Distribution and Speciation of Nutrient Elements around Micropores

© 2009 Soil Science Society of AmericaIn Australia a class of soils known as duplex soils covers approximately 20% of the continent. Their defining characteristic is a sharp texture contrast between the A (or E) and B horizon. The upper B horizon at the point of contact with the E horizon is often highly sodic and of such a high strength that root growth and proliferation, water conductivity, aeration, water storage, and water uptake are restricted. Roots growing in these soils rely on channels created by previous roots or cracks arising from shrink–swell forces associated with seasonal wetting and drying. Although the characteristics of rhizospheres compared with the soil matrix are well documented there is a paucity of knowledge about how long these changes persist after roots decay. This knowledge is fundamental to our understanding of root growth in duplex soils in which plants rely on pore networks formed by previous plants to proliferate in the subsoil. In this study we investigated the heterogeneous chemistry of micropores in situ using synchrotron-based µ-x-ray fluorescence spectroscopy (XRF), µ-x-ray absorption near edge structure spectroscopy (XANES), and extended µ-x-ray absorption fine structure spectroscopy (EXAFS). The distribution maps of Ca, Mn, Fe, Cu, and Zn at micrometer resolution were collected using µ-XRF. Subsequently, specific locations with higher concentrations (hot spots) of Mn, Fe, Cu, or Zn were selected and XANES and EXAFS spectra were collected to study the speciation of these elements around the micropore compared with the soil matrix. The µ-XRF maps showed that Mn was depleted around one of the micropores studied but accumulated around another micropore. Copper and Zn accumulated around the micropores, whereas Ca was predominantly inside micropores. There was no difference between matrix and micropore surface with respect to the distribution of Fe. Around micropores Mn was present in reduced form (Mn II) and Fe was in its oxidized form (Fe III). Manganese and Cu were present in the form of phosphates, Fe as Fe oxides, and Zn as Zn phosphates and adsorbed Zn.Laurence Jassogne, Ganga Hettiarachchi, David Chittleborough and Ann McNeil

Rhizodeposition and the enhanced mineralization of 2,4-dichlorophenoxyacetic acid in soil from the Trifolium pratense rhizosphere

Enhanced biodegradation of organic xenobiotic compounds in the rhizosphere is frequently recorded although the specific mechanisms are poorly understood. We have shown that the mineralization of 2,4-dichlorophenoxyacetic acid (2,4-D) is enhanced in soil collected from the rhizosphere of Trifolium pratense[e.g. maximum mineralization rate=7.9 days-1 and time at maximum rate (t1)=16.7 days for 12-day-old T. pratense soil in comparison with 4.7 days-1 and 25.4 days, respectively, for non-planted controls). The purpose of this study was to gain a better understanding of the plant-microbe interactions involved in rhizosphere-enhanced biodegradation by narrowing down the identity of the T. pratense rhizodeposit responsible for stimulating the microbial mineralization of 2,4-D. Specifically, we investigated the distribution of the stimulatory component(s) among rhizodeposit fractions (exudates or root debris) and the influence of soil properties and plant species on its production. Production of the stimulatory rhizodeposit was dependent on soil pH (e.g. t1 for roots grown at pH 6.5 was significantly lower than for those grown at pH 4.4) but independent of soil inorganic N concentration. Most strikingly, the stimulatory rhizodeposit was only produced by T. pratense grown in non-sterile soil and was present in both exudates and root debris. Comparison of the effect of root debris from plant species (three each) from the classes monocotyledon, dicotyledon (non-legume) and dicotyledon (legume) revealed that legumes had by far the greatest positive impact on 2,4-D mineralization kinetics. We discuss the significance of these findings with respect to legume-rhizobia interactions in the rhizosphere

Nickel adsorption by soils in relation to pH, organic matter, and iron oxides Adsorção de níquel em solos em função de pH, matéria orgânica e óxidos de ferro

