Evaluation of trace element levels in muscles, liver and gonad of fish species from Sao Francisco River of the Parana Brazilian state by using SR-TXRF technique

This study is focused on the analysis of an accumulation of inorganic elements in muscles, liver and gonad of seven fish species from Sao Francisco River located in the Parana state of Brazil. Concentrations of the elements were determined using the SR-TXRF technique. In the muscles of fish species, negative length dependent relationships were observed for chromium and zinc ion absorption. The obtained results showed that accumulated Cr ions values are above the limits defined in the Brazilian legislative norm on food. (C) 2010 Elsevier Ltd All rights reserved.

Water quality assessment of Toledo River and determination of metal concentrations by using SR-TXRF technique

The region of Toledo River, Parana, Brazil is characterized by intense anthropogenic activities. Hence, metal concentrations and physical-chemical parameters of Toledo River water were determined in order to complete an environmental evaluation catalog. Samples were collected monthly during one year period at seven different sites from the source down the river mouth, physical-chemical variables were analyzed, and major metallic ions were measured. Metal analysis was performed by using the synchrotron radiation total reflection X-ray fluorescence technique. A statistical analysis was applied to evaluate the reliability of experimental data. The analysis of obtained results have shown that a strong correlation between physical-chemical parameters existed among sites 1 and 7, suggesting that organic pollutants were mainly responsible for decreasing the Toledo River water quality.

Evaluation of the bioaccumulation kinetics of gold nanorods in vital mammalian organs by mean of TXRF spectrometry

This work presents the first application of total-reflection X-ray fluorescence (TXRF) spectrometry, a new and powerful alternative analytical method, to evaluation of the bioaccumulation kinetics of gold nanorods (GNRs) in various tissues upon intravenous administration in mice. The analytical parameters for developed methodology by TXRF were evaluated by means of the parallel analysis of bovine liver certified reference material samples (BCR-185R) doped with 10 μg/g gold. The average values (n = 5) achieved for gold measurements in lyophilized tissue weight were as follows: recovery 99.7%, expanded uncertainty (k = 2) 7%, repeatability 1.7%, detection limit 112 ng/g, and quantification limit 370 ng/g. The GNR bioaccumulation kinetics was analyzed in several vital mammalian organs such as liver, spleen, brain, and lung at different times. Additionally, urine samples were analyzed to study the kinetics of elimination of the GNRs by this excretion route. The main achievement was clearly differentiating two kinds of behaviors. GNRs were quickly bioaccumulated by highly vascular filtration organs such as liver and spleen, while GNRs do not show a bioaccumulation rates in brain and lung for the period of time investigated. In parallel, urine also shows a lack of GNR accumulation. TXRF has proven to be a powerful, versatile, and precise analytical technique for the evaluation of GNRs content in biological systems and, in a more general way, for any kind of metallic nanoparticles.

Inorganic elements in the fat bodies of Diatraea saccharalis (Lepidoptera: Crambidae) larvae parasitized by Cotesia flavipes (Hymenoptera: Braconidae)

Koinobiont parasitoids use several strategies to regulate the host`s physiological processes during parasitism. Although many aspects of host-parasitoid interactions have been explored, studies that attempted to assess the effects of parasitism on the availability of inorganic elements in the host are virtually nonexistent. Therefore, we aimed to evaluate the effects of parasitism on the concentrations of inorganic elements in the fat bodies of larvae of Diatraea saccharalis (Lepidoptera: Crambidae) during the development of the parasitoid Cotesia flavipes (Hymenoptera: Braconidae), by using total reflection X-ray fluorescence (TXRF). TXRF analysis allowed comparisons of the changes in the availability of the elements P. S. K, Ca, Cr, Fe, Ni, Cu, and Zn in the fat body tissues of D. saccharalis larvae parasitized by C. flavipes. Overall, the concentration of inorganic elements was higher early in parasitoid development (1 and 3 days after parasitism) compared to non-parasitized larvae, but much lower towards the end of parasitoid development (7 and 9 days after parasitism). Ca, K, and S were reduced after the fifth day of parasitism, which affected the total abundance of inorganic elements observed in the fat bodies of the parasitized hosts. The regulatory mechanisms or pathological effects related to the observed variation of the host inorganic elements induced by the parasitoid remain unknown, but there might be a strategy to make these elements available to the parasitoid larvae at the end of their development, when higher metabolic activity of the host fat body is required to sustain parasitoid growth. The observed variation of the host`s inorganic elements could also be related to the known effects of parasitism on the host`s immune response. (C) 2010 Elsevier Inc. All rights reserved.

