Influence of soil pH on inorganic phosphorus sorption and desorption in a humid brazilian Ultisol

Liming is a common practice to raise soil pH and increase phosphorus (P) bioavailability in tropical regions. However, reports on the effect of liming on P sorption and bioavailability are controversial. The process of phosphorus desorption is more important than P sorption for defining P bioavailability. However few studies on the relationship between soil pH and P desorption are available, and even fewer in the tropical soils. The effects of soil pH on P sorption and desorption in an Ultisol from Bahia, Brazil, were investigated in this study. Phosphorus sorption decreased by up to 21 and 34 % with pH increases from 4.7 to 5.9 and 7.0, respectively. Decreasing Langmuir K parameter and decreasing partition coefficients (Kd) with increasing pH supported this trend. Phosphorus desorption was positively affected by increased soil pH by both the total amount of P desorbed and the ratio of desorbed P to initially sorbed P. A decreased K parameter and increased Kd value, particularly at the highest pH value and highest P-addition level, endorsed this phenomenon. Liming the soil had the double effect of reducing P sorption (up to 4.5 kg ha-1 of remaining P in solution) and enhancing P desorption (up to 2.7 kg ha-1 of additionally released P into solution).

Competitive sorption and desorption of phosphate and citrate in clayey and sandy loam soils

The increase of organic acids in soils can reduce phosphorus sorption. The objective of the study was to evaluate the competitive sorption of P and citrate in clayey and sandy loam soils, using a stirred-flow system. Three experiments were performed with soil samples (0-20 cm layer) of clayey (RYL-cl) and sandy loam (RYL-sl) Red Yellow Latosols (Oxisols). In the first study, the treatments were arranged in a 2 × 5 factorial design, with two soil types and five combinations of phosphorus and citrate application (only P; P + citrate; and citrate applied 7, 22, 52 min before P); in the second, the treatments were arranged in a 2 × 2 factorial design, corresponding to two soils and two forms of P and citrate application (only citrate and citrate + P); and in the third study, the treatments in a 2 × 2 × 6 factorial design consisted of two soils, two extractors (citrate and water) and six incubation times. In the RYL-cl and RYL-sl, P sorption was highest (44 and 25 % of P application, respectively), in the absence of citrate application. Under citrate application, P sorption was reduced in all treatments. The combined application of citrate and P reduced P sorption to 25.8 % of the initially applied P in RYL-cl and to 16.7 % in RYL-sl, in comparison to P without citrate. Citrate sorption in RYL-cl and RYL-sl was highest in the absence of P application, corresponding to 32.0 and 30.2 % of the citrate applied, respectively. With P application, citrate sorption was reduced to 26.4 and 19.7 % of the initially applied citrate in RYL-cl and RYL-sl, respectively. Phosphorus desorption was greater when citrate was used. Phosphorus desorption with citrate and water was higher in the beginning (until 24 h of incubation of P) in RYL-cl and RYL-sl, indicating a rapid initial phase, followed by a slow release phase. This suggests that according to the contact time of P with the soil colloids, the previously adsorbed P can be released to the soil solution in the presence of competing ligands such as citrate. In conclusion, a soil management with continuous input of organic acids is desirable, in view of their potential to compete for P sorption sites, especially in rather weathered soils.

MERCURY QUANTIFICATION IN SOILS USING THERMAL DESORPTION AND ATOMIC ABSORPTION SPECTROMETRY: PROPOSAL FOR AN ALTERNATIVE METHOD OF ANALYSIS

Despite the considerable environmental importance of mercury (Hg), given its high toxicity and ability to contaminate large areas via atmospheric deposition, little is known about its activity in soils, especially tropical soils, in comparison with other heavy metals. This lack of information about Hg arises because analytical methods for determination of Hg are more laborious and expensive compared to methods for other heavy metals. The situation is even more precarious regarding speciation of Hg in soils since sequential extraction methods are also inefficient for this metal. The aim of this paper is to present a technique of thermal desorption associated with atomic absorption spectrometry, TDAAS, as an efficient tool for quantitative determination of Hg in soils. The method consists of the release of Hg by heating, followed by its quantification by atomic absorption spectrometry. It was developed by constructing calibration curves in different soil samples based on increasing volumes of standard Hg2+ solutions. Performance, accuracy, precision, and quantification and detection limit parameters were evaluated. No matrix interference was detected. Certified reference samples and comparison with a Direct Mercury Analyzer, DMA (another highly recognized technique), were used in validation of the method, which proved to be accurate and precise.

Ammonia nitrogen desorption from sanitary landfill leachate in filling towers

Sanitary landfill leachates present high concentrations of carbonaceous and nitrogenous materials. The crucial point is that carbonaceous materials are of difficult biodegradation, what compromises the performance of biological treatment processes, while nitrogenous materials, such as ammonia nitrogen, probably preclude the use of biological treatments. Therefore, the aim of this work was to study the desorption process of ammonia nitrogen from sanitary landfill leachate in filling towers. Desorption was carried out in filling towers of 35 L capacity. The leachate was collected from a sanitary landfill located in João Pessoa, Paraíba State, Brazil. Desorption efficiency for the pH values ​​adopted in four treatments was 93% minimum and 95.5% maximum, with aeration mean time ranging from 3 to 6 hours. The limiting factors of ammonia nitrogen desorption from sanitary landfill leachates in filling towers are associated with the use of alkalizer species for pH correction, and electricity costs for aeration.

