Adsorção de fósforo em frações argila na presença de ácido fúlvico

Os ácidos orgânicos podem ser adsorvidos aos coloides do solo, favorecendo maior disponibilidade de P às plantas. Por meio de isotermas, avaliou-se a influência de ácido fúlvico (AF) sobre a adsorção de P na fração argila de dois Latossolos Vermelhos (LVdf e LVd), caulinita natural pouco cristalizada (KGa2), goethita (Gt) e hematita (Hm) sintéticas. As isotermas de adsorção de P ajustadas pelo modelo de Langmuir na presença de AF foram adequadas somente para a região de baixa concentração de P. De maneira geral, a presença de AF incubado nas frações argila estudadas foi capaz de reduzir a adsorção de P. Na fração argila do LVdf, a adsorção de P em baixas e altas concentrações desse nutriente teve pequena influência da sequência de incubação de P com AF, enquanto para a fração argila do LVd as sequências de incubação com P e AF influenciaram a adsorção de P. A redução da adsorção de P sobre a fração argila da KGa2 em baixas concentrações de P nas isotermas não dependeu da sequência de incubação de P e AF, e sim da presença do AF. Na região de altas concentrações de P, a sequência de incubação de P e AF influenciou a adsorção desse elemento. A adsorção de P sobre Gt foi dependente da sequência de incubação com AF, e a incubação prévia do AF promoveu redução da adsorção de P. A sequência de incubação do P e AF na Hm influenciou a adsorção de P quando em baixas e altas concentrações nas isotermas. Os menores valores de adsorção de P ocorreram com a incubação de P juntamente ao AF ou incubação de AF precedida da do P.

Relação entre óxidos de ferro e de manganês e a sorção de fósforo em solos no Rio Grande do Sul

Os solos utilizados para a cultura de arroz irrigado por alagamento no Estado do Rio Grande do Sul são oriundos de diferentes materiais de origem e estão sujeitos às variações temporais das condições de oxidação e redução. Essas condições contribuem para as variações nos teores totais e na crista-linidade de óxidos de Fe e de Mn, as quais estão relacionadas aos processos de sorção e dessorção, afetando a disponibilidade de P para a cultura de arroz irrigado. Com o objetivo de verificar a sorção de P e a sua disponibilidade para o arroz em solos oriundos de diferentes materiais de origem, foram desenvolvidos dois estudos: o primeiro para determinar os teores totais de Fe e de Mn e a capacidade máxima de adsorção de P (CMAP) pelas isotermas de Langmuir; além disso, foram associados a CMAP e os teores totais de Fe e de Mn, na razão FeOx6/Fe dit, razão MnOx6/Mn dit argila e da matéria orgânica. O segundo estudo foi para quantificar a sorção de P durante quatro períodos de alagamento do solo. Os solos oriundos de sedimento de basalto (Luvissolo, Vertissolo e Chernossolo) apresentaram maior CMAP do que os oriundos de sedimento de granito e arenito (Planossolos e Gleissolos), devido aos maiores teores totais de Fe e também às razões de Fe extraído por oxalato de amônio a pH 6 (Fe ox6)/ferro extraído por ditionito (Fe dit) e Mn extraído por oxalato de amônio a pH 6 (Mn ox6)/Mn dit. A razão Fe ox6/Fe dit apresentou a maior associação com a CMAP em todos os solos utilizados. O Planossolo teve menor sorção de P do que os solos oriundos de sedimento de basalto em todos os períodos de alagamento.

Phosphorus accumulation and pollution potential in a hapludult fertilized with pig manure

Successive applications of pig litter to the soil surface can increase the phosphorus (P) content and alter its adsorption, promoting P transfer to surface or subsurface waters. The purpose of this study was to evaluate P accumulation and the pollution potential of a soil after application of pig litter. In March 2010, eight years after the installation of an experiment in Braço do Norte, Santa Catarina, SC, Brazil, on a Typic Hapludult, soil was sampled (layers 0-2.5, 2.5-5, 5-10, 10-15, 15-20 and 20-30 cm) after the following fertilization treatments: no pig litter fertilization, pig slurry application and pig manure application. In this period, 694 and 1,890 kg P2O5 ha-1 were applied in the treatments with pig slurry and pig manure, respectively. The P content was determined, based on Mehlich-1, anion exchange resin (AER), 0.01 mol L-1 CaCl2 and total P in the samples. The adsorption isotherm parameters were also determined by the Langmuir and Koski-Vähälä & Hartikainem models in the layers 0-2.5 and 20-30 cm. The application of 1,890 kg P2O5 ha-1 in the form of pig manure led to P accumulation, as evidenced by Mehlich-1, down to a depth of 15 cm, by AER and 0.01 mol L-1 CaCl2 down to 20 cm and by total P to 30 cm. After application of 1,890 kg P2O5 ha-1 in the form of pig manure, the values of maximum P adsorption capacity were lowest in the deepest layer (20-30 cm), indicating the occupation of part of the adsorption sites of the particles. The application of swine manure to the soil over eight years increased the P quantity in the soil solution of the surface layer, indicating environmental contamination risk for surface and subsurface waters.

