Comparison of different methods for the determination of total organic carbon and humic substances in Brazilian soils

ABSTRACTAiming to compare three different methods for the determination of organic carbon (OC) in the soil and fractions of humic substances, seventeen Brazilian soil samples of different classes and textures were evaluated. Amounts of OC in the soil samples and the humic fractions were measured by the dichromate-oxidation method, with and without external heating in a digestion block at 130 °C for 30 min; by the loss-on-ignition method at 450 °C during 5 h and at 600 °C during 6 h; and by the dry combustion method. Dry combustion was used as reference in order to measure the efficiency of the other methods. Soil OC measured by the dichromate-oxidation method with external heating had the highest efficiency and the best results comparing to the reference method. When external heating was not used, the mean recovery efficiency dropped to 71%. The amount of OC was overestimated by the loss-on-ignition methods. Regression equations obtained between total OC contents of the reference method and those of the other methods showed relatively good adjustment, but all intercepts were different from zero (p < 0.01), which suggests that more accuracy can be obtained using not one single correction factor, but considering also the intercept. The Walkley-Black method underestimated the OC contents of the humic fractions, which was associated with the partial oxidation of the humin fraction. Better results were obtained when external heating was used. For the organic matter fractions, the OC in the humic and fulvic acid fractions can be determined without external heating if the reference method is not available, but the humin fraction requires the external heating.

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.

Simultaneous multielement extraction with the Mehlich-1 solution for Southern Brazilian soils determined by ICP-OES and the effects on the nutrients recommendations to crops

The amounts of macro (P, K, Ca and Mg) and micronutrients (Cu and Zn) extracted with the Mehlich-1 (M1) solution, by the 1.0 mol L-1 KCl (KCl) and with the 0.1 mol L-1 HCl (HCl) for representative soil types of the Rio Grande do Sul state (Brazil) were compared with those extracted with the Mehlich-1 solution determined with the inductively coupled plasma optical emission spectroscopy (ICP). The amounts of nutrients extracted by the different methods showed high correlation coefficients. On average, the Mehlich-1 solution extracted similar amounts of P, determined with colorimetric and ICP methods, and, K determined with emission and ICP. The amounts of Ca and Mg extracted with the Mehlich-1 solution, determined by ICP, were similar to those extracted with the KCl solution determined by the atomic absorption spectrophotometry. The amounts of Cu and Zn extracted with the Mehlich-1 solution, determined by the ICP, were higher than those extracted with the 0.1 mol L-1 HCl determined by the atomic absorption spectrophotometry. The results indicate that the Mehlich-1 solution and ICP can be used for simultaneous multielement extraction and determination for Southern Brazilian soils. However, a conversion factor for values interpretation is needed. The use of the conversion factor to determine the K availability index in soils is adequate and does not affect the K recommendations for crops in southern Brazilian soils.

Evaluation of Sikora instead of SMP buffer to estimate the potential acidity of brazilian soils

Despite the efficiency of the Shoemaker, McLean, Pratt (SMP) buffer method in estimating soil acidity, the presence of p-nitrophenol and potassium chromate in the solution, both hazardous substances, has caused increasing environmental concerns. The purpose of this study was to test Sikora method (Sikora, 2006) as an alternative to the adapted SMP buffer method, generally used to estimate potential acidity of Southern Brazilian soils. For the test, 21 soils in the South and Cerrado regions of Brazil were sampled. (1) The potential acidity values of these soils range from 35.95 to 4.02 cmol c kg-1 of soil, reflecting a wide acidity variation. The Sikora buffer does not mimic the adapted SMP buffer used in Southern Brazil, since the former has a low ability to distinguish soils with different acidity from each other, probably due to the higher buffer capacity than of the adapted SMP solution.

