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.

Comparison of H/Al stoichiometry of mineral and organic soils in Brazil

Exchangeable Al has been used as a criterion for the calculation of lime requirement in several Brazilian States. However, the laboratory method with extraction by a 1 mol L-1 KCl solution followed by indirect alkaline titration is not accurate for some Brazilian soils, mainly in the case of soils with high organic matter content. The objective of this study was therefore to evaluate the stoichiometry of H+/Al3+ in KCl soil extracts. The results suggested that organically complexed Al is the main contributor to exchangeable acidity in soils enriched with organic matter. Liming recommendations for organic soils based exclusively on exchangeable Al determined by the NaOH titration method should therefore be revised.

Occurrence of plant growth-promoting traits in clover-nodulating rhizobia strains isolated from different soils in Rio Grande do Sul state

In the last decades, the use of plant growth-promoting rhizobacteria has become an alternative to improve crop production. Rhizobium leguminosarum biovar trifolii is one of the most promising rhizobacteria and is even used with non-legume plants. This study investigated in vitro the occurrence of plant growth-promoting characteristics in several indigenous R. leguminosarum biovar trifolii isolated from soils in the State of Rio Grande do Sul, Brazil. Isolates were obtained at 11 locations and evaluated for indoleacetic acid and siderophore production and inorganic phosphate solubilization. Ten isolates were also molecularly characterized and tested for antagonism against a phytopathogenic fungus and for plant growth promotion of rice seedlings. Of a total of 252 isolates, 59 produced indoleacetic acid, 20 produced siderophores and 107 solubilized phosphate. Some degree of antagonism against Verticillium sp. was observed in all tested isolates, reducing mycelial growth in culture broth. Isolate AGR-3 stood out for increasing root length of rice seedlings, while isolate ELD-18, besides increasing root length in comparison to the uninoculated control, also increased the germination speed index, shoot length, and seedling dry weight. These results confirm the potential of some strains of R. leguminosarum biovar trifolii as plant growth-promoting rhizobacteria.

Soil-applied silicon decreases severity of wheat spot blotch on silicon-deficient soils

Spot bloth caused by Bipolaris sorokiniana is an important wheat desease mainly in hot and humid regions. The aim of this study was to evaluate the response of wheat to different sources and modes of Si application, as related to the severity of wheat spot blotch and plant growth, in two Si-deficient Latosols (Oxisols). An greenhouse experiment was arranged in a 2 x 5 factorial completely randomized design, with eight replications. The treatments consisted of two soils (Yellow Latosol and Red Latosol) and five Si supply modes (no Si application; Si applied as calcium silicate and monosilicic acid to the soil; and Si applied as potassium silicate or monosilicic acid to wheat leaves). No significant differences were observed between the two soils. When Si was applied to the soil, regardless the Si source, the disease incubation period, the shoot dry matter yield and the Si content in leaves were greater. Additionally, the final spot blotch severity was lower and the area under the spot blotch disease progress curve and the leaf insertion angle in the plant were smaller. Results of Si foliar application were similar to those observed in the control plants.

Plant availability of trace elements in sewage sludge-treated soils: methodology¹

Synthetic root exudates were formulated based on the organic acid composition of root exudates derived from the rhizosphere of aseptically grown corn plants, pH of the rhizosphere, and the background chemical matrices of the soil solutions. The synthetic root exudates, which mimic the chemical conditions of the rhizosphere environment where soil-borne metals are dissolved and absorbed by plants, were used to extract metals from sewage-sludge treated soils 16 successive times. The concentrations of Zn, Cd, Ni, Cr, and Cu of the sludge-treated soil were 71.74, 0.21, 15.90, 58.12, and 37.44 mg kg-1, respectively. The composition of synthetic root exudates consisted of acetic, butyric, glutaric, lactic, maleic, propionic, pyruvic, succinic, tartaric, and valeric acids. The organic acid mixtures had concentrations of 0.05 and 0.1 mol L-1 -COOH. The trace elements removed by successive extractions may be considered representative for the availability of these metals to plants in these soils. The chemical speciation of the metals in the liquid phase was calculated; results showed that metals in sludge-treated soils were dissolved and formed soluble complexes with the different organic acid-based root exudates. The most reactive organic acid ligands were lactate, maleate, tartarate, and acetate. The inorganic ligands of chloride and sulfate played insignificant roles in metal dissolution. Except for Cd, free ions did not represent an important chemical species of the metals in the soil rhizosphere. As different metals formed soluble complexes with different ligands in the rhizosphere, no extractor, based on a single reagent would be able to recover all of the potentially plant-available metals from soils; the root exudate-derived organic acid mixtures tested in this study may be better suited to recover potentially plant-available metals from soils than the conventional extractors.

