V. F. Nascimento Filho

Concentrations of Fe, Cu and Zn in rum by EDXRF using APDC preconcentration

Ten rum (“aguardente”) samples commercialized in Piracicaba region, São Paulo State, Brazil Southeast, were analysed by energy-dispersive X-ray fluorescence (EDXRF) using ammonium pyrrolidinedithiocarbamate (APDC) preconcentration in order to determine Fe, Cu and Zn concentrations. The effect of sucrose (2%) was also studied in this methodology, using a multielemental standard solution (40% ethanol). Copper concentrations in two samples were higher than the value allowed by Brazilian law. Limits of detection for these elements were in the ng.ml-1 range.

Limits of detection of a total reflection x-ray fluorescence system with double reflection module

An X-ray tube with a Mo target and Zr filter, operated at 45 kV/20 mA, was used to excite samples (5 ΜL deposited on a quartz support) and the total reflection angle condition was obtained with a double reflector module built with two 10-cm-long 7-mm-thick quartz crystals placed 50 Μm apart. A high-resolution spectrometer based on a Si(Li) detector coupled to a multichannel analyzer was used for X-ray detection and the spectra were interpreted with the AXIL software.The system was calibrated with standard chemical solutions containing Cr, Fe, Cu, Zn, and Pb, and Y was used as an internal standard to correct eventual geometric errors and high-voltage instabilities of the X-ray generator. The limits of detection were 19, 9, 5, and 4 ng/mL for Cr, Fe, Cu, and Zn, respectively, analyzed through characteristicKkα X-rays, and 7 ng/mL for Pb, throughLkα X-rays, considering 50 ΜL samples deposited and dried on a quartz support, to be excited/ detected for 1000 s.

Quantitative analysis by energy dispersive X-ray fluorescence by the transmission method applied to geological samples

Three certified samples of different matrices (Soil-5, SL-1/IAEA and SARM-4/SABS) were quantitatively analysed by energy dispersive X-ray fluorescence with radioisotopic excitation. The observed errors were about 10-20% for the majority of the elements and less than 10% for Fe and Zn in the Soil-5, Mn in SL-1, and Ti, Fe and Zn in SARM-4 samples. Annular radioactive sources of Fe-55 and Cd-109 were utilized for the excitation of elements while a Si(Li) semiconductor detector coupled to a multichannel emulation card inserted in a microcomputer was used for the detection of the characteristic X-rays. The fundamental parameters method was used for the determination of elemental sensitivities and the irradiator or transmission method for the correction of the absorption effect of characteristic X-rays of elements on the range of atomic number 22 to 42 (Ti to Mo) and excitation with Cd-109. For elements in the range of atomic number 13 to 23 (Al to V) the irradiator method cannot be applied since samples are not transparent for the incident and emergent X-rays. In order to perform the absorption correction for this range of atomic number excited with Fe-55 source, another method was developed based on the experimental value of the absorption coefficients, associated with absorption edges of the elements.

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 hosts 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 3days after parasitism) compared to non-parasitized larvae, but much lower towards the end of parasitoid development (7 and 9days 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 hosts inorganic elements could also be related to the known effects of parasitism on the hosts immune response.

Study on vinasse dynamics in soil usin energy dispersive X-ray fluorescence with radioisotopic excitation

A distribuicao de S, Cl, K e Ca ao longo de perfis de dois solos de diferentes texturas (Podzolico Vermelho Amarelo e Latossolo Vermelho Escuro), tratados com uma dose de vinhaca equivalente a 4000 m3/ha, foi estudada utilizando a fluorescencia de raios X por dispersao de energia, observando-se um acrescimo significativo dos teores destes elementos. O mesmo efeito foi observado nos teores de Cu, Zn, Rb e Sr nos solos tratados com vinhaca em relacao as testemunhas. As concentracoes de Al, Si, Ti, Mn, Fe e Zr tambem puderam ser avaliadas, mas nao houve variacao nos perfis, devido a alta concentracao inicial nos solos acompanhada de baixa concentracao na vinhaca. Na excitacao dos elementos presentes nas amostras de solo tratados ou nao com vinhaca foram empregadas fontes radioativas anelares de Fe-55 e Cd-109, e na deteccao dos raios X caracteristicos um detector semicondutor de Si (Li), acoplado a uma placa analisadora de pulsos multicanal, inserida em um microcomputador.

ANÁLISE QUANTITATIVA DE AMOSTRAS GEOLÓGICAS UTILIZANDO A TÉCNICA DE FLUORESCÊNCIA DE RAIOS X POR DISPERSÃO DE ENERGIA

A quantitative analytical methodology is proposed for geological samples presenting a high fraction of light elements (atomic number less than 13), using the energy dispersive X-ray fluorescence technique with radioisotopic excitation. The proposed procedure is based on the method of the Fundamental Parameters for analytical element (Z ³ 13) evaluation, and coherent and incoherent scattered radiation for the quantitation of the light fraction of the matrix. In this method, standard samples made of pure elements and simple compounds of previously known composition and superficial density were used to estimate the relationship between the fluorescence intensity and the element concentration through elemental sensitivity and geometry factor for fluorescence. The relationship between scattered intensities and matrix light fraction was based on geometry and scattering factors as well as deferential cross sections. In order to obtain the characteristic X-rays of the elements in the Mn to Zr range a Cd-109 annular radioactive source (1.70 GBq) was used, and for Al to Cr, Fe-55 (0.74 GBq). For the X-ray detection a Si(Li) detector coupled to a multichanel emulation card was employed. The characteristic X-ray net intensity as well as the coherent and incoherent scattered intensities were obtained by using the AXIL software for spectra analysis. To test the proposed procedure, six certified samples (Soil-5/AIEA, SL-2/AIEA, SARM-2/SABS, SARM-3/SABS, SARM-4/SABS and SARM-6/SABS) were analyzed. The samples were diluted with boric acid in a 1:4 proportion to make pellets with superficial density of approximately 100 mg. cm-2.