In the present paper, the adsorption of cysteine on hematite, magnetite and ferrihydrite was studied using FT-IR, electron paramagnetic resonance (EPR), Mössbauer spectroscopy and X-ray diffractometry. Cysteine was dissolved in artificial seawater (two different pHs) which contains the major constituents. There were two main findings described in this paper. First, after the cysteine adsorption, the FT-IR spectroscopy and X-ray diffractometry data showed the formation of cystine. Second, the Mössbauer spectroscopy did not show any increase in the amount of Fe(2+) as expected due the oxidation of cysteine to cystine. An explanation could be that Fe(2+) was oxidized by the oxygen present in the seawater or there occurred a reduction of cystine by Fe(2+) generating cysteine and Fe(3+). The specific surface area and pH at point of zero charge of the iron oxides were influenced by adsorption of cysteine. When compared to other iron oxides, ferrihydrite adsorbed significantly (p < 0.05) more cysteine. The pH has a significant (p < 0.05) effect only on cysteine adsorption on hematite. The FT-IR spectroscopy results showed that cystine remains adsorbed on the surface of the iron oxides even after being mixed with KCl and the amine and carboxylic groups are involved in this interaction. X-ray diffractometry showed no changes on iron oxides mineralogy and the following precipitated substances were found along with the iron oxides after drying the samples: cysteine, cystine and seawater salts. The EPR spectroscopy showed that cysteine interacts with iron oxides, changing the relative amounts of iron oxides and hydroxide.

In the present work the interactions of nucleic acid bases with and adsorption on clays were studied at two pHs (2.00, 7.00) using different techniques. As shown by Mössbauer and EPR spectroscopies and X-ray diffractometry, the most important finding of this work is that nucleic acid bases penetrate into the interlayer of the clays and oxidize Fe(2+) to Fe(3+), thus, this interaction cannot be regarded as a simple physical adsorption. For the two pHs the order of the adsorption of nucleic acid bases on the clays was: adenine ≈ cytosine > thymine > uracil. The adsorption of adenine and cytosine on clays increased with decreasing of the pH. For unaltered montmorillonite this result could be explained by electrostatic forces between adenine/cytosine positively charged and clay negatively charged. However for montmorillonite modified with Na(2)S, probably van der Waals forces also play an important role since both adenine/cytosine and clay were positively charged. FT-IR spectra showed that the interaction between nucleic acid bases and clays was through NH(+) or NH (2) (+) groups. X-ray diffractograms showed that nucleic acid bases adsorbed on clays were distributed into the interlayer surface, edge sites and external surface functional groups (aluminol, silanol) EPR spectra showed that the intensity of the line g ≈ 2 increased probably because the oxidation of Fe(2+) to Fe(3+) by nucleic acid bases and intensity of the line g = 4.1 increased due to the interaction of Fe(3+) with nucleic acid bases. Mössbauer spectra showed a large decreased on the Fe(2+) doublet area of the clays due to the reaction of nucleic acid bases with Fe(2+).

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SUMMARYSynthetic aluminum-substituted maghemites were characterized by total chemical analysis, powder X-ray diffraction (XRD), Mössbauer spectroscopy (ME), and vibrating sample magnetometry (VSM). The aim was to determine the structural, magnetic, and hyperfine properties of γ γ γ γ γ-Fe 2-x Al x O 3 as the Al concentration is varied. The XRD results of the synthetic products were indexed exclusively as maghemite. Increasing Al for Fe substitution decreased the mean crystalline dimension and shifted all diffraction peaks to higher o 2θ θ θ θ θ angles. The a 0 dimension of the cubic unit cell decreased with increasing Al according to the equation a o = 0.8385 -3.63 x 10 -5 Al (R 2 = 0.94). Most Mössbauer spectra were composed of one sextet, but at the highest substitution rate of 142.5 mmol mol -1 Al, both a doublet and sextet were obtained at ≈ 300 K. All hyperfine parameters from the sub-spectra were consistent with high-spin Fe 3+ (0.2 a 0.7 mms -1 ) and suggested a strong superparamagnetic component associated with the doublet. The magnetic hyperfine field of the sextets decreased with the amount of Al-substitution [B hf (T) = 49.751 -0.1202Al; R 2 = 0.94] while the linewidth increased linearly. The saturation magnetization also decreased with increasing isomorphous substitution.Index terms: isomorphous substitution, hyperfine parameters, spinel, ferromagnetic.( RESUMO: CARACTERIZAÇÃO ESTRUTURAL E MAGNÉTICA DE MAGHEMITAS PREPARADAS A PARTIR DE MAGNETITAS SUBSTITUÍDAS COM AlMaghemitas sintéticas substituídas com Al foram caracterizadas por meio de análise química total, difratometria de raios-X (DRX), espectroscopia Mössbauer (EM) e magnetometria de amostra vibrante (MAV). Objetivou-se com este trabalho determinar as propriedades estruturais, magnéticas e hiperfinas de γ-Fe 2-x Al x O 3, conforme a variação da concentração de Al.Os resultados de DRX dos produtos sintéticos foram indexados somente para maghemita. Com o aumento da substituição de Fe por Al, o diâmetro médio do cristalito diminuiu e levou todos os picos de difração para maiores ângulos o 2θ. A dimensão a 0 da cela unitária cúbica decresceu com o aumento de Al, de acordo com a equação a o = 0,8385 -3,63 x 10 -5 Al (R 2 = 0,94). A maioria dos espectros Mössbauer foi composta de um sexteto, mas na taxa mais alta de substituição de 142,5 mmol mol -1 Al um doubleto e sexteto foram obtidos a ≈ 300 K. Todos os parâmetros hiperfinos do subespectro foram consistentes com o alto spin Fe 3+ (0,2 a 0,7 mms -1 ) e sugeriram um forte componente superparamagnético associado com o dubleto. O campo magnético hiperfino dos sextetos decresceram com a substituição de Al [B hf (T) = 49,751 -0,1202Al; R 2 = 0,94], enquanto as larguras da linha aumentaram de forma linear. A magnetização de saturação também diminuiu com o aumento da substituição isomórfica.Termos de indexação: substituição isomórfica, parâmetros hiperfinos, espinélio, ferrimagnético.

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