volatile composition, were obtained with a PA coating fibre at 308C during an extraction time of 60 min with a constant stirring at 750 rpm, after saturation of the sample with NaCl (30%, w/v). More than sixty volatile compounds, belonging to different biosynthetic pathways, have been identified, including fatty acid ethyl esters, higher alcohols, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, and monoterpenols/C13-norisoprenoids.

Proteômica diferencial da Chromobacterium violaceum em resposta ao estresse oxidativo induzido por peróxido de hidrogênio

The β-proteobacterium Chromobacterium violaceum is a Gram-negative, free-living, saprophytic and opportunistic pathogen that inhabits tropical and subtropical ecosystems among them, in soil and water of the Amazon. It has great biotechnological potential, and because of this potential, its genome was completely sequenced in 2003. Genome analysis showed that this bacterium has several genes with functions related to the ability to survive under different kinds of environmental stresses. In order to understand the physiological response of C. violaceum under oxidative stress, we applied the tool of shotgun proteomics. Thus, colonies of C. violaceum ATCC 12472 were grown in the presence and absence of 8 mM H2O2 for two hours, total proteins were extracted from bacteria, subjected to SDS-PAGE, stained and hydrolysed. The tryptic peptides generated were subjected to a linear-liquid chromatography (LC) followed by mass spectrometer (LTQ-XL-Orbitrap) to obtain quantitative and qualitative data. A shotgun proteomics allows to compare directly in complex samples, differential expression of proteins and found that in C. Violaceum, 131 proteins are expressed exclusively in the control condition, 177 proteins began to be expressed under oxidative stress and 1175 proteins have expression in both conditions. The results showed that, under the condition of oxidative stress, this bacterium changes its metabolism by increasing the expression of proteins capable of combating oxidative stress and decreasing the expression of proteins related processes bacterial growth and catabolism (transcription, translation, carbon metabolism and fatty acids). A tool with of proteomics as an approach of integrative biology provided an overview of the metabolic pathways involved in the response of C. violaceum to oxidative stress, as well as significantly amplified understanding physiological response to environmental stress. Biochemical and "in silico" assays with the hypothetical ORF CV_0868 found that this is part of an operon. Phylogenetic analysis of superoxide dismutase, protein belonging to the operon also showed that the gene is duplicated in genome of C. violaceum and the second copy was acquired through a horizontal transfer event. Possibly, not only the SOD gene but also all genes comprising this operon were obtained in the same manner. It was concluded that C. violaceum has complex, efficient and versatile mechanisms in oxidative stress response

Estudo de adulteração em méis brasileiros através de razão isotópica do carbono

Neste trabalho, objetivou-se analisar isotopicamente méis comercializados nas regiões Sul e Sudeste do Brasil, para a detecção de fraude. Foram colhidas amostras comerciais com registro no Serviço de Inspeção Federal, Estadual ou Municipal. As amostras foram submetidas à combustão no Analisador Elementar EA 1108 CHN e analisadas no espectrômetro de massas de razão isotópica DELTA-S (Finningan Mat). Os valores isotópicos (δ13C) dos méis in natura foram comparados aos de suas respectivas proteínas (padrão interno). Foram consideradas adulteradas as amostras cuja diferença entre o valor isotópico da proteína e do mel foi igual ou inferior a -1 . As amostras consideradas adulteradas pela análise isotópica foram submetidas a testes químicos qualitativos que não foram capazes de indicar adulteração para algumas delas. Das 61 amostras analisadas, 18,0% encontram-se adulteradas, sendo 11,5% na Região Sudeste e 6,5% na Região Sul. Ao contrário dos testes químicos, a análise isotópica mostrou-se eficaz em identificar e quantificar a adulteração de méis comerciais.

Sazonalidade dos ductos secretores e óleo essencial de Foeniculum vulgare var. vulgare Mill. (Apiaceae)

Este trabalho teve como objetivo analisar os ductos secretores e o óleo essencial das folhas de Foeniculum vulgare em diferentes épocas do ano. Para esta finalidade, foram realizados estudos de caracterização anatômica, bem como anatomia comparada dos ductos secretores e testes histoquímicos das folhas. O óleo essencial foi obtido de folhas e frutos, por hidrodestilação em aparelho de Clevenger e analisados quantitativamente e qualitativamente por cromatografia em fase gasosa acoplada ao espectrômetro de massa, realizando-se análises seguidas de três réplicas para folhas coletadas durante o inverno e primavera, e frutos no verão. Os resultados encontrados para os ductos secretores de óleo corresponderam à redução do teor de óleo essencial nas folhas coletadas no final da primavera. O componente majoritário do óleo essencial de folhas e frutos foi o trans-anetol, durante todas as estações do ano. Portanto, evidenciou-se que os ductos secretores e teor de óleo essencial estão relacionados, bem como os constituintes químicos também estão sujeitos a sazonalidade, conforme o estágio fenológico da planta.