Assessment of micronutrient extractants from soils of Paraná, Brazil

In Brazil, plant-available micronutrients in the soil can be determined by several chemical extractants, the most common of which are dilute acid and chelating solutions. The purpose of this study was to assess the extractants 0.1 mol L-1 HCl, Mehlich-1, Mehlich-3 and DTPA for analysis of the micronutrients Cu, Zn, Fe, and Mn in soils from the state of Paraná. In samples from 12 soils (0-20 cm layer), wheat was planted (Triticum aestivum), grown for 42 days after emergence, and then bean (Phaseolus vulgaris) for 38 days. At the end of each planting period, the soil was sampled again. All extractants tested to assess the availability of Cu, Zn, Fe, and Mn correlated with each other. The efficiency of the extractants HCl, Mehlich-3 and DTPA in assessing plant-available Cu was similar, unlike Mehlich-1, which proved less efficient. The extractants HCl, Mehlich-1 and Mehlich-3 were less efficient in estimating plant-available Zn and Fe, and the most indicated extractant is DTPA. The efficiency of the extractants HCl, Mehlich-1, Mehlich-3 and DTPA in assessing plant-available Mn in soils from Paraná was similar.

Application of alkaline waste from pulp industry to acid soil with pine

In Brazil extensive areas are covered with pine forests, planted for pulp and paper production. This industry generates solid alkaline waste, such as dregs. The application of this dregs to forest soils is an alternative for soil acidity correction and plant nutrient supply, as well as a solution for its proper disposal. The purpose of this study was to compare the residual effect of surface application of dregs and dolomitic lime on (a) changes in the physical and chemical properties of an acidic soil and (b) pine tree development. The experiment was carried out in 2004 in Bocaina do Sul, Santa Catarina, consisting of the application of increasing dreg and lime rates to a Pinus taeda L. production area, on a Humic Cambisol, in a randomized block design with four replications and 10 x 10 m plots. The treatments consisted of levels of soil acidity amendments corresponding to the recommendations by the SMP method to reach pH 5.5 in the 0-20 cm layer, as follows: no soil amendment; dregs at 5.08 (1/4 SMP), 10.15 (1/2 SMP) and 20.3 Mg ha-1 (1 SMP); and lime at 8.35 (1/2 SMP) and 16.7 Mg ha-1 (1 SMP). Soil layers were sampled in 2010 for analyses of soil chemical and physical properties. The diameter at breast height of the 6.5 year old pine trees was also evaluated. Surface application of dregs improved soil chemical fertility by reducing acidity and increasing base saturation, similar to liming, especially in surface layers. Dregs, comparable to lime, reduced the degree of clay flocculation, but did not affect the soil physical quality. There was no effect of the amendments on increase in pine tree diameter. Thus, the alternative to raise the pH in forest soils to 5.5 with dregs is promising for the forestry sector with a view to dispose of the waste and increase soil fertility.

Organic matter quality and dynamics in tropical soils amended with sugar industry residue

Soil organic matter depletion caused by agricultural management systems have been identified as a critical problem in most tropical soils. The application of organic residues from agro-industrial activities can ameliorate this problem by increasing soil organic matter quality and quantity. Humic substances play an important role in soil conservation but the dynamics of their transformations is still poorly understood. This study evaluated the effect of compost application to two contrasting tropical soils (Inceptisol and Oxisol) for two years. Soil samples were incubated with compost consisting of sugarcane filter cake, a residue from the sugar industry, at 0, 40, 80, and 120 Mg ha-1. Filter cake compost changed the humic matter dynamics in both content and quality, affecting the soil mineralogical composition. It was observed that carbon mineralization was faster in the illite-containing Inceptisol, whereas humic acids were preserved for a longer period in the Oxisol. In both soils, compost application increased fulvic acid contents, favoring the formation of small hydrophilic molecules. A decrease in fluorescence intensity according to the incubation time was observed in the humic acids extracted from amended soils, revealing important chemical changes in this otherwise stable C pool.

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.

Silicate fertilization of tropical soils: silicon availability and recovery index of sugarcane

Sugarcane is considered a Si-accumulating plant, but in Brazil, where several soil types are used for cultivation, there is little information about silicon (Si) fertilization. The objectives of this study were to evaluate the silicon availability, uptake and recovery index of Si from the applied silicate on tropical soils with and without silicate fertilization, in three crops. The experiments in pots (100 L) were performed with specific Si rates (0, 185, 370 and 555 kg ha-1 Si), three soils (Quartzipsamment-Q, 6 % clay; Rhodic Hapludox-RH, 22 % clay; and Rhodic Acrudox-RA, 68 % clay), with four replications. The silicon source was Ca-Mg silicate. The same Ca and Mg quantities were applied to all pots, with lime and/or MgCl2, when necessary. Sugarcane was harvested in the plant cane and first- and second-ratoon crops. The silicon rates increased soil Si availability and Si uptake by sugarcane and had a strong residual effect. The contents of soluble Si were reduced by harvesting and increased with silicate application in the following decreasing order: Q>RH>RA. The silicate rates promoted an increase in soluble Si-acetic acid at harvest for all crops and in all soils, except RA. The amounts of Si-CaCl2 were not influenced by silicate in the ratoon crops. The plant Si uptake increased according to the Si rates and was highest in RA at all harvests. The recovery index of applied Si (RI) of sugarcane increased over time, and was highest in RA.