Measurement of lead concentration in biological tissues by atomic spectroscopy techniques

Dissertation for the degree of Doctor of Philosophy in Physics

ELEMENTOS-TRAÇO EM ÁREAS DE VEGETAÇÃO NATIVA E AGRICULTURA INTENSIVA DO ESTADO DE MATO GROSSO DETERMINADOS POR FLUORESCÊNCIA DE RAIOS-X POR REFLEXÃO TOTAL

A espectroscopia de raios-X por reflexão total (TXRF) é uma técnica promissora para análise de elementos-traço (ETs), principalmente por não ser necessária a digestão das amostras, reduzindo assim a geração de resíduos e emissão de vapores tóxicos. Este trabalho comparou os teores dos ETs: Cr, Mn, Ni, Zn, Cu, As, Se, Hg e Pb, coletados em solos de área de agricultura intensiva e vegetação nativa, determinados por TXRF e por espectrometria de absorção atômica de chama ou forno de grafite (FAAS/GFAAS). Adicionalmente, compararam-se os teores dos ET com valores de referência para solos não contaminados. As amostras de solo foram coletadas na profundidade 0,0-0,2 m em municípios representativos de cada região agrícola do Estado de Mato Grosso (Rondonópolis, Alto Garça, Primavera do Leste, Campo Novo, Nova Mutum, Lucas do Rio Verde, Sorriso, Sinop, Campo Novo dos Parecis, Campos de Julho e Vila Bela da Santíssima Trindade). Em cada município, foram selecionadas seis áreas, totalizando 72 amostras, todas georreferenciadas. Para a leitura dos teores de ET no aparelho de TXRF S2 Picofox™, foram preparadas suspensões de solo usando Triton X-100 a 5 % v/v utilizando gálio como padrão interno, enquanto no FAAS/GFAAS as amostras foram submetidas à digestão ácida pelo método 3051A. Considerando área cultivada e área nativa, respectivamente, os teores médios dos ET por TXRF, em mg kg-1, foram: Cr, 69 e 62; Zn, 16 e 8; Pb, 28 e 21; Mn, 56 e 42; As, 2 e 2; Cu, 9 e 8; e Ni, 2 e 2. O Cd, Se e Hg não foram detectados por TXRF nas amostras analisadas. Para As, Cr, Mn, Zn, Ni, Cu e Pb, houve correlação linear (p<0,001) positiva entre as técnicas e, no geral, os teores obtidos para esses ET em TXRF foram superiores aos do FAAS/GFAAS. Os teores de todos os elementos detectados pelo TXRF, exceto o Cr, estão dentro das faixas dos relatados para solos não contaminados e muito inferiores aos limites de alerta estipulados na literatura.

Selenium cycling in volcanic environments: the role of soils as reactive interfaces

Selenium (Se) is an element with important health implications that is emitted in significant amounts from volcanoes. Attracted by the fertility of volcanic soils, around 10% of the world population lives within 100 km of an active volcano. Nevertheless, the behaviour of Se in volcanic environments is poorly understood. Therefore, the main aim of this thesis is to investigate the role of soils in the Se cycling in volcanic environments. Prior to the geochemical studies, precise and accurate methods for the determination of Se contents, speciation and isotopic signatures were developed. Afterwards, a combination of field studies and lab controlled experiments were performed with soils from two contrasting European volcanic settings: Mount Etna in Sicily (Italy) and Mount Teide in Tenerife (Spain). The results showed a strong link between Se behaviour and soil development, indicating that Se mobility in volcanic soils is controlled by sorption processes and soil mineralogy.

Chromium ions phytoaccumulation by three floating aquatic macrophytes from a nutrient medium

In the present work, the trivalent and hexavalent chromium phytoaccumulation by three living free floating aquatic macrophytes Salvinia auriculata, Pistia stratiotes, and Eicchornia crassipes was investigated in greenhouse. These plants were grown in hydroponic solutions supplied with non-toxic Cr3+ and Cr6+ chromium concentrations, performing six collections of nutrient media and plants in time from a batch system. The total chromium concentrations into Cr-doped hydroponic media and dry roots and aerial parts were assayed, by using the Synchrotron radiation X-ray fluorescence technique. The aquatic plant-based chromium removal data were described by using a nonstructural kinetic model, obtaining different bioaccumulation rate, ranging from 0.015 to 0.837 1 mg(-1) d(-1). The Cr3+ removal efficiency was about 90%, 50%, and 90% for the E. crassipes, P. stratiotes, and S. auriculata, respectively; while it was rather different for Cr6+ one, with values about 50%, 70%, and 90% for the E. crassipes, P. stratiotes, and S. auriculata.