Produção de fitomassa, teor e produtividade do óleo essencial de Baccharis dracunculifolia DC. em função da adubação orgânica

Objetivou-se avaliar a produção de fitomassa, teor e produtividade do óleo essencial de Baccharis dracuculifolia DC., em função de doses de adubo orgânico, e foram utilizadas mudas produzidas por semente, e mantidas sob sombrite pelo período de 84 dias até serem transplantadas para o campo, no espaçamento de 1,0 x 1,0 m, com irrigação por gotejamento. O delineamento estatístico utilizado foi em blocos ao acaso, com quatro repetições, e as doses de composto orgânico foram: 0, 10, 20, 30, 40 e 50 t ha-1. Foi realizada uma colheita, aos 150 dias após o transplante das mudas. O óleo essencial foi extraído por hidrodestilação e analisado em cromatógrafo a gás acoplado a espectrômetro de massas (Shimadzu, QP-5000). Todos os resultados foram submetidos à análise de variância pelo teste F seguido da análise de regressão e o teste Tukey para os dados: massa seca útil da parte aérea, teor e produtividade do óleo essencial. Para as variáveis massa seca total e massa seca útil da parte aérea, as dosagens estudadas influenciaram as plantas, que apresentaram os melhores resultados na dose 50 t ha-1. Para teor de óleo não houve influência significativa para as dosagens estudadas, porém a dose 30 t ha-1 apresentou o melhor resultado. Entretanto para a produtividade do óleo essencial, as dosagens estudadas influenciaram as plantas, que na dosagem 30 t ha-1 obtiveram os melhores resultados.

Extração do óleo essencial de Cymbopogom winterianus J. com CO2 pressurizado

The extraction with pressurized fluids has become an attractive process for the extraction of essential oils, mainly due the specific characteristics of the fluids near the critical region. This work presents results of the extraction process of the essential oil of Cymbopogon winterianus J. with CO2 under high pressures. The effect of the following variables was evaluated: solvent flow rate (from 0.37 to 1.5 g CO2/min), pressure (66.7 and 75 bar) and temperature (8, 10, 15, 20 and 25 ºC) on the extraction kinetics and the total yield of the process, as well as in the solubility and composition of the C. winterianus essential oil. The experimental apparatus consisted of an extractor of fixed bed and the dynamic method was adopted for the calculation of the oil solubility. Extractions were also accomplished by conventional techniques (steam and organic solvent extraction). The determination and identification of extract composition were done by gas chromatography coupled with a mass spectrometer (GC-MS). The extract composition varied in function of the studied operational conditions and also related to the used extraction method. The main components obtained in the CO2 extraction were elemol, geraniol, citronellol and citronellal. For the steam extraction were the citronellal, citronellol and geraniol and for the organic solvent extraction were the azulene and the hexadecane. The most yield values (2.76%) and oil solubility (2.49x10-2 g oil/ g CO2) were obtained through the CO2 extraction in the operational conditions of T = 10°C, P = 66.7 bar and solvent flow rate 0.85 g CO2/min

Avaliação físico-química e funcional da algaroba prosopis juliflora proveniente da mesorregião agreste do Rio Grande do Norte

