Some aspects of the interaction of humic substances with metal ions

Humic substances are the major organic constituents of soils and sediments. They are heterogeneous, polyfunctional, polydisperse, macromolecular and have no accurately known chemical structure. Their interactions with radionuclides are particularly important since they provide leaching mechanisms from disposal sites. The central theme to this research is the interaction of heavy metal actinide analogues with humic materials. Studies described focus on selected aspects of the characteristics and properties of humic substances. Some novel approaches to experiments and data analysis are pursued. Several humic substances are studied; all but one are humic acids, and those used most extensively were obtained commercially. Some routine characterisation techniques are applied to samples in the first instance. Humic substances are coloured, but their ultra-violet and visible absorption spectra are featureless. Yet, they fluoresce over a wide range of wavelengths. Enhanced fluorescence in the presence of luminescent europium(III) ions is explained by energy transfer from irradiated humic acid to the metal ion in a photophysical model. Nuclear magnetic resonance spectroscopy is applied to the study of humic acids and their complexes with heavy metals. Proton and carbon-13 NMR provides some structural and functionality information; Paramagnetic lanthanide ions affect these spectra. Some heavy metals are studied as NMR nuclei, but measurements are restricted by their sensitivity. A humic acid is fractionated yielding a broad molecular weight distribution. Electrophoretic mobilities and particle radii determined by Laser Doppler Electrophoretic Light Scattering are sensitive to the conditions of the supporting media, and the concentration and particle size distribution of humic substances. In potentiometric titrations of humate dispersions, the organic matter responds slowly and the mineral acid addition is buffered. Proton concentration data is modelled and a mechanism is proposed involving two key stages, both resulting in proton release after some conformational changes.

Carbon in humic fractions of organic matter in soil treated with organic composts under mango cultivation.

Soil organic matter (SOM) plays a key role in maintaining the productivity of tropical soils, providing energy and substrate for the biological activity and modifying the physical and chemical characteristics that ensure the maintenance of soil quality and the sustainability of ecosystems. This study assessed the medium-term effect (six years) of the application of five organic composts, produced by combining different agro-industrial residues, on accumulation and chemical characteristics of soil organic matter. Treatments were applied in a long-term experiment of organic management of mango (OMM) initiated in 2005 with a randomized block design with four replications. Two external areas, one with conventional mango cultivation (CMM) and the other a fragment of regenerating Caatinga vegetation (RCF), were used as reference areas. Soil samples were collected in the three management systems from the 0.00-0.05, 0.05-0.10, and 0.10-0.20 m layers, and the total organic carbon content and chemical fractions of organic matter were evaluated by determining the C contents of humin and humic and fulvic acids. Organic compost application significantly increased the contents of total C and C in humic substances in the experimental plots, mainly in the surface layer. However, compost 3 (50 % coconut bagasse, 40 % goat manure, 10 % castor bean residues) significantly increased the level of the non-humic fraction, probably due to the higher contents of recalcitrant material in the initial composition. The highest increases from application of the composts were in the humin, followed by the fulvic fraction. Compost application increased the proportion of higher molecular weight components, indicating higher stability of the organic matter.

Sequential exhaustive extraction of a Mollisol soil, and characterizations of humic components, including humin, by solid and solution state NMR.

A comprehensive sequential extraction procedure was applied to isolate soil organic components using aqueous solvents at different pH values, base plus urea (base-urea), and finally dimethylsulfoxide (DMSO) plus concentrated H2SO4 (DMSO-acid) for the humin-enriched clay separates. The extracts from base-urea and DMSO-acid would be regarded as 'humin' in the classical definitions. The fractions isolated from aqueous base, base-urea and DMSO-acid were characterized by solid and solution state NMR spectroscopy. The base-urea solvent system isolated ca. 10% (by mass) additional humic substances. The combined base-urea and DMSO-acid solvents isolated ca. 93% of total organic carbon from the humin-enriched fine clay fraction (<2 ?m). Characterization of the humic fractions by solid-state NMR spectroscopy showed that oxidized char materials were concentrated in humic acids isolated at pH 7, and in the base-urea extract. Lignin-derived materials were in considerable abundance in the humic acids isolated at pH 12.6. Only very small amounts of char-derived structures were contained in the fulvic acids and fulvic acids-like material isolated from the base-urea solvent. After extraction with base-urea, the 0.5 m NaOH extract from the humin-enriched clay was predominantly composed of aliphatic hydrocarbon groups, and with lesser amounts of aromatic carbon (probably including some char material), and carbohydrates and peptides. From the combination of solid and solution-state NMR spectroscopy, it is clear that the major components of humin materials, from the DMSO-acid solvent, after the exhaustive extraction sequence, were composed of microbial and plant derived components, mainly long-chain aliphatic species (including fatty acids/ester, waxes, lipids and cuticular material), carbohydrate, peptides/proteins, lignin derivatives, lipoprotein and peptidoglycan (major structural components in bacteria cell walls). Black carbon or char materials were enriched in humic acids isolated at pH 7 and humic acids-like material isolated in the base-urea medium, indicating that urea can liberate char-derived material hydrogen bonded or trapped within the humin matrix.

