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.

Influência das características das substâncias húmicas aquáticas na eficiência da coagulação com o cloreto férrico

The aim of this study was to verify the influence of the apparent molecular size of aquatic humic substances on the effectiveness of coagulation with ferric chloride. Coagulation-filtration tests using jar test and bench-scale sand filters were carried out on samples of water with true color of approximately 100 Hazen units, prepared with aquatic humic substances of different molecular sizes (F1: < 0.45 µm, F2: 100 kDa - 0.45 µm, F3: 30 - 100 kDa and F4': < 30 kDa). For the water samples with lower apparent molecular size fractions, greater dosages of coagulant was needed to remove the color around 5.0 Hanzen units, mainly because these water samples contain higher concentrations of fulvic acids, which exhibited a larger number of negatively-charged groups.

Acompanhamento químico da vermicompostagem de lodo de esgoto doméstico

This research aims to monitor the humification process of domestic sewage sludge resulted from the vermicomposting, evaluating, also, the possibility of using the final product (vermicompost) in agricultural soils. The monitored chemical variables during the 90 days of vermicomposting were: humidity rate, organic matter content, nitrogen and phosphorus content, pathogenic organisms concentration, total organic carbon, acidity, CEC, C/N ratio, CEC/TOC ratio, and humic and fulvic acids content. The change in these variables during the vermicomposting process showed that this technique is effective for use in the maturation of the residue.

Characterization of humic substances in salt marsh soils under sea rush (Juncus maritimus)

Humic substances (HS) from salt marsh soils were characterized and the relationships among HS composition and some geochemical factors were analysed. For this, three salt marshes with the same vegetation cover (Juncus maritimus), but with different geochemical characteristics, were selected. The qualitative characterization of the soil humic acids and fulvic acids was carried out by elemental analysis, FTIR spectroscopy, fluorescence spectroscopy and VACP/MAS (13)C NMR spectroscopy. HS from salt marsh soils under sea rush (Juncus maritimus) displayed some shared characteristics such as low degree of humification, low aromatic content and high proportion of labile compounds, mainly polysaccharides and proteins. However, although the three salt marsh soils under study were covered by the same type of vegetation, the HS showed some important differences. HS composition was found to be determined not only by the nature of the original organic material, but also by environmental factors such as soil texture, redox conditions and tidal influence. In general. an increase in the humification process appeared to be related to aerobic conditions and predominance of sand in the mineral fraction of the soil, while the preservation of labile organic compounds may be associated with low redox potential values and fine soil texture. (C) 2008 Elsevier Ltd. All rights reserved.

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.

Contribution of humic substances from different composts to the synthesis of humin in a tropical soil

The contribution of humic substances of different composts to the synthesis of humin in a tropical soil was evaluated. Increasing doses (0, 13, 26, 52, and 104 Mg ha-1) of five different composts consisting of agroinpowderrial residues were applied to a Red-Yellow Latosol. These composts were chemically characterized and 13C NMR determined and the quantity of the functional alkyl groups of humic acids applied to the soil as compost was estimated. Thirty days after application of the treatments, organic matter samples were collected for fractionation of humic acids (HA), fulvic acids (FA) and humin (HU), from which the ratios HA/FA and (HA + FA)/HU were calculated. The application of the composts based on castor cake resulted in the highest HU levels in the soil; alkyl groups of the HA fraction of the composts were predominant in the organic components added to the HU soil fraction.

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.

Root growth of tomato seedlings intensified by humic substances from peat bogs

Peats are an important reserve of humified carbon in terrestrial ecosystems. The interest in the use of humic substances as plant growth promoters is continuously increasing. The objective of this study was to evaluate the bioactivity of alkaline soluble humic substances (HS), humic (HA) and fulvic acids (FA) isolated from peats with different decomposition stages of organic matter (sapric, fibric and hemic) in the Serra do Espinhaço Meridional, state of Minas Gerais. Dose-response curves were established for the number of lateral roots growing from the main plant axis of tomato seedlings. The bioactivity of HA was greatest (highest response in lateral roots at lowest concentration) while FA did not intensify root growth. Both HS and HA stimulated root hair formation. At low concentrations, HS and HA induced root hair formation near the root cap, a typical hormonal imbalance effect in plants. Transgenic tomato with reporter gene DR5::GUS allowed the observation that the auxin-related signalling pathway was involved in root growth promotion by HA.

SOIL ORGANIC MATTER FRACTIONS IN PRESERVED AND DISTURBED WETLANDS OF THE CERRADO BIOME

Veredas are humid tropical ecosystems, generally associated to hydromorphic soils and a shallow water table. The soils of these ecosystems are affected by the use of the areas around these veredas. The objective of this study was to determine soil organic matter (SOM) fractions in veredas adjacent to preserved (native savanna) and disturbed environments (agricultural areas and pastures) in the Cerrado biome. Soil samples were collected from the 0-10 and 10-20 cm layers along reference lines drawn along the relief following the upper, middle and lower positions of one of the slopes, in the direction of the draining line of the vereda. The soil analysis determined: total soil OC, total nitrogen and C:N ratio; C and N contents and C:N ratio in particulate and mineral-associated fractions (of SOM); fulvic acids, humic acids and humin fractions and ratio between humic and fulvic acids. The agricultural use around the veredas induced changes in the SOM fractions, more pronounced in the lower part of the slope. In the soil surface of this part, the OC levels in the humic substances and the particulate fraction of SOM, as well as total soil OC were reduced in the vereda next to crop fields.

