Chemical and structural characterization of soil humic substances under agroforestry and conventional systems

Studies have proven that the agroforestry systems in the semi-arid region of the State of Ceará, Brazil, induce an increase in soil organic C levels. Notwithstanding, there is no information if this increase also results in qualitative changes in different pools of soil organic matter. The objective of this study was to verify the possible chemical and structural alterations in fulvic and humic acids of a Luvisol in areas adopting agroforestry, traditional intensive cultivation and native forest in a long-term experiment conducted in the semi-arid region of Ceará State, Brazil. The study was conducted in an experimental area of the National Goat Research Center (Embrapa) in Sobral, CE. The following treatments were evaluated: agrosilvopasture (AGP), silvopasture (SILV), intensive cultivation under fallow (ICF), and areas with native forest (NF). Soil fulvic and humic acids fractions were extracted from the 0-6 and 6-12 cm layers and characterized by elemental composition, thermogravimetry and infrared spectroscopy analyses. The elemental composition analysis of humic acids confirmed the data found for fulvic acids, showing reduction in the C, H and N levels, followed by an increase in O contents in the AGP and ICF treatments over SILV and NF. In all treatments, except to SILV in the 0-6 cm layer, the percentage of mass loss was highest (300-600 °C) for humic acids in the thermally most stable region. Despite the similarity between infrared spectra, soil fulvic acids in the SILV treatment extracted from 6-12 cm depth decrease the absorption bands at 1708 and 1408 cm-1 followed by an increase in the absorption band at 1608 cm-1 attributed to aromatic C=C groups. This behavior suggests an increase in the aromatic character of the structure. The AGP and ICF treatments, which increase the soil tilling, favored the maintenance of humic substances with a more aromatic character in the soil than SILV and NF. The less aromatic humic substances in the SILV treatment resulted in an increase of exchange sites of soil organic matter, indicating improved nutrient cycling and maintenance of productivity in the system.

Carbon in Humic Fractions of Organic Matter in Soil Treated with Organic Composts under Mango Cultivation

ABSTRACT 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.

A direct potentiometric titration study of the dissociation of humic acid with selectively blocked functional groups

A direct potentiometric titration method was applied to commercial and soil humic acids in order to determine their carboxyl and phenol group concentrations and apparent and intrinsic pK. In that context, acid-base properties of humic acids are interpreted by selective blocking of carboxylic and phenolic groups by esterification and acetylation. Differences in underivatized and derivatized HA's acid-base properties are ascribed to carboxyl and phenol groups influence on total humic acidity. Potentiometric data were treated with the modified Henderson-Hasselbalch equation. Infra red results, the acidic group contents and the average values of apparent and intrinsic pK for underivatized and derivatized HAs confirmed the selectivity of esterification derivatization method. After blocking of the functional groups, the values of acidic group contents decreased, while the value of apparent pK increased after derivatization. Phenol groups cannot be specifically identified by the acetylation method, due to low selectivity of the acetylation method.

Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Sorptional Behaviour of Metals on the Sediments and Humic acid of Mangrove Ecosystem

Humic substances are complex polymeric structures.No other polymers with such a wide range of properties are so widely distributed in nature.But still their moleculer structures are unknown. A structural knowledge is essential in determining their reactivity with metals.In the present work structural elucidation of humic acids from three different mangrove ecosystems of Cochin area is done with the available data from functional group analysis and various spectroscopic methods.13C NMR spectra of the solid samples with CPMAS,IR and SEM are very promising in revealing the complex structures of these polymeric substances.Sorptional studies on the sediment and humic acid of mangrove ecosystem reveals that the major portion of the organic matter is not extractable with Sodium hydroxide and humic acid only a small portion of the total organic matter. Humic acid is a good complexing agent and scavenger. Due to the nonextractable nature of the organic matter present with the sediment left after alkali extraction it is a better scavenger.

Structural description of humic substances from subtropical coastal environments using elemental analysis, FT-IR and C-13-solid state NMR data

Elemental composition and spectroscopic properties (FT-IR and CP/MAS C-13-NMR) of sedimentary humic substances (HS) from aquatic subtropical environments (a lake, an estuary and two marine sites) are investigated. Humic acids (HA) are relatively richer in nitrogen and in aliphatic chains than fulvic acids (FA) from the same sediments. Conversely, FA are richer in carboxylic groups and in ring polysaccharides than HA. Nitrogen is mostly present as amide groups and for lake and marine HS the FT-IR peaks around 1640 cm(-1) and 1540 cm(-1) identify polypeptides. Estuarine HS exhibit mixed continental-marine influences, these being highly influenced by site location. Overall, the data suggest that aquatic and mixed HS are more aliphatic than has been proposed in current models and also that amide linkages form an important part of their structural configuration.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).

Interactions of chlorine with tropical aquatic fulvic acids and formation of intermediates observed by fluorescence spectroscopy

The interactions of tropical aquatic fulvic acids (AFA) with chlorine and formation of trihalomethanes were characterized by fluorescence spectroscopy. The aquatic humic substances (AHS) were isolated from a dark-brown stream (located in a environmental protection area near Cubatão city in São Paulo State, Brazil) by means of the collector XAD 8 according the procedure recommended by the International Humic Substances Society. The photoluminescence measurements were made by using a Perkin Elmer spectrometer; AHS, aquatic humic acids (AHA) and AFA samples were assayed. The interactions of AFA and chlorine were characterized by using different reaction times (1, 24, 48, 72 and 168 h) and chlorine concentrations (2.5, 5.0, 10.0 and 20.0 mg L-1). The relative fluorescence intensity for AFA was significantly decreased with the increasing of chlorine concentration and reaction time. The reduction of fluorescence intensity in the region of longer wavelength was interpreted as an indicative of interaction between condensed aromatic groups of AFA and chlorine.