There is little information on nickel adsorption by Brazilian soils. The objective of this experiment was to determine the effect of pH, organic matter, and iron oxides on nickel adsorption by three soils: a clayey Anionic "Rhodic" Acrudox, a sandy clay loam Anionic "Xanthic" Acrudox, and a clayey Rhodic Hapludalf. Soil samples were collected from the 0-0.2 m layer and treated to eliminate organic matter and iron oxides. The nickel adsorption was evaluated in the original samples and in those treated to remove organic matter and to remove both, organic matter and iron oxides, using 2 g soil + 20 mL of 0.01 mol L-1 CaCl2 solution containing 5 mg L-1 Ni, pH varying from 3.5 to 7.5. The nickel adsorption decreased with the elimination of organic matter. For the samples without organic matter and iron oxides, adsorption decreased only in the Anionic "Rhodic" Acrudox. The pH was the main factor involved in nickel adsorption variation, and for soil samples without organic matter and iron oxides, the maximum adsorption occurred at higher pH values.<br>Há poucas informações disponíveis na literatura quanto à adsorção de níquel em solos do Brasil. O objetivo deste trabalho foi determinar a influência do pH, da matéria orgânica, e dos óxidos de ferro na adsorção de níquel em amostras da camada superficial (0 a 0,20 m) de um Latossolo Vermelho acriférrico típico (LVwf), textura argilosa, um Latossolo Amarelo ácrico típico (LAw), textura argilo-arenosa e um Nitossolo Vermelho eutroférrico (NVef), textura muito argilosa. Foram utilizadas amostras de solo natural, de solo sem matéria orgânica (MO), e de solo sem matéria orgânica e sem óxidos de ferro, para fazer envelopes de adsorção (2,0 g de solo + 20 mL de solução contendo 5 mg L-1 de Ni em CaCl2 0,01 mol L-1, variando o pH de 3,5 a 7,5). A adsorção de níquel diminuiu com a eliminação da MO; a eliminação de MO e de óxidos de Fe só provocou diminuição na média de adsorção no LVwf; o pH foi o principal fator de variação na adsorção de níquel e, com a eliminação da MO e dos óxidos de Fe, os picos de adsorção foram atingidos a valores mais elevados de pH

Efeito da natureza do eletrólito e da força iônica na energia livre da reação de adsorção de níquel em solos Effect of electrolyte nature and ionic strength in the free energy of nickel adsorption reaction in soils

A adsorção é o principal processo responsável pelo acúmulo de metais pesados na superfície dos colóides do solo. O conhecimento detalhado desse fenômeno pode fornecer subsídios para o aprimoramento das práticas de remediação de solos contaminados. Avaliou-se a energia livre (deltaG0) de adsorção de Ni em amostras superficiais (0,0-0,2 m) e subsuperficiais (na maior expressão do horizonte B) de um Latossolo Vermelho acriférrico típico textura argilosa (LVwf) e de um Nitossolo Vermelho eutroférrico textura muito argilosa (NVef), utilizando-se soluções de NaCl e CaCl2 em três forças iônicas (1,0, 0,1 e 0,01 mol L-1). As amostras de solo receberam 2, 5, 10, 20, 30, 40, 50 e 70 mg dm-3 de Ni, na proporção solo:solução de 1:10. A adsorção de Ni pelos solos foi espontânea, visto que a deltaG0 apresentou valores negativos em todas as concentrações estudadas. Os valores de deltaG0 diminuíram com o aumento da dose de Ni adicionada. O NVef apresentou maior deltaG0 que o LVwf devido, principalmente, às suas características químicas e mineralógicas. Os horizontes superficiais apresentaram, em geral, maior deltaG0 em relação aos subsuperficiais, em razão do elevado teor de matéria orgânica encontrado em superfície. A deltaG0 foi maior para as menores forças iônicas do meio, tanto para CaCl2 quanto para NaCl.<br>The adsorption is the main process responsible for the accumulation of heavy metals in the surface of soil colloids. Detailed knowledge of this phenomenon can contribute to improve the remediation practices for contaminated soil. The free energy (deltaG0) of Ni adsorption was evaluated in surface (0.0-0.2 m) and subsurface (in the maximum expression of B horizon) samples of a clayey Rhodic Acrudox (RA) and a very clayey Eutric Kandiudalf (EK). Ni was added (2, 5, 10, 20, 30, 40, 50, and 70 mg dm-3), in a 1:10 soil:solution ratio. Two background electrolytes (NaCl and CaCl2) and three ionic strengths - IS (1.0; 0.1 and 0.01 mol L-1) were tested. The Ni adsorption reaction was spontaneous, since the deltaG0 values were negative in all concentrations. Values of DG0 decreased with the increasing Ni doses. deltaG0 was higher in the EK presented than in RA, mainly due to its chemical and mineralogical characteristics. In surface samples, deltaG0 was generally higher than in subsurface samples due to their higher organic matter contents. The deltaG0 was higher for solutions with lower IS, regardless of the electrolyte type