Sorption of fomesafen in Brazilian soils

The study of the dynamics of a herbicide in the soil focus on the interactions with environmental components to obtain agronomic efficiency, ensuring selectivity to the culture and risk reduction of environmental impact. This study evaluated the sorption process of fomesafen in the Brazilian soils Ultisol, Cambisol, and Organosol. Besides soil, washed sand was used as an inert material for determination of the sorption ratio of fomesafen in the soil. The bioassay method was applied, using Sorghum vulgare plants as bio-indicator of herbicide presence. Plant poisoning evaluation and harvest for dry matter determination were carried out 21 days after sorghum sowing. To calculate C50, the nonlinear log-logistic model was applied and sorption ratios of the herbicide were obtained in different soils. The decreasing sorption ratio of formesafen in the soils was: Organosol > Ultisol > Cambisol. It was concluded that the contents of organic matter and clay in the soils were the attributes that most influenced fomesafen sorption.

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.

Availability of heavy metals in contaminated soil evidenced by chemical extractants

Heavy metals have been accumulating in Brazilian soils, due to natural processes, such as atmospheric deposition, or human industrial activities. For certain heavy metals, when in high concentrations in the soil, there is no specific extractant to determine the availability of these elements in the soil. The objective of the present study was to evaluate the availability of Cd, Cu, Fe, Mn, Pb and Zn for rice and soybeans, using different chemical extractants. In this study we used seven soil samples with different levels of contamination, in completely randomized experimental design with four replications. We determined the available concentrations of Cd, Cu, Fe, Mn, Pb and Zn extracted by Mehlich-1, HCl 0.1 mol L-1, DTPA, and organic acid extractants and the contents in rice and soybeans, which extracts were analyzed by ICP-OES. It was observed that Mehlich-1, HCl 0.1 mol L-1 and DTPA extractants were effective to assess the availability of Cd, Cu, Pb and Zn for rice and soybeans. However, the same was not observed for the organic acid extractant.

Characterization of verdete rock as a potential source of potassium

Potassium is a nutrient found at low levels in Brazilian soils, requiring large inputs of fertilizers to achieve satisfactory crop yields. Brazil has high external dependence and limited reserves of soluble K mineral, which is traditionally exploited for the production of fertilizers. On the other hand, it is common the occurrence in the country of potassium-rich silicate minerals which are not commercially exploited. This study aimed to characterize mineralogically and chemically samples of verdete rock separated into size fractions and evaluate its potential as potassium fertilizer. The mineral composition of verdete rock is based on glauconite, quartz and feldspar. The total K2O content in verdete rock ranged from 5.18 to 9.0 dag/kg. The K content extracted in water or 2% citric acid was 2.4% below the total of K, indicating low reactivity of verdete rock and limitations for direct use as K source. The processes of physical fractionation and sedimentation in water are inefficient to promote the concentration of K in the different verdete rock fractions. The total K content in some samples are considerable and may enable the use of this rock as raw material for production of more reactive potassium fertilizers.

Studies on the Bacillus sphaericus Larvicidal Activity against Malarial Vector Species in Amazonia

In this work, bioassays were carried out in laboratory conditions (average temperature 26 ± 2ºC) to test ten strains of Bacillus sphaericus, isolated from Brazilian soils against third instar larvae from anopheline species recorded as malaria vectors in Amazonian - Anopheles nuneztovari and An. darlingi. With the former mosquito, three strains - S2, S20 and S46 showed relative activity, in 24 and 48 hr exposure to the B. spahericus strains. With the latter only the S2 and S20 were effective in the 48 hr reading. The studied strains that showed the most adequate response in the Amazonian region were S2 and S20 showing broader and more efficient results. Therefore, S2 was the most effective when the 24 and 48 hr readings were considered, because it showed the greatest relative activity values.

Organic sulfur oxidation to sulfate in soil samples for total sulfur determination by turbidimetry