Studies on the interaction between humic substances and conducting polymers for sensor application

The interaction between humic substances and poly(o-ethoxyaniline) (POEA), a conducting polymer, was investigated for both solution and self-assembled films. The results have shown that the humic substances induce a doping of POEA by protonation, as indicated by UV-Vis and Raman spectroscopies. The atomic force microscopy (AFM) studies on the self-assembled films have shown that the average roughness of the polymer film has increased after exposing it to humic substances (fulvic and humic acids), consistent with the interaction between POEA and humic substances. However, this change in morphology is reversible by washing the films with water in agreement with the electrical data allowing using this system in sensor applications. Here, the sensor formed by an array of different sensing units was able to detect and distinguish humic substances in aqueous solution, as shown by multivariate analysis (principal component analysis). The motivation to detect humic substance comes due to its importance in terms of quality control of water or soil. ©2005 Sociedade Brasileira de Química.

Fractionation of aquatic humic substances and dynamic of chromium species in an aquatic body influenced by sugarcane cultivation

This study had as main objectiveto evaluate the influence of AHS obtained from an area under sugarcane cultivation on the dynamics of chromium species (Cr(III) and Cr(VI)). Was studied complexing capacity (CC) with the AHS of chromium species and these were characterized using UV/Vis spectrophotometry, molecular fluorescence, elemental analysis and infrared. AHS with and without fractionation showed a greater aromaticity degree and a predominance of humic acids, and the E4/E6 and E2/E4 ratios suggested aromatic rings and a greater contribution from plants, which indicates lignin structures. The highest CCs were observed for the AHS fractionated, being fraction with molecular-size < 10 kDa and 10-30 kDa showed the highest ability to complex Cr(III) and Cr(VI) ions, respectively. These results are corroborating with C/H/N and UV/Vis data, where we can conclude that the AHS without fractionation had the greatest aromaticity and a predominance of humic acids in their structure.

Seasonal variability of a conditional stability constant and the characterization of sedimentary humic substances from typical agricultural and urban areas

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

Study of the interactions of Neptunium with humic substances and the clay mineral montmorillonite by direct and non direct speciation methods

For the safety assessment of radioactive waste, the possibility of radionuclide migration has to be considered. Since Np (and also Th due to the long-lived 232-Th) will be responsible for the greatest amount of radioactivity one million years after discharge from the reactor, its (im)-mobilization in the geosphere is of great importance. Furthermore, the chemistry of Np(V) is quite similar (but not identical) to the chemistry of Pu(V). Three species of neptunium may be found in the near field of the waste disposal, but pentavalent neptunium is the most abundant species under a wide range of natural conditions. Within this work, the interaction of Np(V) with the clay mineral montmorillonite and melanodins (as model substances for humic acids) was studied. The sorption of neptunium onto gibbsite, a model clay for montmorillonite, was also investigated. The sorption of neptunium onto γ-alumina and montmorillonite was studied in a parallel doctoral work by S. Dierking. Neptunium is only found in ultra trace amounts in the environment. Therefore, sensitive and specific methods are needed for its determination. The sorption was determined by γ spectroscopy and LSC for the whole concentration range studied. In addition the combination of these techniques with ultrafiltration allowed the study of Np(V) complexation with melanoidins. Regrettably, the available speciation methods (e.g. CE-ICP-MS and EXAFS) are not capable to detect the environmentally relevant neptunium concentrations. Therefore, a combination of batch experiments and speciation analyses was performed. Further, the preparation of hybrid clay-based materials (HCM) montmorillonitemelanoidins for sorption studies was achieved. The formation of hybrid materials begins in the interlayers of the montmorillonite, and then the organic material spreads over the surface of the mineral. The sorption of Np onto HCM was studied at the environmentally relevant concentrations and the results obtained were compared with those predicted by the linear additive model by Samadfam. The sorption of neptunium onto gibbsite was studied in batch experiments and the sorption maximum determined at pH~8.5. The sorption isotherm pointed to the presence of strong and weak sorption sites in gibbsite. The Np speciation was studied by using EXAFS, which showed that the sorbed species was Np(V). The influence of M42 type melanodins on the sorption of Np(V) onto montmorillonite was also investigated at pH 7. The sorption of the melanoidins was affected by the order in which the components were added and by ionic strength. The sorption of Np was affected by ionic strength, pointing to outer sphere sorption, whereas the presence of increasing amounts of melanoidins had little influence on Np sorption.

Organic carbon and humic substances contents, carbon isotope composition and peroxidase activity in sediments from DSDP Sites 15-147 and 75-532

Sediment samples from the Cariaco Trench (DSDP Leg 15) and the Walvis Ridge (DSDP Leg 75) ranging in age from Holocene to Upper Miocene (approximately 8 million years BP) and in depth from 5 to 258 m were extracted with basic sodium pyrophosphate and the extract analyzed for enzymic activity. Since no dehydrogenase, alkaline phosphatase or esterase activity was found, it is estimated from these data that the maximum bacterial population does not exceed 1000 cells per gram dry sediment. Peroxidase activity was, however, found in most samples: this showed marked dependence on the humic substance concentration (expressed as percent of the organic carbon content) and increased with depth at a rate of 33 units per meter. To explain this observation, we favor an hypothesis based on the presence of active humic-enzyme association. The humic substances absorb and stabilize peroxidase which is liberated throughout the sediment column by lysis of cells. The association of the enzyme with the humic substances protects it from biodegradation and denaturation. This hypothesis agrees with laboratory experiments which show the enhanced stability of humic-enzyme complexes towards degradation by biological, chemical and thermal effects.