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.

Contributions of humic substances to the dissolved organic carbon pool in wetlands from different climates

Wetlands are an important source of DOM. However, the quantity and quality of wetlands’ DOM from various climatic regions have not been studied comprehensively. The relationship between the concentrations of DOM (DOC), humic substances (HS) and non-humic substances (NHS) in wetland associated sloughs, streams and rivers, in cool temperate (Hokkaido, Japan), sub-tropical (Florida, USA), and tropical (Sarawak, Malaysia) regions was investigated. The DOC ranged from 1.0 to 15.6 mg C L−1 in Hokkaido, 6.0–24.4 mg C L−1 in Florida, and 18.9–75.3 mg C L−1 in Sarawak, respectively. The relationship between DOC and HS concentrations for the whole sample set was regressed to a primary function with y-intercept of zero (P < 0.005) and a slope value of 0.841. A similar correlation was observed between DOC and NHS concentrations, with a smaller slope value of 0.159. However, the correlation coefficient of the latter was much larger when the data was regressed to a logarithmic curve. These observations suggest the presence of a general tendency that the increased DOC in the river waters was mainly due to the increased supply of HS from wetland soils, whereas the rate of the increase in the NHS supply has an upper limit which may be controlled by primary productivity.

Development of a new analytical approach based on cellulose membrane and chelator for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L-1 of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L-1) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems. (c) 2006 Elsevier B.V. All rights reserved.

Reduction capability of soil humic substances from the Rio Negro basin, Brazil, towards Hg(II) studied by a multimethod approach and principal component analysis (PCA)

This paper characterizes humic substances (HS) extracted from soil samples collected in the Rio Negro basin in the state of Amazonas, Brazil, particularly investigating their reduction capabilities towards Hg(II) in order to elucidate potential mercury cycling/volatilization in this environment. For this reason, a multimethod approach was used, consisting of both instrumental methods (elemental analysis, EPR, solid-state NMR, FIA combined with cold-vapor AAS of Hg(0)) and statistical methods such as principal component analysis (PCA) and a central composite factorial planning method. The HS under study were divided into groups, complexing and reducing ones, owing to different distribution of their functionalities. The main functionalities (cor)related with reduction of Hg(II) were phenolic, carboxylic and amide groups, while the groups related with complexation of Hg(II) were ethers, hydroxyls, aldehydes and ketones. The HS extracted from floodable regions of the Rio Negro basin presented a greater capacity to retain (to complex, to adsorb physically and/or chemically) Hg(II), while nonfloodable regions showed a greater capacity to reduce Hg(II), indicating that HS extracted from different types of regions contribute in different ways to the biogeochemical mercury cycle in the basin of the mid-Rio Negro, AM, Brazil. (c) 2007 Published by Elsevier B.V.

Thermal Decomposition Kinetics of Humic Substances Extracted from Mid-Rio Negro (Amazon Basin) Soil Samples

In this work humic substances (HS) extracted from non-flooded (Araca) and flooded (Iara) soils were characterized through the calculation of stability and activation energies associated with the dehydration and thermal decomposition of HS using TGA and DTA, electronic paramagnetic resonance and C/H, C/N and C/O atomic ratios. For HS extracted from flooded soils, there was evidence for the influence of humidity on the organic matter humification process. Observations of thermal behaviour, with elemental analysis, indicated the presence of fossilized organic carbon within clay particles, which only decomposed above 800 C. This characteristic could explain the different thermal stability and pyrolysis activation energies for Iara HS compared to Araca HS.

Peat humic substances enriched with nutrients for agricultural applications: Competition between nutrients and non-essential metals present in tropical soils

Improved agricultural productivity, and reduction of environmental impacts, require studies of the interactions between different soil components. Fertilizers marketed as "organic" or "natural", such as peats or humic substances (HS) extracted from peats, are enriched with macro and micronutrients that, according to the manufacturers, are released to the plant in accordance with its needs. This work investigates the complexation capacity of HS for macro and micronutrient metal species, considering the competition, for HS complexation sites, between non-essential metals (aluminium and lead), present in the soil, and the nutrients. Humic substances were found to possess strong affinities for Pb(II) and Al(III), forming stable complexes, with concomitant release of complexed nutrients. Although HS are already used commercially as organic fertilizers, further studies of methods of HS enrichment, aimed at avoiding losses, are highly desirable from environmental and economic perspectives. (C) 2009 Elsevier B.V. All rights reserved.

Potential valorization as fertilizers of Humic Substances extracted from landfill leachate

In this study, four leachates samples from 3 different landfills localized in the north of Portugal were characterized and fractionated, to understand the decomposition degree and to evaluate their potential as an agent for fertilization. Humic substances (HS) were extracted, quantified, chemical characterized and further fractionated in humic acid (HA) and fulvic acid (FA). Keeping in mind the purpose to use these fractions as fertilizers, the phytotoxicity of HS, HA and FA solutions was evaluated on cress seed germination. The HS concentration was similar for all the leachates evaluated and was higher than 780 mg/L of total organic carbon. All the leachates analysed registered higher FA concentration than HA. The chemical characterization indicated that HA had a relatively higher aromatic character than the FA obtained from same sources. These results suggest that the HS from landfill leachates were in an early stage of humification, once the degree of humification increase as the landfilling age increase. Overall, the HS extracts showed absence of phytotoxicity, with germination index greater than 80% for samples treated to achieve low electric conductivity values. This suggests that the HS from the leachate may be used to produce liquid organic fertilizers.

Estudo da labilidade de Cu(II), Cd(II), Mn(II) e Ni(II) em substâncias húmicas aquáticas utilizando-se membranas celulósicas organomodificadas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterização estrutural das substâncias húmicas aquáticas extraídas dos rios itapanhaú e ribeira de iguape

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Distribuição de metais e caracterização das constantes de troca entre espécies metálicas e frações húmicas aquáticas de diferentes tamanhos moleculares

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Redução de crômio hexavalente por substâncias húmicas aquáticas imobilizadas em aminopropil sílica

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Substâncias húmicas aquáticas: fracionamento molecular e caracterização de rearranjos internos após complexação com íons metálicos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterização e dinâmica de metais em rios da Bacia Hidrográfica do Turvo/Grande. -

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

O papel das substâncias húmicas na disponibilidade de metais e benzo[a]pireno e indução de metalotioneínas em peixes

Pós-graduação em Química - IBILCE