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.

Water-Stable Aggregates and Associated Carbon in a Subtropical Rice Soil Under Variable Tillage

ABSTRACT Tillage systems can influence C sequestration by changing aggregate formation and C distribution within the aggregate. This study was undertaken to explore the impact of no-tillage without straw (NT-S) and with straw (NT+S), and moldboard plow without straw (MP-S) and with straw (MP+S), on soil aggregation and aggregate-associated C after six years of double rice planting in a Hydragric Anthrosol in Guangxi, southwest of China. Soil samples of 0.00-0.05, 0.05-0.20 and 0.20-0.30 m layers were wet-sieved and divided into four aggregate-size classes, >2 mm, 2.00-0.25 mm, 0.25-0.053 and <0.053 mm, respectively, for measuring aggregate associated C and humic and fulvic acids. Results showed that the soil organic carbon (SOC) stock in bulk soil was 40.2-51.1 % higher in the 0.00-0.05 m layer and 11.3-17.0 % lower in the 0.05-0.20 m layer in NT system (NT+S and NT-S) compared to the MP system (MP+S and MP-S), respectively. However, no statistical difference was found across the whole 0.00-0.30 m layer. The NT system increased the proportion of >2 mm aggregate fraction and reduced the proportion of <0.053 mm aggregates in both 0.00-0.05 and 0.05-0.20 m layers. The SOC concentration, SOC stock and humic and fulvic acids within the >0.25 mm macroaggregate fraction also significantly increased in the 0.00-0.5 m layer in NT system. However, those within the 2.00-0.25 mm aggregate fraction were significantly reduced in the 0.05-0.200 m layer under NT system. Straw incorporation increased not only the SOC stock in bulk soil, but also the proportion of macroaggregate, aggregate associated with SOC and humic and fulvic acids concentration within the aggregate. The effect of straw on C sequestration might be dependent on the location of straw incorporation. In conclusion, the NT system increased the total SOC accumulation and humic and fulvic acids within macroaggregates, thus contributing to C sequestration in the 0.00-0.05 m layer.

Chemical nature of soil humified fractions and their bioactivity

The aim of this work was to evaluate the humus composition from an Ultisol from Campos dos Goytacazes, RJ, Brazil. Soil samples of four depths (0-0.05, 0.05-0.10, 0.10-0.20 and 0.20-0.40 m) and its chemical nature were analysed by elemental composition, E4/E6 ratios and Fourier transformed infrared spectroscopy. The bioactivity of these humified substances was evaluated through their action on maize root growth and H+-ATPase activity of roots microsomes. In topsoil, the content of high condensed alkaline soluble humic substances is greater than that found in the subsuperficial layers. The chemical nature of humic and fulvic acids also varied with the soil depth. The humic acids isolated from the soil samples exhibited higher bioactivity compared with the fulvic acids. Moreover, the results suggest that more condensed humic substances can promote highest stimulation of the microsomal H+-ATPases from maize roots. These data reinforce the concept that the activity of the H+ pumps can be used as a biochemical marker for evaluation of humic substances bioactivity.

Reproducing the organic matter model of anthropogenic dark earth of Amazonia and testing the ecotoxicity of functionalized charcoal compounds

The objective of this work was to obtain organic compounds similar to the ones found in the organic matter of anthropogenic dark earth of Amazonia (ADE) using a chemical functionalization procedure on activated charcoal, as well as to determine their ecotoxicity. Based on the study of the organic matter from ADE, an organic model was proposed and an attempt to reproduce it was described. Activated charcoal was oxidized with the use of sodium hypochlorite at different concentrations. Nuclear magnetic resonance was performed to verify if the spectra of the obtained products were similar to the ones of humic acids from ADE. The similarity between spectra indicated that the obtained products were polycondensed aromatic structures with carboxyl groups: a soil amendment that can contribute to soil fertility and to its sustainable use. An ecotoxicological test with Daphnia similis was performed on the more soluble fraction (fulvic acids) of the produced soil amendment. Aryl chloride was formed during the synthesis of the organic compounds from activated charcoal functionalization and partially removed through a purification process. However, it is probable that some aryl chloride remained in the final product, since the ecotoxicological test indicated that the chemical functionalized soil amendment is moderately toxic.

Determinação de carbaril utilizando testes ELISA (Enzyme-linked immunosorbent assay) e CLAE com detecção por arranjo de diodos

ELISAs have been applied to pesticide residue analysis due to their high sensitivity and selectivity. However, some ELISAs performance may be affected by matrix components. In this work, ELISA for carbaryl in water samples was checked for interference by naturally occurring fulvic acids. The results suggested that the high fulvic acid concentration (ž³30 mg L-1) and acidic pH conditions (pH 4.0) interfere with the signal detection decreasing the method sensitivity. A dilution of the samples and adjust to pH 8.0 are appropriate to minimize the matrix interferences in the ELISA method. Good correlation between ELISA and HPLC-DAD results was observed.