Sorption and desorption of picloram in soils under pastures in Brazil

The objective of this work was to determine the coefficients of sorption and desorption of picloram in Ultisol (PVA) and Oxisol (LVA), displaying different physical and chemical characteristics. Samples of soil were collected at the 0 20 cm depth in degraded pasture areas in Viçosa-MG. Firstly, the equilibrium time between the herbicide in solution and the herbicide which was sorbed in the soil was determined by the Batch Equilibrium method. The time required was 24 hours. Sorption and desorption studies were carried out under controlled laboratory conditions; the sorption evaluation consisted in adding 10.0 mL of herbicide solutions at different concentrations to tubes containing 2.00 g of soil, with vertical rotary agitation being maintained during the pre-determined equilibrium time. After centrifugation, supernatant extract cleaning and filtration, herbicide concentration was determined by high performance liquid chromatography (HPLC) with UV detection at 254 nm. Desorption was evaluated using the samples in the tubes after the sorption tests. The Freundlich model was used for interpretation of the sorption process. Ultisol showed higher adsorption coefficient (Kf a) compared with Oxisol, which may be attributed to the lower pH of the soil and its higher organic matter content. Desorption process occurred in both soils; the LVA allowed greater release of the previously sorbed molecules.

Sorption and desorption of Suflafenacil in two soils in the state of São Paulo with different physical and chemical attributes

A study was conducted to evaluate the sorption and desorption of 14C herbicide saflufenacil (pyrimidinedione) in two soils in the State of São Paulo, classified as Red Yellow Latosol with clayey texture (LVA-1) and medium texture (LVA-2), using the batch method through isotherms. The soils were air dried and sieved a 2 mm mesh. The radioactivity was determined by liquid scintillation spectrometry in acclimatized room (25 ± 2 °C). Sorption isotherms were conducted for 5 concentrations of saflufenacil (5.0; 2.5; 1.0; 0.5 and 0.05 μg mL-1) and the results were adjusted to the Freundlich equation, thus obtaining the parameters of sorption followed by two extractions with 0.01 M CaCl2 to determine desorption parameters similarly to sorption. The results showed that saflufenacil sorption was low for both soils studied, being greater for the LVA with higher organic matter content. The desorption coefficients were greater than their sorption coefficients, suggesting the occurrence of hysteresis. The sorption and desorption isotherms (classified as type C isotherms), hysteresis and the t-test between the angular coefficient of the respective isotherms showed that both the sorption and desorption occur with equal intensity.

Candida albicans PROTEIN PROFILE CHANGES IN RESPONSE TO THE BUTANOLIC EXTRACT OF Sapindus saponariaL.

Candida albicans is an opportunistic human pathogen that is capable of causing superficial and systemic infections in immunocompromised patients. Extracts of Sapindus saponaria have been used as antimicrobial agents against various organisms. In the present study, we used a combination of two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) and matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) to identify the changes in protein abundance of C. albicans after exposure to the minimal inhibitory concentration (MIC) and sub-minimal inhibitory concentration (sub-MIC) of the butanolic extract (BUTE) of S. saponaria and also to fluconazole. A total of six different proteins with greater than 1.5 fold induction or repression relative to the untreated control cells were identified among the three treatments. In general, proteins/enzymes involved with the glycolysis (GPM1, ENO1, FBA1), amino acid metabolism (ILV5, PDC11) and protein synthesis (ASC1) pathways were detected. In conclusion, our findings reveal antifungal-induced changes in protein abundance of C. albicans. By using the previously identified components of the BUTE of S. saponaria(e.g., saponins and sesquiterpene oligoglycosides), it will be possible to compare the behavior of compounds with unknown mechanisms of action, and this knowledge will help to focus the subsequent biochemical work aimed at defining the effects of these compounds.

Polyphasic characterisation of Burkholderia cepaciacomplex species isolated from children with cystic fibrosis

Cystic fibrosis (CF) patients with Burkholderia cepacia complex (Bcc) pulmonary infections have high morbidity and mortality. The aim of this study was to compare different methods for identification of Bcc species isolated from paediatric CF patients. Oropharyngeal swabs from children with CF were used to obtain isolates of Bcc samples to evaluate six different tests for strain identification. Conventional (CPT) and automatised (APT) phenotypic tests, polymerase chain reaction (PCR)-recA, restriction fragment length polymorphism-recA, recAsequencing, and matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) were applied. Bacterial isolates were also tested for antimicrobial susceptibility. PCR-recA analysis showed that 36 out of the 54 isolates were Bcc. Kappa index data indicated almost perfect agreement between CPT and APT, CPT and PCR-recA, and APT and PCR-recA to identify Bcc, and MALDI-TOF and recAsequencing to identify Bcc species. The recAsequencing data and the MALDI-TOF data agreed in 97.2% of the isolates. Based on recA sequencing, the most common species identified were Burkholderia cenocepacia IIIA (33.4%),Burkholderia vietnamiensis (30.6%), B. cenocepaciaIIIB (27.8%), Burkholderia multivorans (5.5%), and B. cepacia (2.7%). MALDI-TOF proved to be a useful tool for identification of Bcc species obtained from CF patients, although it was not able to identify B. cenocepacia subtypes.

