Organic acid adsorption and mineralization in oxisols with different textures

Organic acids play an important role in the nutritional conditions of plants. Their relevance is related to their formation dynamics, mineralization rate and adsorption by soil colloids. This study was carried out to evaluate the dynamics of mineralization and adsorption of organic acid (acetic acid - AA, citric acid - CA and humic acid - HA) applied to the soil. Samples of two Oxisols were used: Rhodic Haplustox (LV) and Typic Haplustox (LVA). The mineralization experiment was arranged in a 2 x 3 x 5 factorial design, based on the factors: two soils (LV and LVA) x three organic acid (OA) types (AA, CA and HA) x five OA rates (0, 1, 2, 4, and 8 mmol dm-3). Organic carbon mineralization in samples was measured by the C-CO2 efflux, produced by the microbial activity, in a 30-day (measurements after 4, 8, 12, 21, and 30 days) and in a 4-day experiment (measured after 24, 48, 72 and 96 h). Organic acid adsorption was tested in a 2 x 2 x 5 x 4 factorial design, with the factors and levels: two Oxisols; two organic acids (AA and CA); five OA rates (0, 1, 2, 4, and 8 mmol dm-3) and four adsorption periods (6, 24, 48, and 72 h). The C-CO2 production of soil treated with CA was highest. In the adsorption experiment, the affinity of CA to soil adsorption sites was greatest. The adsorption of organic acids to soils may be an important mechanism by which bioavailability and thus mineralization capacity by microbial activity are reduced.

Rice straw incorporated just before soil flooding increases acetic acid formation and decreases available nitrogen

Incorporation of rice straw into the soil just before flooding for water-seeded rice can immobilize mineral nitrogen (N) and lead to the production of acetic acid harmful to the rice seedlings, which negatively affects grain yield. This study aimed to evaluate the formation of organic acids and variation in pH and to quantify the mineral N concentration in the soil as a function of different times of incorporation of rice straw or of ashes from burning the straw before flooding. The experiment was carried out in a greenhouse using an Inceptisol (Typic Haplaquept) soil. The treatments were as follows: control (no straw or ash); incorporation of ashes from previous straw burning; rice straw incorporated to drained soil 60 days before flooding; straw incorporated 30 days before flooding; straw incorporated 15 days before flooding and straw incorporated on the day of flooding. Experimental units were plastic buckets with 6.0 kg of soil. The buckets remained flooded throughout the trial period without rice plants. Soil samples were collected every seven days, beginning one day before flooding until the 13th week of flooding for determination of mineral N- ammonium (NH4+) and nitrate (NO3-). Soil solution pH and concentration of organic acids (acetic, propionic and butyric) were determined. All NO3- there was before flooding was lost in approximately two weeks of flooding, in all treatments. There was sigmoidal behavior for NH4+ formation in all treatments, i.e., ammonium ion concentration began to rise shortly after soil flooding, slightly decreased and then went up again. On the 91st day of flooding, the NH4+ concentrations in soil was 56 mg kg-1 in the control treatment, 72 mg kg-1 for the 60-day treatment, 73 mg kg-1 for the 30-day treatment and 53 mg kg-1 for the ash incorporation treatment. These ammonium concentrations correspond to 84, 108, 110 and 80 kg ha-1 of N-NH4+, respectively. When the straw was incorporated on the day of flooding or 15 days before, the concentration of N-NH4+ in the soil was 28 and 54 mg kg-1, equivalent to an accumulation of 42 and 81 kg ha-1 of N-NH4+, respectively. There was formation of acetic acid in which toxic concentrations were reached (7.2 mmol L-1) on the 15th day of flooding only for the treatment with straw incorporated on the day of flooding. The pH of the soil solution of all the treatments increased after flooding and this increase was faster in the treatments with incorporation of straw, followed by the ash treatment and then the control. After 60 days of flooding, however, the pH values were around 6.5 for all treatments, except for the control, which reached a pH of 6.3. Rice straw should be incorporated into the soil at least 30 days before flooding; otherwise, it may immobilize part of the mineral N and produce acetic acid in concentrations toxic to rice seedlings.

