Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, C-13 NMR, FTIR and fluorescence spectroscopy

The importance of soil organic matter functions is well known, but structural information, chemical composition and changes induced by anthropogenic factors such as tillage practices are still being researched. In the present paper were characterized Brazilian humic acids (HAs) from an Oxisol under different treatments: conventional tillage/maize-bare fallow (CT1); conventional tillage/maize rotation with soybean-bare fallow (CT2)-, no-till/maize-bare fallow (NT1); no-till/maize rotation with soybean-bare fallow (NT2); no-till/maize-cajanus (NT3) and no cultivated soil under natural vegetation (NC). Soil HA samples were analyzed by electron paramagnetic resonance (EPR), solid-state C-13 nuclear magnetic resonance (C-13 NMR), Fourier transform intra-red (FTIR) and UV-Vis fluorescence spectroscopies and elemental analysis (CHNS). The FTIR spectra of the HAs were similar for all treatments. The level of semiquinone-type free radical determined from the EPR spectra was lower for treatments no-till/maize-cajanus (NT3) and noncultivated soil (1.74 X 10(17) and 1.02 x 10(17) spins g(-1) HA, respectively), compared with 2.3 X 10(17) spins g(-1) HA for other soils under cultivation. The percentage of aromatic carbons determined by C-13 NMR also decreases for noncultivated soil to 24%, being around 30% for samples of the other treatments. The solid-state C-13 NMR and EPR spectroscopies showed small differences in chemical composition of the HA from soils where incorporation of vegetal residues was higher, showing that organic matter (OM) formed in this cases is less aromatic. The fluorescence intensities were in agreement with the percentage of aromatic carbons, determined by NMR (r = 0.97 P < 0.01) and with semiquinone content, determined by EPR (r = 0.97 P < 0.01). No important effect due to tillage system was observed in these areas after 5 years of cultivation. Probably, the studied Oxisol has a high clay content that offers protection to the clay-Fe-OM complex against strong structural alterations. (C) 2003 Elsevier B.V. All rights reserved.

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)

Organic matter fractions and soil fertility under the influence of liming, vermicompost and cattle manure

Os efeitos do vermicomposto de esterco de curral associado à calagem em atributos da fertilidade do solo foram avaliados através de experimento em vasos empregando um Latossolo Vermelho, distrófico, textura média. Cinco doses do vermicomposto (equivalentes a 0; 28; 42; 56 e 70 t ha-1, peso seco) e cinco doses de calcário (visando elevar a saturação por bases a: 20; 30; 40; 50 e 60%) foram combinadas em esquema fatorial, sendo as amostras de solo incubadas por 180 dias. Para comparação entre o vermicomposto e o esterco de curral, amostras do mesmo solo receberam o equivalente a 70 t ha-1 do esterco de curral que originou o vermicomposto e as cinco doses de calcário listadas anteriormente. Através do cálculo do Índice de Eficiência Agronômica, foi verificado que o potencial de fornecimento de K e de Mg pelo esterco é maior do que o do vermicomposto, e que o de P, é semelhante. O vermicomposto aumentou os teores de Ca2+ e de matéria orgânica (MO), os valores de pH em CaCl2 e a CTC a pH 7. Com o aumento das doses de vermicomposto houve diminuição do C-ácidos húmicos e aumento do C-humina e com a calagem o C-total não aumentou mas houve diminuição do C-ácidos húmicos.

Soil organic matter as a function of nitrogen fertilization in crop successions

A interdependência dos ciclos de C e N reflete-se nos teores de matéria orgânica do solo (MOS). em um delineamento experimental em blocos casualizados, com parcelas sub-subdivididas, tendo como tratamento principal cinco doses de nitrogênio de cobertura na cultura do milho (0; 60; 120; 180 e 240 kg ha-1 de N), como tratamento secundário, as sucessões milho-milho e soja-milho, e como sub-subtratamento, duas profundidades de amostragem (0 a 0.2 e 0.2 a 0.4 cm), avaliaram-se os teores de MOS e de C orgânico nas frações solúvel em água (C-SA), ácidos húmicos (C-AH), ácidos fúlvicos (C-AF) e humina (C-H), por meio do método clássico de fracionamento químico, em um Latossolo Vermelho eutrófico, de textura argilosa. A adubação nitrogenada não afetou os teores de MOS, mas favoreceu a síntese de compostos da fração C-AH. Houve efeito quadrático das doses de N nos teores de C-SA e de C-AF na sucessão milho-milho. A sucessão soja-milho resultou em maiores teores de MOS e de C orgânico na fração humina.

Application of chemometric methods in the evaluation of chemical and spectroscopic data on organic matter from Oxisols in sewage sludge applications

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

Alterações na matéria orgânica e na biomassa microbiana em solo de mata natural submetido a diferentes manejos

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

Mutagenic compounds generated from the chlorination of disperse azo-dyes and their presence in drinking water

The water produced by the Cristais River Drinking Water Treatment Plant (CR-DWTP) repeatedly produced mutagenic responses that could not be explained by the presence of disinfection byproducts (DBPs) generated by the reaction of humic acids and chlorine. In order to determine the possible role of chlorinated dye products in this mutagenic activity, solutions of a black dye commercial product (BDCP) composed of C. I. Disperse Blue 373, C. I. Disperse Orange 37, C. I. Disperse Violet 93, and chemically reduced BDCP (R-BDCP) were chlorinated in a manner similar to that used by the CR-DWTP. The resulting solutions were extracted with XAD-4 along with one drinking water sample collected from the CR-DWTP. All extracts showed mutagenic activity in the Salmonella/microsome assay. Dye components of the BDCP as well as its reduced chlorinated (Cl-R-BDCP) derivative were detected in the drinking water sample by analysis with a high performance liquid chromatography/diode array detector (HPLC/DAD). The mutagenicity results of these products suggest that they are, at least in part, accounting for the mutagenic activity detected in the drinking water samples from the Cristais River. The data obtained in this study have environmental and health implications because the chlorination of the BDCP and the R-BDCP leads to the formation of mutagenic compounds (Cl-BDCP and Cl-R-BDCP), which are potentially important disinfection byproducts that can contaminate the drinking water as well as the environment.