Sulfur in the soil occurs in two basic forms, organic and inorganic S. The organic form accounts for 95 % of S in most soils. The effectiveness of organic S to oxidate to sulfate was evaluated for total S determination in soil samples by wet (acid) and dry-ash (alkaline) oxidation methods. To evaluate the wet method and the possible use as a reference when evaluating the dry method proposed here, a reference standard from the US National Institute of Standards and Technology (NIST) was used (Montana Soil - NIST 2710). The dry-ash oxidation process with alkaline oxidizing agents is one of the simplest oxidation methods of organic S to the sulfate form and was compared with the wet process. The objective of the study was to develop a dry method that would be easy to apply and allow the complete conversion of organic S to sulfate in soil samples and later detection by turbidimetry. The effectiveness of organic S oxidation to sulfate was evaluated by means of three alkaline oxidation mixtures: NaHCO3 + Ag2O, Eschka mixture (17 % Na2CO3, 66 % MgO, and 17 % K2CO3), and NaHCO3 + CuO. The procedure to quantify the sulfate concentration was based on the reaction with barium chloride and turbidimetric detection. Sulfur quantification in the standard sample by the wet method proved adequate, precise and accurate. It should also be pointed out that no significant differences were found (95 % reliability) between the wet and dry processes (NaHCO3 and Ag2O oxidation mixture) in six different Brazilian soils. The proposed dry method can therefore be used in the preparation of soil samples for total S determination.

Genesis and classification of Oxisols in a highland toposequence of the upper Jequitinhonha Valley (MG)

The Brazilian System of Soil Classification (SiBCS) is a taxonomic system, open and in permanent construction, as new knowledge on Brazilian soils is obtained. The objective of this study was to characterize the chemical, physical, morphological, micro-morphological and mineralogical properties of four pedons of Oxisols in a highland toposequence in the upper Jequitinhonha Valley, emphasizing aspects of their genesis, classification and landscape development. The pedons occupy the following slope positions: summit - Red Oxisol (LV), mid slope (upper third) - Yellow-Red Oxisol (LVA), lower slope (middle third)- Yellow Oxisol (LA) and bottom of the valley (lowest third) - "Gray Oxisol" ("LAC"). These pedons were described and sampled for characterization in chemical and physical routine analyses. The total Fe, Al and Mn contents were determined by sulfuric attack and the Fe, Al and Mn oxides in dithionite-citrate-bicarbonate and oxalate extraction. The mineralogy of silicate clays was identified by X ray diffraction and the Fe oxides were detected by differential X ray diffraction. Total Ti, Ga and Zr contents were determined by X ray fluorescence spectrometry. The "LAC" is gray-colored and contains significant fragments of structure units in the form of a dense paste, characteristic of a gleysoil, in the horizons A and BA. All pedons are very clayey, dystrophic and have low contents of available P and a pH of around 5. The soil color was related to the Fe oxide content, which decreased along the slope. The decrease of crystalline and low- crystalline Fe along the slope confirmed the loss of Fe from the "LAC". Total Si increased along the slope and total Al remained constant. The clay fraction in all pedons was dominated by kaolinite and gibbsite. Hematite and goethite were identified in LV, low-intensity hematite and goethite in LVA, goethite in LA. In the "LAC", no hematite peaks and goethite were detected by differential X ray diffraction. The micro-morphology indicated prevalence of granular microstructure and porosity with complex stacking patterns.. The soil properties in the toposequence converged to a single soil class, the Oxisols, derived from the same source material. The landscape evolution and genesis of Oxisols of the highlands in the upper Jequitinhonha Valley are related to the evolution of the drainage system and the activity of excavating fauna.

Revisiting Field Capacity (FC): variation of definition of FC and its estimation from pedotransfer functions

Taking into account the nature of the hydrological processes involved in in situ measurement of Field Capacity (FC), this study proposes a variation of the definition of FC aiming not only at minimizing the inadequacies of its determination, but also at maintaining its original, practical meaning. Analysis of FC data for 22 Brazilian soils and additional FC data from the literature, all measured according to the proposed definition, which is based on a 48-h drainage time after infiltration by shallow ponding, indicates a weak dependency on the amount of infiltrated water, antecedent moisture level, soil morphology, and the level of the groundwater table, but a strong dependency on basic soil properties. The dependence on basic soil properties allowed determination of FC of the 22 soil profiles by pedotransfer functions (PTFs) using the input variables usually adopted in prediction of soil water retention. Among the input variables, soil moisture content θ (6 kPa) had the greatest impact. Indeed, a linear PTF based only on it resulted in an FC with a root mean squared residue less than 0.04 m³ m-3 for most soils individually. Such a PTF proved to be a better FC predictor than the traditional method of using moisture content at an arbitrary suction. Our FC data were compatible with an equivalent and broader USA database found in the literature, mainly for medium-texture soil samples. One reason for differences between FCs of the two data sets of fine-textured soils is due to their different drainage times. Thus, a standardized procedure for in situ determination of FC is recommended.

