Iron and aluminum oxides of different brazilian soils

rbcs Revista Brasileira de Ciência do Solo Rev. Bras. Ciênc. Solo 1806-9657 Sociedade Brasileira de Ciência do Solo Viçosa, MG, Brazil To study iron and aluminum oxide characteristics, samples of soils developed from different parent materials and with different development degrees were selected and collected from MG, ES, RS and RR states. The clay fraction was analyzed by X-ray diffraction (XRD), differential thermal analysis, thermogravimetry and electron microscopy. Al, Si and microelement contents were determined from ammonium oxalate (Ox) and dithionite-citrate-bicarbonate (DCB) extractions. Overall, goethite (Gt) was the main iron oxide in the clay fraction. Only the soils developed from basalt and sandstone showed hematite (Hm) as the predominant mineral. The soils from the Barreiras Group (ES and RR states) showed the lowest iron oxide content, reflecting the low iron level of these sediments. A significant correlation between Gt/(Gt + Hm) ratio and water content extracted by DCB (r = 0.70***) was found, suggesting that this relationship comes from the fact that Gt is a hydrated iron oxide. The clay fraction of the younger soils, specially in the C horizon, showed the highest FeOx/FeDCB ratios and the highest levels of amorphous materials extracted by Ox, reaching 28% for sample 17. This amorphous mineral is basically formed by Al plus some Fe-minerals. Some samples showed similar values for the mean crystal diameter (MCD) of Gt in the (110) and (111) directions, suggesting an isodimensional form of this mineral. The higher values of the MCD for Hm resulted in lower surface area in relation to Gt. The substitution of Fe by Al in the Gt was higher than in Hm (average of 218 and 85 mmol mol-1, respectively). Due to Al substitution in the Gt structure, the crystallinity degree and the mineral size, mainly in the c direction, were reduced as shown by the significant correlation between substitution of Fe by Al and MCD(111) (r = -0.80***). The correlation between Fe and the microelement contents extracted by DCB were high and significant suggesting that the microelements, as also seen for Al, replace Fe in the iron oxide structure. The MCD of the gibbsite (Gb) crystals were higher than that of the iron oxides. Electron microscopy showed that the Gb crystals from the clay fraction appeared to be small square plates, whereas the ones from the silt fraction appeared to be round. SEÇÃO II - QUÍMICA DO SOLO Características dos óxidos de ferro e de alumínio de diferentes classes de solos(1) Iron and aluminum oxides of different brazilian soils V. F. MeloI; M. P. F. FontesII; R. F. NovaisII; B. SinghIII ; C. E. G. R. SchaeferII IProfessor do Departamento de Solos, Universidade Federal do Paraná - UFPR. CEP 80035-050 Curitiba (PR) IIProfessor do Departamento de Solos da Universidade Federal de Viçosa - UFV. Av. PH Rolfs s/n, CEP 36571-000 Viçosa (MG). Bolsista do CNPq IIIDepartament of Agricultural Chemistry and Soil Science, The University of Sydney, N.S.W. 2006, Australia RESUMO Para avaliar as características dos óxidos de ferro e de alumínio, foram coletadas amostras de solos desenvolvidos de diferentes materiais de origem e estádios de desenvolvimento nos estados de MG, ES, RS e RR. A fração argila das amostras foi estudada por difratometria de raios-X (DRX), análise termodiferencial (ATD), análise termogravimétrica diferencial (ATGD) e microscopia eletrônica. Nos extratos resultantes da extração com oxalato de amônio (OA) e ditionito-citrato-bicarbonato (DCB), determinaram-se os teores de Al, Si e microelementos, inclusive Fe. Em geral, a goethita (Gt) foi o principal óxido de ferro da fração argila. Apenas para os solos desenvolvidos de basalto e de arenito, verificou-se o predomínio de hematita (Hm). Os solos do Grupo Barreiras (ES) apresentaram os menores teores de óxidos de ferro em decorrência do intenso processo de desferrificação sofrido pelos sedimentos. Por ser a Gt um óxido hidratado, quanto maior a relação Gt/(Gt + Hm), maior o teor de água extraída pelo DCB (r = 0,70***). Os solos menos desenvolvidos, principalmente no horizonte C, apresentaram os maiores teores de material menos cristalino extraído