Thermodynamic Characterization of Humic Acid-surfactant Interaction: New Insights into the Characteristics and Structure of Humic Acids

ABSTRACT Humic acids (HA) are a component of humic substances (HS), which are found in nearly all soils, sediments, and waters. They play a key role in many, if not most, chemical and physical properties in their environment. Despite the importance of HA, their high complexity makes them a poorly understood system. Therefore, understanding the physicochemical properties and interactions of HA is crucial for determining their fundamental role and obtaining structural details. Cationic surfactants are known to interact electrostatically and hydrophobically with HA. Because they are a very well-known and characterized system, they offer a good choice as molecular probes for studying HA. The objective of this study was to evaluate the interaction between cationic surfactants and HA through isothermal titration calorimetry in a thermodynamic manner, aiming to obtain information about the basic structure of HA, the nature of this interaction, and if HA from different origins show different basic structures. Contrary to what the supramolecular model asserts, HA structure is not loosely held, though it may separate depending on the conditions the HA are subjected to in their milieu. It did not show any division or conformational change when interacting with surfactants. The basic structure of the HA remains virtually the same regardless of the different sources and compositions of these HA.

Characterization of Ornamental Rock Residue and Potassium Liberation Via Organic Acid Application

ABSTRACT Organic acids present in organic matter and, or, exudates by microorganisms and plants can increase the liberation of potassium present in minerals. The objective of this study was to characterize the residue from ornamental rocks and evaluate the release of K from these residues after the application of organic acids. The experiment was conducted under laboratory conditions and followed a 2 × 3 × 5 factorial design with three replicates. The studied factors were: two organic acids (citric acid and malic acid), three ornamental rock residues (R1, R2 and R3) and five organic acid rates (0, 5, 10, 20 and 40 mmol L-1). After agitation, K concentrations were determined in the equilibrium solution. Successive extractions were performed (1, 5, 10, 15, 30 and 60 days after the start of the experiment). The organic acids used (citric and malic) promoted the release of up to 4.86 and 4.34 % of the total K contained in the residue, respectively, reinforcing the role of organic acids in the weathering of minerals and in providing K to the soil. The K quantities were, on average, 6.1 % higher when extracted with citric acid compared to malic acid.

Diallel analysis for grain yield and mineral absorption rate of soybeans grown in acid brazilian savannah soil

High available aluminium and low levels of calcium below the ploughed zone of the soil are limiting factors for agricultural sustainability in the Brazilian Cerrados (Savannahs). The mineral stresses compound with dry spells effect by preventing deep root growth of cultivated plants and causes yield instability. The mode of inheritance for grain yield and mineral absorption ratio of a diallel cross in soybeans [Glycine max (L.) Merrill] grown in high and low Al areas was identified. Differences among the genotypes for grain yield were more evident in the high Al, by grouping tolerant and non-tolerant genotypes for their respective arrays in the hybrids. A large proportion of genetic variance was additive for grain yield and mineral absorption ratio in both environments. High heritability values suggest that soybeans can be improved by crosses among Al-tolerant genotypes, using modified pedigree, early generation and recurrent selection schemes.