Disponibilidade de zinco para milho pelos extratores Mehlich-1, Mehlich-3 e DPTA em solos de Minas Gerais, na presença e ausência de calagem Zinc availability to maize in different soils with and without liming determined by Mehlich-1, Mehlich-3 and DTPA

No Brasil, diversos extratores químicos são utilizados na determinação de Zn disponível para as plantas, destacando-se Mehlich-1 e DTPA. Este trabalho foi realizado com o objetivo de estudar a disponibilidade de Zn em solos de Minas Gerais em função de doses de Zn e de calcário e extratores químicos, utilizando-se milho como planta indicadora. Os extratores estudados foram: (a) Mehlich-1 com filtragem lenta após a extração (M-1f); (b) Mehlich-1 com retirada do sobrenadante após 16 h de repouco (M-1s); (c) Mehlich-3 (M-3); e (d) DTPA. As amostras receberam adubação básica com macro e micronutrientes (-Zn) e cinco doses de Zn na forma de ZnSO4 (0, 2, 4 6 e 8 mg dm-3 de Zn) na ausência ou presença de calagem. Quinze dias após a fertilização, subamostras foram coletadas para a determinação de Zn pelos extratores. Para Mehlich-1, o extrato foi obtido por meio de dois procedimentos: filtragem logo após extração (M-1f) e retirada de alíquota após 16 h (M-1s). O restante do solo foi acondicionado em vasos plásticos, para o cultivo do milho durante 50 dias. A capacidade de extração variou na seguinte ordem: M-1s > M-1f > M-3 > DTPA, para todos os solos, na ausência e na presença de calagem. O M-1s e o M-3 não apresentaram diferenças na capacidade de extração com a calagem, enquanto M-1f e DTPA foram sensíveis à calagem. Os teores de Zn obtidos com todos os extratores correlacionaram-se significativa e negativamente com o teor de argila e a capacidade de campo dos solos, tanto na ausência como na presença de calagem. Os teores obtidos com DTPA apresentaram maior correlação com características de solo na presença de calagem, indicando que esse extrator aumentou sua sensibilidade à capacidade-tampão em valores mais elevados de pH. Todos os extratores mostraram correlações com o conteúdo de Zn na planta; portanto, podem ser utilizados na avaliação da disponibilidade de Zn do solo.<br>In Brazil, plant-available Zn in the soil is determined by several chemical procedures, of which the most commonly used are Mehlich-1 and DTPA. The objective of this study was to evaluate Zn availability in soils of Minas Gerais State, under different Zn and lime rates, using the extractors Mehlich-1, Mehlich-3 and DTPA and maize as indicator plant. Seven soil samples were incubated with lime to reach pH 6.0. The samples were treated with Zn in the form of ZnSO4, in the absence or presence of lime, and with a basic Zn-free fertilization of macro and micronutrients. Fifteen days after fertilization, sub-samples were collected for Zn determination by the extractors. For Mehlich-1 the extract was obtained by two procedures: filtering soon after extraction (M-1f) and aliquot withdrawal from the supernatant after 16 h (M-1s). The remaining soil was filled into plastic pots for maize cultivation during 50 days. The extraction capacity diminished in the following order: M-1s > M-1f > M-3 > DTPA, in all soils, with or without liming. M-1s and M-3 did not differ in extraction capacity in limed soil, whereas M-1f and DTPA were sensitive to liming. The Zn concentration values obtained with all extractors were negative and significantly correlated with clay content and soil water field capacity, with or without liming. The extraction capacity of DTPA was better correlated with soil properties in the presence of lime, indicating that the response of this extractor is better in higher-pH soils. All extractors were correlated with plant Zn content, and can therefore be used in the evaluation of soil Zn availability