Efeitos dos ácidos húmicos provenientes de aterro sanitário em plantas

O processo de tratamento biológico dos lixiviados de aterros sanitários resulta na geração de grandes quantidades de lodo, caracterizados por conterem altas taxas de matéria orgânica. Por meio do fracionamento químico da matéria orgânica são obtidos os ácidos húmicos (AH), fração de comprovada eficiência sobre o crescimento vegetal, promovendo melhorias no desenvolvimento das plantas. Este trabalho teve como objetivo caracterizar quimicamente os AH extraídos do lodo de lixiviado de aterro sanitário e avaliar os efeitos da aplicação de diferentes doses dos AH por meio de análises biológicas em plantas, visando minimizar os potenciais riscos da utilização do lodo in natura. Por meio de caracterizações químicas, o ácido húmico apresentou elevados teores de carbono e nitrogênio, podendo constituir uma importante fonte de nutrientes para as plantas. Além disso, foram observadas alterações nas taxas de absorção, na bioconcentração e na translocação de alguns nutrientes. Com relação à análise das enzimas antioxidantes, foi possível observar aumento na atividade de algumas enzimas com a aplicação de diferentes doses de AH. Além disto, foram constatadas alterações citogenéticas por meio da análise de células meristemáticas e F1 de Allium cepa. Influências sobre o crescimento da planta também são reportadas, por meio de aumentos expressivos na área radicular e na altura de Zea mays. Em geral, os dados de crescimento revelaram um maior investimento da planta na parte aérea, provavelmente associado com a melhor eficiência do sistema radicular. Além disso, também foram reportadas alterações na espessura da epiderme. Neste contexto, apesar dos benefícios nutricionais e da comprovada atuação dos AH sobre o metabolismo vegetal, os seus efeitos biológicos sobre enzimas do estresse oxidativo e a sua capacidade citotóxica precisam ser melhor investigados. Devido à complexidade do resíduo, a utilização de análises químicas, genéticas, enzimáticas, fisiológicas e anatômicas foi uma importante ferramenta para a avaliação da possível aplicação dos ácidos húmicos em plantas.

Ácidos húmicos extraídos do lodo de esgoto sanitário e seus efeitos em plantas

O lodo de esgoto possui alto teor de matéria orgânica porém, também estão presentes diferentes poluentes e patógenos. Desta forma, neste trabalho foi extraído ácido húmico (AH) o qual é um composto resultante do fracionamento de substâncias húmicas que compreendem um grupo de compostos de carbono gerados na decomposição de resíduos orgânicos que sofrem ressíntese formando o húmus. O ácido húmico promove diversos benefícios nos vegetais, como crescimento, elongação celular, tolerância a estresses e aumento da permeabilidade da membrana plasmática. Com base nestas características, o presente trabalho teve como objetivo avaliar os efeitos citogenéticos (ensaio Allium cepa), fisiológicos, anatômicos e bioquímicos do ácido húmico do lodo de esgoto sanitário. Foi realizada caracterização elementar do material para a definição das doses. Após 20 dias de tratamento, foram realizadas coletas do material e, posteriormente, analisadas. A caracterização química do AH indicou-o como bom condicionador para culturas apresentando elevadas taxas de C, H e N. Não foi observado efeito de toxicidade, citotoxicidade, genotoxicidade e mutagenicidade do AH. Foi verificado aumento expressivo de todos os pigmentos fotossintéticos vegetais nas concentrações mais altas (2 mM C L-1 e 4 mM C L-1). Houve aumento da expressão da ATPAse em todos os tratamentos e das enzimas do estresse oxidativo (CAT, SOD, APX, GST) em diferentes concentrações. A integração destas análises permitiu concluir que o ácido húmico do lodo de esgoto pode ser utilizado como adubo orgânico, pois foi observado benefícios no vegetal tais como maior crescimento vegetal e aumento da atividade nas enzimas do estresse oxidativo.