Differences in ureide and amino acid content of water stressed soybean inoculated with Bradyrhizobium japonicum and B. elkanii

The objective of this work was to study the response to water stress of a drought sensitive soybean cultivar inoculated with Bradyrhizobium japonicum (strain CB1809, Semia 586) and B. elkanii (strain 29W, Semia 5019). CB1809 nodulated plants produced a significantly higher root fraction (19%) than 29W (14.6%). Plants inoculated with CB1809 produced less nodules and accumulated more nitrogen than those inoculated with 29W. In general, low amounts of ureides in nodules were found in watered plants inoculated with either CB1809 or 29W strains, but those levels were five-fold increased in stressed plants inoculated with CB1809. Nodules formed by strain CB1809 had aspartate and glutamate as major amino acids, while those formed by 29W had glutamate, asparagine and alanine. In nodules of plants inoculated with CB1809 aspartate showed the highest accumulation (5 µmol g-1); in stressed plants this amino acid reached a value of 26 µmol g-1, and asparagine was not detected. Nodules formed by the strain 29W accumulated 1 µmol g-1 of aspartate, whether plants were stressed or not. Asparagine was the major amino acid found in nodules from watered plants (6 µmol g-1) and the amount of this amino acid was six-fold increased when plants were water stressed.

Evaluation of acid digestion techniques to estimate chromium contents in cattle feces

The objective of this work was to evaluate the accuracy of digestion techniques using nitric and perchloric acid at the ratios of 2:1, 3:1, and 4:1 v v-1, in one- or two-step digestion, to estimate chromium contents in cattle feces, using sodium molybdate as a catalyst. Fecal standards containing known chromium contents (0, 2, 4, 6, 8, and 10 g kg-1) were produced from feces of five animals. The chromium content in cattle feces is accurately estimated using digestion techniques based on nitric and perchloric acids, at a 3:1 v v-1 ratio, in one-step digestion, with sodium molybdate as a catalyst.

Effect of gibberellic acid and the biostimulant stimulate® on the initial growth of tamarind

Plant growth regulators and biostimulants have been used as an agronomic technique to optimize the production of seedlings in various crops. This study aimed to evaluate the influence of gibberellic acid and the biostimulant Stimulate® on the initial growth of tamarind (Tamarindus indica L.). The experiments were conducted in a nursery with 50% shading, in a randomized block design with five replications and five plants per plot. Thirty eight days after sowing, the leaves were sprayed seven times a day with 0.0 (control), 0.8, 1.6, 2.4 and 3.2 mL of gibberellic acid L-1 aqueous solution and with 0.0 (control), 6.0,12.0, 18.0, and 24.0 mL Stimulate® L-1 aqueous solution. Stem diameter (SD), plant height (PH), longest root length (LRL), shoot dry mass (SDM), root dry mass (RDM) and RDM:SDM ratio were evaluated ninety days after sowing. Variance and regression analysis showed that GA3 at 4% promoted plant growth (height), but had no significant effect on stem diameter, longest root length, shoot and root dry mass and the RDM:SDM ratio. On the other hand, all concentrations of Stimulate® significantly increased plant height and shoot and root dry mass of tamarind seedlings.

Caracterização de ácidos húmicos de vermicomposto de esterco bovino compostado durante 3 e 6 meses

The main objective of this research was the characterization of the humic fractions isolated from vermicomposting, originating from cattle manure and treated with Eisenea foetida or Lumbricus rubellus, during 3 and 6 months. Elemental analysis and Infrared and UV-vis spectroscopy were used for their characterizations. The results obtained shown that both humic acids are very similar, but six-month humic acid shown lower percentage of organic material than three month humic acid. The spectroscopy analysis shown that the humic acid studied can be compared with other humic acids reported in the literature. By comparing both vermicomposts, the one produced in three months presents a great potential as fertilizer and it is more economical than the vermicompost produced during a six month period.