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.

MICROBIAL CHARACTERISTICS OF SOILS UNDER AN INTEGRATED CROP-LIVESTOCK SYSTEM

Integrated crop-livestock systems (ICLs) are a viable strategy for the recovery and maintenance of soil characteristics. In the present study, an ICL experiment was conducted by the Instituto Agronômico do Paraná in the municipality of Xambre, Parana (PR), Brazil, to evaluate the effects of various grazing intensities. The objective of the present study was to quantify the levels of microbial biomass carbon (MBC) and soil enzymatic activity in an ICL of soybean (summer) and Brachiaria ruziziensis (winter), with B. ruziziensis subjected to various grazing intensities. Treatments consisted of varying pasture heights and grazing intensities (GI): 10, 20, 30, and 40 cm (GI-10, GI-20, GI-30, and GI-40, respectively) and a no grazing (NG) control. The microbial characteristics analysed were MBC, microbial respiration (MR), metabolic quotient (qCO2), the activities of acid phosphatase, β-glucosidase, arylsuphatase, and cellulase, and fluorescein diacetate (FDA) hydrolysis. Following the second grazing cycle, the GI-20 treatment (20-cm - moderate) grazing intensity) contained the highest MBC concentrations and lowest qCO2 concentrations. Following the second soybean cycle, the treatment with the highest grazing intensity (GI-10) contained the lowest MBC concentration. Soil MBC concentrations in the pasture were favoured by the introduction of animals to the system. High grazing intensity (10-cm pasture height) during the pasture cycle may cause a decrease in soil MBC and have a negative effect on the microbial biomass during the succeeding crop. Of all the enzymes analyzed, only arylsuphatase and cellulase activities were altered by ICL management, with differences between the moderate grazing intensity (GI-20) and no grazing (NG) treatments.

Methods to Quantify Nickel in Soils and Plant Tissues

In comparison with other micronutrients, the levels of nickel (Ni) available in soils and plant tissues are very low, making quantification very difficult. The objective of this paper is to present optimized determination methods of Ni availability in soils by extractants and total content in plant tissues for routine commercial laboratory analyses. Samples of natural and agricultural soils were processed and analyzed by Mehlich-1 extraction and by DTPA. To quantify Ni in the plant tissues, samples were digested with nitric acid in a closed system in a microwave oven. The measurement was performed by inductively coupled plasma/optical emission spectrometry (ICP-OES). There was a positive and significant correlation between the levels of available Ni in the soils subjected to Mehlich-1 and DTPA extraction, while for plant tissue samples the Ni levels recovered were high and similar to the reference materials. The availability of Ni in some of the natural soil and plant tissue samples were lower than the limits of quantification. Concentrations of this micronutrient were higher in the soil samples in which Ni had been applied. Nickel concentration differed in the plant parts analyzed, with highest levels in the grains of soybean. The grain, in comparison with the shoot and leaf concentrations, were better correlated with the soil available levels for both extractants. The methods described in this article were efficient in quantifying Ni and can be used for routine laboratory analysis of soils and plant tissues.

Genesis, Characterization, and Classification of Mangrove Soils in the Subaé River Basin, Bahia, Brazil

ABSTRACT Preservation of mangroves, a very significant ecosystem from a social, economic, and environmental viewpoint, requires knowledge on soil composition, genesis, morphology, and classification. These aspects are of paramount importance to understand the dynamics of sustainability and preservation of this natural resource. In this study mangrove soils in the Subaé river basin were described and classified and inorganic waste concentrations evaluated. Seven pedons of mangrove soil were chosen, five under fluvial influence and two under marine influence and analyzed for morphology. Samples of horizons and layers were collected for physical and chemical analyses, including heavy metals (Pb, Cd, Mn, Zn, and Fe). The moist soils were suboxidic, with Eh values below 350 mV. The pH level of the pedons under fluvial influence ranged from moderately acid to alkaline, while the pH in pedons under marine influence was around 7.0 throughout the profile. The concentration of cations in the sorting complex for all pedons, independent of fluvial or marine influence, indicated the following order: Na+>Mg2+>Ca2+>K+. Mangrove soils from the Subaé river basin under fluvial and marine influence had different morphological, physical, and chemical characteristics. The highest Pb and Cd concentrations were found in the pedons under fluvial influence, perhaps due to their closeness to the mining company Plumbum, while the concentrations in pedon P7 were lowest, due to greater distance from the factory. For containing at least one metal above the reference levels established by the National Oceanic and Atmospheric Administration (United States Environmental Protection Agency), the pedons were classified as potentially toxic. The soils were classified as Gleissolos Tiomórficos Órticos (sálicos) sódico neofluvissólico in according to the Brazilian Soil Classification System, indicating potential toxicity and very poor drainage, except for pedon P7, which was classified in the same subgroup as the others, but different in that the metal concentrations met acceptable standards.

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.