SPATIAL DEPENDENCE OF ELECTRICAL CONDUCTIVITY AND CHEMICAL PROPERTIES OF THE SOIL BY ELECTROMAGNETIC INDUCTION

Brazilian soils have natural high chemical variability; thus, apparent electrical conductivity (ECa) can assist interpretation of crop yield variations. We aimed to select soil chemical properties with the best linear and spatial correlations to explain ECa variation in the soil using a Profiler sensor (EMP-400). The study was carried out in Sidrolândia, MS, Brazil. We analyzed the following variables: electrical conductivity - EC (2, 7, and 15 kHz), organic matter, available K, base saturation, and cation exchange capacity (CEC). Soil ECa was measured with the aid of an all-terrain vehicle, which crossed the entire area in strips spaced at 0.45 m. Soil samples were collected at the 0-20 cm depth with a total of 36 samples within about 70 ha. Classical descriptive analysis was applied to each property via SAS software, and GS+ for spatial dependence analysis. The equipment was able to simultaneously detect ECa at the different frequencies. It was also possible to establish site-specific management zones through analysis of correlation with chemical properties. We observed that CEC was the property that had the best correlation with ECa at 15 kHz.

Bacterial diversity of soil under eucalyptus assessed by 16S rDNA sequencing analysis

Studies on the impact of Eucalyptus spp. on Brazilian soils have focused on soil chemical properties and isolating interesting microbial organisms. Few studies have focused on microbial diversity and ecology in Brazil due to limited coverage of traditional cultivation and isolation methods. Molecular microbial ecology methods based on PCR amplified 16S rDNA have enriched the knowledge of soils microbial biodiversity. The objective of this work was to compare and estimate the bacterial diversity of sympatric communities within soils from two areas, a native forest (NFA) and an eucalyptus arboretum (EAA). PCR primers, whose target soil metagenomic 16S rDNA were used to amplify soil DNA, were cloned using pGEM-T and sequenced to determine bacterial diversity. From the NFA soil 134 clones were analyzed, while 116 clones were analyzed from the EAA soil samples. The sequences were compared with those online at the GenBank. Phylogenetic analyses revealed differences between the soil types and high diversity in both communities. Soil from the Eucalyptus spp. arboretum was found to have a greater bacterial diversity than the soil investigated from the native forest area.

Addition of nitrogen had no effect on yield and quality of apples in an high density orchard carrying a dwarf rootstock

The effect of N addition on apple yield and quality may vary according to the tree vigor. Apple trees developed over vigorous rootstocks had shown no response to N application in Brazil. In this study it was evaluated the effect of N addition to the soil on yield and quality of ´Royal Gala´ apples grafted on a dwarf rootstock (M.9). The orchard was planted in 1995 (2,857 trees ha-1) on an Oxisol containing 40 g kg-1 of organic matter and pH 6.0. The experiment was carried out from 1998 up to 2005. Treatments consisted of rates of N (0, 50, 100 and 150 kg ha-1 year-1 from 1998 to 2001, and respectively 0, 100, 200 and 300 kg ha-1 afterwards), all broadcasted within the tree row in two equal splits, at bud break and after harvest, as ammonium sulfate. Addition of N to the soil had no effect on fruit yield over the six years regardless of the applied rate. Averaged across treatments and years, fruit yield was 52.3 t ha-1. Nitrogen in the leaves (average of 24 g kg-1) or in the fruits (average of 346 mg kg-1) as well as some attributes related to fruit quality (color, firmness, acidity, soluble solids, physiological disorders) were unaffected by N addition. Some plant parameters related to tree vigor, however, grew higher with the increase on N rate. Thus, it is not necessary to apply N to deep Brazilian soils containing high organic matter in order to assure good fruit quality and yield on high-density orchards carrying dwarf rootstocks probably because the N required for tree growth and fruit production is supplied from soil organic matter decay.