Initial performance of pineapple and utilization of rock phosphate applied in combination with organic compounds to leaf axils

Rock phosphates have low solubility in water, but good solubility in acid. The use of organic compounds together with these phosphorus sources applied to the basal leaf axils of pineapple can increase the solubility of this phosfate source and increase the P availability to the crop. A greenhouse experiment was conducted using Araxá rock phosphate (10 g) in combination or not with solutions containing increasing concentrations of humic acids (0 to 40 mmol L-1 of carbon), with or without citric acid (0.005 mmol L-1), applied to basal leaf axils of pineapple cv. Pérola. Growth and nutritional characteristics of aerial plant parts were assessed. Growth rates of aerial parts and N, P, K, Ca and Mg contents increased curvilinearly with increasing concentration of carbon in the form of humic acids. Maximum values were found for the concentration of 9.3 mmol L-1 of carbon combined with 0.005 mmol L-1 of citric acid and natural phosphate.

DINAMICA MICROBIANA Y CALIDAD DE LA MATERIA ORGANICA DEL SUELO COMO INDICADORES DE SUSTENTABILIDAD EN EL CHACO ARIDO DE LA PROVINCIA DE CORDOBA Microbial dynamic and organic matter quality as indicators of soil sustainability in Dry Chaco of Córdoba Province

Se propone analizar el efecto del uso productivo en el Chaco Árido de la provincia de Córdoba, mediante la aplicación de indicadores de sustentabilidad relacionados con la calidad de la materia orgánica y la liberación de nutrientes en el suelo, con la finalidad de aportar a un tema de suma interes para la provincia de Córdoba como es la formulación de criterios y pautas de manejo para la implementación de la Ley de Bosques (N° 26331). Se trabajará en la localidad de San Miguel en el departamento Pocho, en un sitio de bosque no disturbado y en tres sistemas productivos: desmonte selectivo con implantación de pasturas; desmonte total con agricultura bajo riego y desmonte total sobrepastoreado. En cada sitio se medirá “in situ” la emisión de CO2 y se tomaran muestras de suelo a las que se les determinará: a) contenido de materia orgánica total (MO), b) contenido de sustancias húmicas (SH), diferenciando ácidos húmicos (AH) y fúlvicos (AF), c) abundancia y actividad de microorganismos nitrificadores y d) propiedades químicas de los AH y AF. Se calcularán los siguientes índices de sustentabilidad a) materia orgánica biodisponible (MOB=MO–SH); b) índice de humificación (IH=SH/MO); c) tipo de humus (TH=AF/AH; d) índice de mineralización de C (IMC=CO2/MO); e) índice de nitrificación (IN=actividad/abundancia); y f) índice de estabilidad de las fracciones humificadas: compuestos aromáticos/ alifáticos. Los datos serán analizados estadísticamente mediante ANOVA y comparación de medias por LSD (P<0.05) y tests multivariados. We proposed analyze the effect of land use in Arid Chaco of Cordoba province, using sustainability indicators related to organic matter quality and nutrient release in soil, with the aim to formulate management criteria for the implementation of the Ley de Bosques (N° 26331) in Córdoba province. The study will be conducted in San Miguel village in Pocho department, in one undisturbed forest site and three productive systems: selective clearing with grass sowing; total clearing with irrigation agriculture and total clearing with overgrazed. In each site "in situ" CO2 emission will be measured and soil samples will be taken, in which the following parameters will be determined: a) total organic matter content (MO), b) humic substances content (SH), in humic acids (AH) and fulvic acids (AF), c) abundance and activity of nitrifier microorganisms and d) chemical properties of AH and AF. The sustainability indexes will be calculated: biodisponible organic matter (MOB=MO–SH); b) humification index (IH=SH/MO); c) humus type (TH=AF/AH; d) C mineralization index (IMC=CO2/MO); e) nitrifying index (IN=activity/abundance); and f) humic fractions stability index: aromatic/aliphatic compounds. The data will be statistically analyzed by ANOVA and the means will be compared by LSD (P<0.05) and multivariate tests.