Glyphosate behavior in a Rhodic Oxisol under no-till and conventional agricultural systems

The behavior of glyphosate in a Rhodic Oxisol, collected from fields under no-till and conventional management systems in Ponta Grossa, Parana state (Brazil) was investigated. Both agricultural systems had been in production for 23 years. Glyphosate mineralization, soil-bound forms, sorption and desorption kinetics, sorption/desorption batch experiments, and soil glyphosate phythoavailability (to Panicum maximum) were determined. The mineralization experiment was set up in a completely randomized design with a 2 x 2 factorial scheme (two management systems and two 14C radiolabelled positions in the glyphosate), with five replicates. 14CO2 evolution was measured in 7-day intervals during 63 days. The glyphosate sorption kinetics was investigated in a batch experiment, employing a glyphosate concentration of 0.84 mg L-1. The equilibration solution was 0.01 mol L-1 CaCl2 and the equilibration times were 0, 10, 30, 60, 120, 240, and 360 min. Sorption/desorption of glyphosate was also investigated using equilibrium batch experiments. Five different concentrations of the herbicide were used for sorption (0.42, 0.84, 1.68, 3.36, and 6.72 mg L-1) and one concentration for desorption. Glyphosate phytoavailability was analyzed in a 2 x 5 factorial scheme with two management systems and five glyphosate concentrations added to soil (0, 4.2, 8.4, 42.0, and 210.0 µg g-1) in a completely randomized design. Phytotoxicity symptoms in P. maximum were evaluated for different periods. The soil under both management systems showed high glyphosate sorption, which impeded its desorption and impaired the mineralization in the soil solution. Practically the total amount of the applied glyphosate was quickly sorbed (over 90 % sorbed within 10 min). Glyphosate bound to residues did not have adverse effects on P. maximum growth. The mineralization of glyphosate was faster under no-till and aminomethylphosphonic acid was the main glyphosate metabolite.

Phosphorus availability in oxidic soils treated with lime and silicate applications

Based on the assumption that silicate application can raise soil P availability for crops, the aim of this research was to compare the effect of silicate application on soil P desorption with that of liming, in evaluations based on two extractors and plant growth. The experiment was carried out in randomized blocks with four replications, in a 3 × 3 × 5 factorial design, in which three soil types, three P rates, and four soil acidity correctives were evaluated in 180 experimental plots. Trials were performed in a greenhouse using corn plants in 20-dm³ pots. Three P rates (0, 50 and 150 mg dm-3) were applied in the form of powder triple superphosphate and the soil was incubated for 90 days. After this period, soil samples were collected for routine chemical analysis and P content determination by the extraction methods resin, Mehlich-1 and remaining P. Based on the results, acidity correctives were applied at rates calculated for base saturation increased to 70 %, with subsequent incubation for 60 more days, when P content was determined again. The acidity correctives consisted of: dolomitic lime, steelmaking slag, ladle furnace slag, and wollastonite. Therefore, our results showed that slags raised the soil P content more than lime, suggesting a positive correlation between P and Si in soil. Silicon did not affect the extractor choice since both Mehlich-1 and resin had the same behavior regarding extracted P when silicon was applied to the soil. For all evaluated plant parameters, there was significant interaction between P rates and correctives; highest values were obtained with silicate.

Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR) spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure). All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

Imazaquin sorption in surface and subsurface soil samples

The objective of this work was to study the sorption and desorption of imazaquin, in surface and subsurface soil samples from Brazil. Sorption and desorption steps were carried out using batch equilibration and high performance liquid chromatography analytical routines. The value of Kf,ads was positively correlated with clay content, and negatively correlated with pH of supernatant. Samples from Typic Haplustox, clayey soil profile having high clay content, provided higher Kf,ads values, and negative correlation with organic carbon, silt content, cation exchange capacity and pH.

Metodologia para o crescimento de esferas monocristalinas de metais nobres

This paper describes in detail a technique employed to grow quasi-spherical single crystals of noble metals for electrochemical applications, using platinum as an example. The metal beads were formed by melting the extremity of a wire in an oxygen / butane flame. X-ray techniques were used to check the crystallization and to determine the orientation of the crystals. Treatment with a pure hydrogen flame followed by a cooling procedure in a hydrogen / argon atmosphere were used for conditioning the well-defined platinum single crystal surfaces. Finally, electrochemical characterization of the Pt(111), Pt(110) and Pt(100) surfaces was done in diluted sulfuric acid solution in the hydrogen adsorption / desorption potential region.

Estudos da eletrodeposição de metais em regime de subtensão

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111), Pt(100) e Pt(110)

Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100), Pt(110) and Pt(111), in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.