pelo OA (chegando a 28% para a amostra 17) e os maiores valores para a relação FeOA/FeDCB. Este material menos cristalino é constituído principalmente por Al, com menor participação de Fe. Parte das amostras apresentou valores próximos para o diâmetro médio do cristal (DMC) da Gt nas direções (110) e (111), indicando formato isodimensional do mineral. Os maiores valores de DMC para a Hm resultaram na menor superfície específica em relação à Gt. A substituição isomórfica de Fe por Al (SI) na Gt foi consideravelmente superior à da Hm (média de 218 e 85 mmol mol-1, respectivamente). Com a entrada de Al na estrutura da Gt, verificou-se redução no tamanho, principalmente na direção do eixo Z (r entre SI e DMC(111) = -0,80***), e no grau de cristalinidade do mineral. As correlações entre teor de ferro e outros elementos extraídos pelo DCB foram altas e significativas. Os microelementos, como verificado para o Al, substituem isomorficamente o Fe na estrutura dos óxidos. O DMC da gibbsita (Gb) foi consistentemente superior ao dos óxidos de ferro. Por meio de observações em microscópio eletrônico, a Gb, na fração argila, apresentou o formato de pequenas placas retangulares e, na fração silte, verificou-se tendência de formato esférico. Termos de indexação: hematita, goethita, gibbsita, DRX, análises térmicas, microscopia eletrônica. SUMMARY To study iron and aluminum oxide characteristics, samples of soils developed from different parent materials and with different development degrees were selected and collected from MG, ES, RS and RR states. The clay fraction was analyzed by X-ray diffraction (XRD), differential thermal analysis, thermogravimetry and electron microscopy. Al, Si and microelement contents were determined from ammonium oxalate (Ox) and dithionite-citrate-bicarbonate (DCB) extractions. Overall, goethite (Gt) was the main iron oxide in the clay fraction. Only the soils developed from basalt and sandstone showed hematite (Hm) as the predominant mineral. The soils from the Barreiras Group (ES and RR states) showed the lowest iron oxide content, reflecting the low iron level of these sediments. A significant correlation between Gt/(Gt + Hm) ratio and water content extracted by DCB (r = 0.70***) was found, suggesting that this relationship comes from the fact that Gt is a hydrated iron oxide. The clay fraction of the younger soils, specially in the C horizon, showed the highest FeOx/FeDCB ratios and the highest levels of amorphous materials extracted by Ox, reaching 28% for sample 17. This amorphous mineral is basically formed by Al plus some Fe-minerals. Some samples showed similar values for the mean crystal diameter (MCD) of Gt in the (110) and (111) directions, suggesting an isodimensional form of this mineral. The higher values of the MCD for Hm resulted in lower surface area in relation to Gt. The substitution of Fe by Al in the Gt was higher than in Hm (average of 218 and 85 mmol mol-1, respectively). Due to Al substitution in the Gt structure, the crystallinity degree and the mineral size, mainly in the c direction, were reduced as shown by the significant correlation between substitution of Fe by Al and MCD(111) (r = -0.80***). The correlation between Fe and the microelement contents extracted by DCB were high and significant suggesting that the microelements, as also seen for Al, replace Fe in the iron oxide structure. The MCD of the gibbsite (Gb) crystals were higher than that of the iron oxides. Electron microscopy showed that the Gb crystals from the clay fraction appeared to be small square plates, whereas the ones from the silt fraction appeared to be round. Index Terms: Hematite, goethite, gibbsite, XRD, thermal analysis, electron microscopy. Texto completo disponível apenas em PDF. Full text available only in PDF format. LITERATURA CITADA Recebido para publicação em Dezembro de 1998 Aprovado em setembro de 2000 (1 ) Parte da Tese de Doutorado do primeiro autor. ANAND, R.R.; GILKES, R.J.; ARMITAGE, T.M. & HILLER, J.W. Feldspar weathering in lateritic saprolite. Clays Clay Miner., 33:31-43, 1985. Feldspar weathering in lateritic saprolite Clays Clay Miner. 1985 31 43 33 ANAND R.R. GILKES R.J. 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