Algaroba (Prosopis juliflora) is a typical legume from arid and semi arid regions, which is composed by sugar-rich pods and high protein seeds. Phenolic compounds are secondary metabolites recognized as potent bioactive compounds, found in several vegetables.Therefore, the objective of this work is to characterize the algaroba flour in terms of its physicalchemical composition, total phenolic content, antioxidant activity by DPPH and ABTS methods, a-amylase and a-glycosidase inhibition, as well as to analyze its organic compounds by high performance liquid chromatography (HPLC). Three experimental groups were investigated (seeds, seeds and pod together and only pod), which were prepared by oven drying and posterior grinding. Water and ethanol extracts (70, 80, 100% v/v) were prepared and used for functional studies. Organic compounds were detected by using HPLC equipment coupled to mass spectrometer. Results show important physical-chemical differences among the experimental groups, seeds, seeds and pod together and only pod. The algarroba seed flour is high in protein (49.49%) and fat (3.10%), while the pod flour is especially rich in sugar (60.3% to 67.9%). Algaroba phenolics are concentrated in pod flour, mainly in water extracts (1.30 mg GAEQ/100g sample). All seed extracts showed high DPPH activity and maximum antioxidant activity was registered for ethanol 80% extracts (19.81 μM Trolox/g sample). The ABTS activity ranged from 9.73 to 12.74 μM Trolox/g sample. Nearly all the extracts were able to inhibit α-amylase activity mildly (30.50% to 48.80%), while the maximum α-glycosidase inhibition was observed for pod water extracts (81.03%). Algaroba water extracts proven to be especially rich in organic compounds, observed by the high number of chromatographic peaks. Results demonstrate that algaroba is a potential candidate for further investigations concerning its possible functional applications

Implementação da técnica de difração de elétrons de baixa energia

The purpose of this study is to describe the implementation of the Low Energy Electron Diffaction (LEED) technique in the Laboratory of Magnetic Nanostructures and Semiconductors of the Department of Theoretical and Experimental Physics of the Universidade Federal do Rio Grande do Norte (UFRN), Natal, Brazil. During this work experimental apparatus were implemented for a complete LEED set-up. A new vacuum system was also set up. This was composed of a mechanical pump, turbomolecular pump and ionic pump for ultra-high vacuum and their respective pressure measurement sensors (Pirani gauge for low vacuum measures and the wide range gauge -WRG); ion cannon maintenance, which is basically mini-sputtering, whose function is sample cleaning; and set-up, maintenance and handling of the quadrupole mass spectrometer, whose main purpose is to investigate gas contamination inside the ultra-high vacuum chamber. It should be pointed out that the main contribution of this Master's thesis was the set-up of the sample heating system; that is, a new sample holder. In addition to the function of sample holder and heater, it was necessary to implement the function of sustaining the ultra-high vacuum environment. This set of actions is essential for the complete functioning of the LEED technique

Geoquímica de sedimentos de fundo dos rios Trairí, Ararí e da Laguna Nísia Floresta (RN)

The metal concentrations (Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn ) and phosforus(P) had been determined analyzed through Plasma Inductively Coupled Plasme Mass Spectrometer for fine fraction, < 0,63 mm in 22 samples. The sample preparation for analysis had been make in the laboratories of geology of the UFRN. This samples procedures consists in register, dry, bolt and send to analysis in external laboratory (LAKEFIELD GEOSOL) in Belo Horizonte (MG, Brazil). The studied area involves the rivers Trairi, Ararí and Nísia Floresta lagoon, that empties in the sea, situated in the Rio Grande do Norte State. The study objects (Rivers Trairí, Ararí and Nísia Floresta lagoon) receive influences from urban dumpies, agrotoxics and fertilizer, shrimps tank, pastoral, with this, the concentrations of metals (Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, P, Zn) (except phosforus) in some points of the study area had been above of the value of reference what it leads to classify them as not polluted to moderately polluted, as the calculated Igeo. In front of discussed, can say about the environmental problems found in Trairi, Ararí and Nísia Floresta Lagoon are still in small scale, since when regard the studied área is over human activity effects

Estudo dos principais fatores que influenciam na solubilização dos hpas em águas

Polycyclic aromatic hydrocarbons (PAHs) constitute a family of compounds characterized by having two or more condensed aromatic rings and for being a class of substances that are widely distributed in the environment as a complex mixture, being very persistent in the environment due to its low solubility in water. The application of chemometric methods to analytical chemistry has provided excellent results in studying the solubility of PAHs in aqueous media in order to understand the mechanisms involved in environmental contamination. The method consists in analyzing the solubilization of PAHs from diesel oil in water varying parameters such as stirring time, volume of oil added and pH, using a full factorial design of two levels and three factors. PAHs were extracted with n-hexane and analyzed by fluorescence spectroscopy because they have molecular characteristics fluorescent due to the large number of condensed rings and links, and gas chromatography coupled to a mass spectrometer (GC-MS). The results of fluorescence analysis showed that only the stirring time and pH influenced the solubility of PAHs in diesel fuel. How is a non-selective technique for the study of fluorescence was performed on form and semi-quantitative. And for the chromatographic analysis the results showed that the solubility of the different PAHs is influenced differently so that you can classify them into groups by the results of the effects

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR