Heavy‐metal cations can be introduced into agricultural soils by application of fertilizers, liming materials, sewage sludge, composts, and other industrial and urban waste materials. Therefore, heavy‐metal adsorption reactions, in a competitive system, are important to determine heavy‐metal availability to plants and their mobility throughout the soil. This study was conducted to evaluate the selectivity sequence and estimate the competitive adsorption of several heavy metals in seven soils with different chemical and mineralogical characteristics. Distribution coefficients (Kd), which represent the sorption affinity of metals for the solid phase, were obtained for each soil and heavy‐metal cation. On the basis of these Kd, the selectivity sequence was evaluated. The most common sequences were Cr > Pb > Cu > Cd > Zn > Ni and Pb > Cr > Cu > Cd > Ni > Zn. Chromium, Pb, and Cu were the heavy‐metal cations most strongly adsorbed by all soils, whereas Cd, Ni, and Zn were the least adsorbed, in the competitive situation. Selectivity sequences related to valence for the trivalent Cr. For metals of the same valence, sequences did not exactly follow the order of electronegativity. For individual elements, the Misono softness parameter and hydrolysis properties of the heavy‐metal cations may have influenced the sequences. Correlation analysis showed that soil characteristics that may have affected the heavy‐metals adsorption, represented by the distribution coefficients, were pH and cation‐exchange capacity (CEC) for Cd and Cr; organic carbon, clay, and gibbsite contents for Cu; pH and CEC for Ni and Pb.

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Twelve Oxisols from the Triangulo Mineiro region, Minas Gerais state, Brazil, derived from four different parent materials were studied to provide insight into their Fe‐oxide mineralogy. The clay fraction (<2 µm) of all soils consisted of kaolinite and Fe oxides (hematite and/or goethite); gibbsite and anatase were found in most of the soils; maghemite was detected in several of them. Citratedithionite (CD) treatment of the soil clays showed hematite preferentially dissolved compared with goethite, and a higher dissolution rate for poorly crystalline than for well‐crystalline goethite. The calculated values for Al substitution in the Fe oxides, based on the CD extracts of the total clay corrected for Al soluble in acid ammonium oxalate, and of clay treated for gibbsite removal gave fair to good agreement with Al substitution determined by differential x‐ray diffraction (DXRD) for those samples in which the Fe‐oxide fraction was dominated by either goethite or hematite. Aluminum‐substituted maghemite, detected by DXRD, was present only in soils from mafic rocks, suggesting its formation through oxidation of the magnetite present in the parent material. Aluminum substitution, determined by DXRD, varied from 17 to 36 mol % for goethites, 6 to 15 mol % for hematites, and 16 to 26 mol % for maghemites. The mean crystallite dimension (MCDkkl) of some hematite samples determined from DXRD showed preferential crystal development in the X‐Y direction, suggesting a platy nature.

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Highly weathered kaolinitic soils in Brazil often have adequate levels of K and Mg to support plant growth. The source of K and Mg in these soils and their relationship with the dominant mineral, kaolinite, is addressed in this article. Crystallographic, chemical, and morphological properties of kaolinite, from selected highly weathered Brazilian soils, were investigated by x‐ray diffraction (XRD), analytical electron microscopy (AEM), chemical, and thermal methods. Kaolinite properties showed significant variations such as d(001) spacing ranging between 0.713 to 0.728 nm, width at half height (WHH) between 0.30 to 0.97 °2θ, and dehydroxylation temperature between 489 to 518°C. Kaolinite in the clay fraction has relatively poor crystal order with a mean crystallinity index value(CI) of 12.7. The dominant forms of the clay‐fraction kaolinite were elongated and rounded, with relatively lower proportions of hexagonal particles. The silt‐fraction kaolinite showed a tendency to form subspherical large aggregates with high stability. The average Fe2O3 level in the kaolinite of the clay fraction (19.1 g kg−1) was higher than that obtained for the silt fraction (6.6 g kg−1). The smaller kaolinite particles of the clay fraction showed a lower degree of crystal order, higher K and Mg levels, and lower dehydroxylation temperatures. From the strong relationship between the asymmetry index (AI) of the (001) diffraction line and the level of K in kaolinite from the younger soils, we believe that both K and Mg in kaolinite are part of residual micaceous layers interleaved in kaolinite crystals.

In order to better understand the relationship between soil characteristics and mobility of some heavy metals, correlation studies were conducted in samples of unlimed and limed A, B and C horizons of three Brazilian soils, representative of the majority of the tropical soils. A number of chemical and mineralogical characteristics of one Oxisol and two Ultisols were related to the retardation factors (Rf) for zinc (Zn), cadmium (Cd), copper (Cu) and lead (Pb). The retardation factors, obtained in leaching column experiments, were used as an estimate of solute movement in the profile. Soil types and soil horizons were found to influence metal retardation factors which, in turn, correlated better with the chemical than the mineralogical soil characteristics. For the unlimed soil samples, the soil characteristics that significantly correlated with Zn-Rf and Cd-Rf were the sum of exchangeable bases (SB), and soil exchangeable (Ca-KCl) and non-exchangeable (Ca-HCl) calcium contents. These results showed the strong influence of the cation exchange phenomenon on the retention and mobility of these two metals. For Cu and Pb, not only SB, cation exchange capacity (CEC) and Ca-KCl and Ca-HCl but also the organic matter correlated well with the Rf, showing that complex or chelate formation may play an important role in the movement of these elements. The important soil chemical characteristics related to the retardation factors in the limed soil samples were SB for Cd, and Ca-HCl for Cu and Pb, suggesting that precipitation may also influence the mobility and retention of the latter two heavy metals in these soil samples. Soil pH influenced the heavy metals adsorption and movement as shown by the significant correlation with the retardation factors when the combined data for the unlimed and limed soil samples was considered.

RESUMOPara 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

O conhecimento das propriedades eletroquímicas das partículas minerais dos solos altamente intemperizados é imprescindível para o avanço dos estudos em diferente áreas da Ciência do Solo, como, Física, Manejo e Conservação, Fertilidade e Poluição do Solo. Nesse contexto, o comportamento das cargas superficiais e seu relacionamento com a mineralogia dos solos de carga variável é de importância fundamental para o entendimento e a melhoria da capacidade preditiva de diversos fenômenos, tais como dispersão e floculação de colóides, troca catiônica, adsorção de ânions, especialmente os fosfatos, adsorção de metais pesados, etc. Assim, essa revisão de literatura faz uma abordagem científica do tema "Eletroquímica das partículas coloidais e sua relação com a mineralogia de solos altamente intemperizados", na qual é contemplado o histórico da evolução do conhecimento nesse campo e os desafios para o aprofundamento das pesquisas futuras na área. As diferentes tendências e posicionamentos existentes na literatura sobre Pontos de Carga Zero (PCZs), Caracterização e Medição de Cargas, Nomenclatura e Simbologia de PCZs e Relacionamento entre Cargas e Minerais de solos altamente intemperizados são também apresentados. Conceituações básicas são revisitadas e conceitos novos ou pouco utilizados na Ciência do Solo são apresentados e discutidos, com o intuito de se melhorar o entendimento e aprimorar a interpretação de tão importante ramo da Química, Mineralogia e Poluição de Solos.