Chemical characterization and infrared spectroscopy of soil organic matter from two southern brazilian soils

Soil organic matter from the surface horizon of two Brazilian soils (a Latosol and a Chernosol), in bulk samples (in situ SOM) and in HF-treated samples (SOM), was characterized by elemental analyses, diffuse reflectance (DRIFT) and transmission Fourier transform infrared spectroscopy (T-FTIR). Humic acids (HA), fulvic acids (FA) and humin (HU) isolated from the SOM were characterized additionally by ultraviolet-visible spectroscopy (UV-VIS). After sample oxidation and alkaline treatment, the DRIFT technique proved to be more informative for the detection of "in situ SOM" and of residual organic matter than T-FTIR. The higher hydrophobicity index (HI) and H/C ratio obtained in the Chernosol samples indicate a stronger aliphatic character of the organic matter in this soil than the Latosol. In the latter, a pronounced HI decrease was observed after the removal of humic substances (HS). The weaker aliphatic character, the higher O/C ratio, and the T-FTIR spectrum obtained for the HU fraction in the Latosol suggest the occurrence of surface coordination of carboxylate ions. The Chernosol HU fraction was also oxygenated to a relatively high extent, but presented a stronger hydrophobic character in comparison with the Latosol HU. These differences in the chemical and functional group composition suggest a higher organic matter protection in the Latosol. After the HF treatment, decreases in the FA proportion and the A350/A550 ratio were observed. A possible loss of FA and condensation of organic molecules due to the highly acid medium should not be neglected.

Redox index of soil carbon stability

As an alternative to the relatively complex and expensive spectroscopic methods, the redox properties of humic acids, determined by potentiometric titrations, have been used to evaluate the stability of soil organic C. The objective of the present study was to establish a Redox Index of C Stability (RICS) and to correlate it with some properties of the humic acids extracted from different modal soils in Brazil (distinct weathering stages or management) to facilitate system comparison. The RICS was efficient for soil comparison and variations were comparable to those of the chemical and spectroscopic methods used for humic acid characterization. The values of soil pH, point of zero salt effect, sum of bases, exchangeable Ca content, weathering index, as well as the humic acid O/C ratio, quinone and semiquinone free radical contents, aromatic C and fluorescence intensity were closely related with the RICS. The RICS was higher in less weathered soils, with more active clays and higher fertility. The RICS values of soils under long-term sugarcane management were ranked in decreasing order: unburned, burned with vinasse, burned without vinasse.

Pedochronology and development of peat bog in the environmental protection area pau-de-fruta - Diamantina, Brazil

In the region of the Serra do Espinhaço Meridional, peat bog is formed in hydromorphic environments developed in sunken areas on the plain surfaces with vegetation adapted to hydromorphic conditions, favoring the accumulation and preservation of organic matter. This pedoenvironment is developed on the regionally predominant quartzite rocks. Peat bog in the Environmental Protection Area - APA Pau-de-Fruta, located in the watershed of Córrego das Pedras, Diamantina,Brazil, was mapped and three representative profiles were morphologically characterized and sampled for physical, chemical and microbiological analyses. The organic matter was fractionated into fulvic acid (FA), humic acids (HA) and humin (H). Two profiles were sampled to determine the radiocarbon age and δ13C. The structural organization of the three profiles is homogeneous. The first two layers consist of fibric, the two subsequent of hemic and the four deepest of sapric peat, showing that organic matter decomposition advances with depth and that the influence of mineral materials in deeper layers is greater. Physical properties were homogeneous in the profiles, but varied in the sampled layers. Chemical properties were similar in the layers, but the Ca content, sum of bases and base saturation differed between profiles. Contents of H predominated in the more soluble organic matter fractions and were accumulated at a higher rate in the surface and deeper layers, while HA levels were higher in the intermediate and FA in the deeper layers. Microbial activity did not vary among profiles and was highest in the surface layers, decreasing with depth. From the results of radiocarbon dating and isotope analysis, it was inferred that bog formation began about 20 thousand years ago and that the vegetation of the area had not changed significantly since then.