Chemical constituents from Bakeridesia pickelii Monteiro (Malvaceae) and the relaxant activity of kaempferol-3-O-beta-D-(6"-E-p -coumaroyl) glucopyranoside on guinea-pig ileum

The phytochemical investigation of Bakeridesia pickelii Monteiro led to the isolation of seven compounds: beta-sitosterol, a mixture of sitosteryl-3-O-beta-D-glucopyranoside and stigmasteryl-3-O-beta-D-glucopyranoside, vanillic acid, p-coumaric acid, quercetin 3-O-beta-D-glucopyranoside (isoquercitrin) and kaempferol-3-O-beta-D-(6"-E-p -coumaroyl) glucopyranoside (tiliroside), which was isolated as the major component. Their structures were elucidated on the basis of spectroscopic data such as IR, ¹H and 13C NMR, including two-dimensional techniques. Tiliroside relaxed the guinea-pig ileum pre-contracted with KCl 40 mM (EC50 = 9.5 ± 1.0 x 10-5 M), acetylcholine 10-6 M (EC50 = 2.3 ± 0.9 x 10-5 M) or histamine 10-6 M (EC50 = 4.1 ± 1.0 x 10-5 M) in a concentration-dependent manner.

Caldensinic acid, a benzoic acid derivative and others compounds from Piper carniconnectivum

A benzoic acid derivative - caldensinic acid; E-phytyl hexadecanoate; β-sitosterol and stigmasterol mixture and phaeophytin a were isolated from the aerial parts of Piper carniconnectivum. The structures of these compounds were established unambiguously by IR, MS, 1D and 2D NMR analysis.

Determination of cinnamic acid in human urine by flow injection chemiluminescence

It was found that cinnamic acid can react with potassium permanganate in the acidic medium and produce chemiluminescence, which was greatly enhanced by glyoxal. Under the optimum conditions, the linear range for the determination of cinnamic acid was 1.0×10-8 to 1.0×10-4 mol L-1 with a detection limit of 8.0×10-9 mol L-1, the relative standard deviation was 1.7% for 2.0×10-6 mol L-1 cinnamic acid solution in nine repeated measurements. This method was found to be novel0simple0fast and sensitive, it was successfully applied to the determination of cinnamic acid in human urine. Furthermore, the possible reaction mechanism was also discussed.

Anti-trypanosomal activity of 1,2,3,4,6-penta-O-galloyl-β -D-glucose isolated from Plectranthus barbatus Andrews (Lamiaceae)

MeOH extract from the leaves of Plectranthus barbatus Andrews (Lamiaceae), showed in vitro anti-trypanosomal activity. The bioassay-guided fractionation resulted in the isolation of a gallic acid derivative, identified as 1,2,3,4,6-penta-O-galloyl-β-D-glucose (PGG), after thorough NMR and MS spectral analysis. Finally, this compound was tested against trypomastigote forms of T. cruzi and displayed an EC50 value of 67 µM, at least 6.6-fold more effective than the standard drug benznidazole. This is the first occurrence of PGG in the Plectranthus genus and the first anti-parasitic activity described for PGG in the literature.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Materials based on tungstophosphoric acid (TPA) immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET) decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH4)3PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO) in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

SYNTHESIS AND BIOLOGICAL EVALUATION OF SPIRO[INDOLINE-3,4’-PYRANO[2,3-C:6,5-C’]DIPYRAZOL]- 2-ONES IN THE PRESENCE OF SBA-Pr-SO3H AS A NANOCATALYST

Sulfonic acid functionalized SBA-15 nanoporous material (SBA-Pr-SO3H) with a large pore size of 6 nm, a high surface area, high selectivity, and excellent chemical and thermal stability was applied as an efficient heterogeneous nanoporous acid catalyst in the reaction of isatin with pyrazolones under mild reaction conditions. A novel class of symmetrical spiro[indoline-3,4'-pyrano[2,3-c:6,5-c']dipyrazol]-2-one derivatives was successfully obtained in high yields. Comparison of these results with those reported in the literature shows that the current method is efficient, and results in better reaction times and yields of the desired products. Other advantages of this new method are its operational simplicity, easy work-up procedure, and the use of SBA-Pr-SO3H as a reusable and environmentally benign nanoreactor, such that the reaction proceeds easily in its nanopores. We also tested the antimicrobial activity of the prepared compounds using the disc diffusion method, and some of the synthesized compounds exhibited the best results against B. subtilis and S. aureus.