A hydride generation flow system for determination of arsenic and selenium by total reflection X-ray fluorescence spectrometry

In this work, a preconcentration and separation system based on continuous flow hydride generation is proposed to improve the determination of As and Se by total reflection X-ray fluorescence spectrometry. The generated hydrides are continuously separated from the liquid phase and collected in a chamber containing 250 mul of HCI/HNO3 1:1 (v/v) solution. Hydride generation conditions and collection of the hydrides were evaluated. Under optimised conditions, enrichment factors of 55 for As and 82 for Se were attained. Detection limits of 0.3 mug l(-1) for As and Se were obtained when 20 ml of sample was used. Analysis of a natural water standard reference material from National Institute of Standard and Technology (SRM-1640) was in agreement with the certified values at the 95% confidence level. (C) 2004 Elsevier B.V. All rights reserved.

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Monte Carlo simulation applied in total reflection X-ray fluorescence: Preliminary results

The X-ray Fluorescence (XRF) analysis is a technique for the qualitative and quantitative determination of chemical constituents in a sample. This method is based on detection of the characteristic radiation intensities emitted by the elements of the sample, when properly excited. A variant of this technique is the Total Reflection X-ray Fluorescence (TXRF) that utilizes electromagnetic radiation as excitation source. In total reflection of X-ray, the angle of refraction of the incident beam tends to zero and the refracted beam is tangent to the sample support interface. Thus, there is a minimum angle of incidence at which no refracted beam exists and all incident radiation undergoes total reflection. In this study, we evaluated the influence of the energy variation of the beam of incident x-rays, using the MCNPX code (Monte Carlo NParticle) based on Monte Carlo method. © 2013 AIP Publishing LLC.

Análise multielementar da mucosa gástrica de roedores tratados com Alchornea glandulosa, Davilla elliptica e Davilla nitida pela técnica de fluorescência de raios-x por reflexão total

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise multielementar pela técnica de fluorescência de raios-X de amostras de cólon de roedores com colite e tratados com prednisolona

Pós-graduação em Biologia Geral e Aplicada - IBB

Viabilidade do Código MCNPX para o Estudo da Técnica de Fluorescência de Raios-X por Reflexão Total

The X-ray fluorescence analysis (XRF) is an important technique for the qualitative and quantitative determination of chemical components in a sample. It is based on measurement of the intensity of the emitted characteristic radiation by the elements of the sample, after being properly excited. One of the modalities of this technique is the total reflection x-ray fluorescence (TXRF). In TXRF, the angle of refraction of the incident beam tends to zero and the refracted beam is tangent to the sample-support interface. Thus, there is a minimum angle of incidence that there is no refracted beam and all the incident radiation undergoes total reflection. As it is implemented in very small samples, in a film format, self-absorption effects should not very relevant. In this study, we evaluated the feasibility of using code MCNPX (Monte Carlo N - Particle eXtended), to simulate a measure implemented by the TXRF technique. In this way, it was verified the quality of response of a system by TXRF spectroscopy using synchrotron radiation as excitation beam for a simple setup, by retrieving the characteristic energies and the concentrations of the elements in the sample. The steps of data processing, after obtaining the excitation spectra, were the same as in a real experiment and included the obtaining of the sensitivity curve for the simulated system. The agreement between the theoretical and simulated values of Ka characteristic energies for different elements was lower than 1 % .The obtained concentration of the elements of the sample had high relatively errors ( between 6 and 60 % ) due mainly to lack of knowing about some realistic physical parameters of the sample , such as density . In this way, this result does not preclude the use of MCNPX code for this type of application

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co. Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500 mu g L-1 of Mn. Co, Ni, Cu, Zn and Pb (4 L at pH 5.5 and ionic strength at 0.05 mol L-1). After retrieval, the DGT units were disassembled and the P81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87 x 10(-6) cm(2) s(-1). The metal retention and phosphate group homogeneities on the P81 membrane was studied by a spot analysis with a diameter of 1 mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48 h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45 mu m dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26 mu g L-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1 mu g L-1). (C) 2012 Elsevier B.V. All rights reserved.