A laser-induced fluorescence spectroscopic study of organic matter in a Brazilian Oxisol under different tillage systems

Laser-induced fluorescence (LIF) spectroscopy has been proposed as new method for determining the degree of humification of organic matter (OM) in whole soils. It can be also used to analyze the OM in whole soils containing large amounts of paramagnetic materials, and which are neither feasible to Electron Paramagnetic Resonance (EPR) nor to C-13 Nuclear Magnetic Resonance (NMR) spectroscopy. In the present study, 3 LIF spectroscopy was used to investigate the OM in a Brazilian Oxisol containing high concentration of Fe+3. Soil samples were collected from two areas under conventional tillage (CT), two areas under no-till management (NT) and from a non-cultivated (NC) area under natural vegetation. The results of LIF spectroscopic analysis of the top layer (0-5 cm) of whole soils showed a less aromatic OM in the non-cultivated than in the cultivated soils. This is consistent with data corresponding to HA samples extracted from the same soils and analyzed by EPR, NMR and conventional fluorescence spectroscopy. The OM of whole soils at 5-10 and 10-20 cm depth was also characterized by LIF spectroscopy.Analysis of samples of NT and NC soils showed a higher OM aromatic content at depth. This is a consequence of the accumulation of plant residues at the soil surface in quantities that are too large for microorganisms to metabolize fully, thus, resulting in less aromatic or less hurnified humic substances. In deeper soil layers, the input of residues was lower and further decomposition of humic substances by microorganisms continued, and the aromaticity and degree of humification increased with soil depth. This data indicates that the gradient of humification of OM in the NT soil was similar to those observed in natural soils. Nevertheless, the degree of humification of the OM in the soils under no-till management varied less than that corresponding to non-cultivated soils. This may be because the former have been managed under these practices for only 5 years, in contrast to the continuous humification process occurring in the natural soils. on the other band, LIF spectroscopic analysis of the CT soils showed less pronounced changes or no change in the degree of humification with depth. This indicates that the ploughing and harrowing involved in CT lead to homogenization of the soil and thereby also of the degree of humification of OM throughout the profile. (c) 2006 Elsevier B.V. All rights reserved.

Multiresidue analysis of pesticides in water from rice cultures by on-line solid phase extraction followed by LC-DAD

An automated on-line solid phase extraction procedure followed by liquid chromatography with diode array detection was investigated for the determination of different classes of pesticides in water samples containing varied amount of humic substances. The different pesticides used were: carbendazin, carbofuran, atrazine, diuron, propanil, molinate, alachlor, parathion-ethyl, diazinon, trifluralin and the degradation products deisopropylatrazine and deethylatrazine. Humic substances extracted from a Brazilian sediment were used from 5 to 80 mg/l and their influence on recoveries was evaluated in neutral and acidic media. Recoveries higher than 70% were obtained for all the pesticides, from the preconcentration of 75 mi of aqueous sample fortified at 2 ng/ml using precolumns packed with PLRP-S. Good recoveries were obtained at neutral pH for most of the analytes up to 40 mg/l of humic acid. Only at 80 mg/l the recoveries were significantly affected, both at acidic and neutral pH. The method was applied to the determination of pesticides in river water spiked at 0.1 to 1 ng/ml. Detection limits obtained for water containing 10 mg/l of humic acid were between 0.05 and 0.3 ng/ml.

Soil humus characteristics in virgin and cleared areas of the paraná river basin in Brazil

A study of the characteristics and distribution of the soil humus fractions in representative ecosystems of central Brazil was carried out with special emphasis on the comparison between the soils under virgin vegetation-Cerrado-and those subjected to cultivation. In spite of the contrasted vegetation and cultural practices in the sites studied, the soil humus showed analogous characteristics: there was a negligible amount of plant residues, the humic and fulvic acids amounted to approximately 70% of the total organic carbon, and about 40% of these humic substances were in extremely stable association with the soil mineral fraction, the HCl-HF treatment being required for their extraction. The stability of such organo-mineral complexes increased slightly in the cultured sites. The study of the humic acid fraction showed increased oxidation and aromaticity in most of the cultivated sites: the lowest values for the IR alkyl vibrations and H/C atomic ratios and the highest ones for the optical density at 465 nm were observed in sites transformed into orchards, whereas the above changes were small in those used as pasture. The 14C NMR spectra confirmed that the proportion of polyalkyl structures decreased in the humic acids of soils subjected to cultivation, as opposed to that of carboxyl groups. In spite of the high stability inferred for the organic matter throughout the wide area examined, the samples from the original Cerrado as well as from those transformed into pastures showed, in laboratory conditions, higher mineralization rates than those from the sites subjected to cultivation. This is partly attributed to the decreased proportions of extractable humic substances in the latter. © 1992.