Adsorção de cádmio em Latossolos sob vegetação de mata nativa e cultivados¹

Os metais pesados podem ser encontrados naturalmente em solos, em baixas concentrações, podendo ter seus teores intensificados por meio de ações antrópicas, tornando-se um dos entraves no manejo de solos tropicais. Esses elementos químicos podem ser encontrados na constituição de adubos orgânicos e inorgânicos, inseticidas, fungicidas, rejeito de mineração e lixo urbano, podendo causar sérios danos ao ambiente e à saúde humana. Nesse sentido, estudos de adsorção são imprescindíveis na avaliação do comportamento de metais pesados no solo. O objetivo deste trabalho foi avaliar a influência dos atributos químicos, granulométricos e mineralógicos sobre a adsorção de Cd, avaliados pelos modelos de Langmuir e de Freundlich, em Latossolos que sofreram ou não ação antrópica. As amostras de solo foram coletadas da camada superficial, 0,00-0,20 m, sendo realizadas análises químicas, granulométricas e mineralógicas. No estudo de adsorção, foram usadas as concentrações 0, 5, 25, 50, 100, 200, 300 e 400 µg L-1 de Cd na forma de Cd(NO3)2. Para a construção das isotermas de adsorção, utilizaram-se os modelos matemáticos empíricos de Langmuir e Freundlich. Os dados obtidos foram analisados por meio de técnicas estatísticas multivariadas, Análise de Agrupamento e Análise de Componentes Principais; no experimento de adsorção os dados ajustaram-se aos modelos de Langmuir e Freundlich. Os solos com menor relação goethita/hematita e maior capacidade de troca de cátions e pH apresentaram maior capacidade máxima de adsorção de Cd.

SOIL PHOSPHORUS THRESHOLDS IN EVALUATING RISK OF ENVIRONMENTAL TRANSFER TO SURFACE WATERS IN SANTA CATARINA, BRAZIL

The State of Santa Catarina, Brazil, has agricultural and livestock activities, such as pig farming, that are responsible for adding large amounts of phosphorus (P) to soils. However, a method is required to evaluate the environmental risk of these high soil P levels. One possible method for evaluating the environmental risk of P fertilization, whether organic or mineral, is to establish threshold levels of soil available P, measured by Mehlich-1 extractions, below which there is not a high risk of P transfer from the soil to surface waters. However, the Mehlich-1 extractant is sensitive to soil clay content, and that factor should be considered when establishing such P-thresholds. The objective of this study was to determine P-thresholds using the Mehlich-1 extractant for soils with different clay contents in the State of Santa Catarina, Brazil. Soil from the B-horizon of an Oxisol with 800 g kg-1 clay was mixed with different amounts of sand to prepare artificial soils with 200, 400, 600, and 800 g kg-1 clay. The artificial soils were incubated for 30 days with moisture content at 80 % of field capacity to stabilize their physicochemical properties, followed by additional incubation for 30 days after liming to raise the pH(H2O) to 6.0. Soil P sorption curves were produced, and the maximum sorption (Pmax) was determined using the Langmuir model for each soil texture evaluated. Based on the Pmax values, seven rates of P were added to four replicates of each soil, and incubated for 20 days more. Following incubation, available P contents (P-Mehlich-1) and P dissolved in the soil solution (P-water) were determined. A change-point value (the P-Mehlich-1 value above which P-water starts increasing sharply) was calculated through the use of segmented equations. The maximum level of P that a soil might safely adsorb (P-threshold) was defined as 80 % of the change-point value to maintain a margin for environmental safety. The P-threshold value, in mg dm-3, was dependent on the soil clay content according to the model P-threshold = 40 + Clay, where the soil clay content is expressed as a percentage. The model was tested in 82 diverse soil samples from the State of Santa Catarina and was able to distinguish samples with high and low environmental risk.

Boron adsorption in soils from the State of São Paulo, Brazil

Boron adsorption was studied in five representative soils (Rhodic Hapludox, Arenic Paleudalf and three Typic Hapludox) from the State of São Paulo, Brazil. Adsorption was higher in the clayey Oxisols, followed by the Alfisol and the coarser Oxisols. Calcium carbonate promoted an increase in the amount of adsorbed boron in all soils, with the most pronounced effect in the coarser-textured Oxisols. High correlation coefficients were found between adsorbed boron and clay and amorphous aluminum oxide contents and specific surface area (r = 0.79, 0.76 and 0.73, respectively, p < 0.01). Clay content, free aluminum oxide, and hot CaCl2 (0.01 mol L-1)-extracted boron explained 93% of the variation of adsorbed boron. Langmuir and Freundlich isotherms fitted well to the adsorbed data, and highest values for maximum boron adsorption were found in clayey soils, which were significantly correlated with contents of total, free and amorphous iron and aluminum oxides, as well with the physical attributes. Ninety four percent of the variation in the maximum adsorption could be related to the free iron content.

Adsorção de boro em solos de várzea do Sul de Minas Gerais

O objetivo deste trabalho foi avaliar a adsorção de B em quatro solos de várzea da região de Lavras, MG, por meio dos parâmetros das isotermas de Langmuir e Freundlich, no período de outubro a novembro de 1998. Amostraram-se solos Aluvial, Glei Pouco Húmico, Glei Húmico, e Orgânico artificialmente drenado, coletados na camada de 0-20 cm e peneirados para 2 mm. Amostras com e sem calagem foram incubadas durante 30 dias. Duplicatas de 4,0 g de solo de cada classe foram acondicionadas em tubos de polietileno com oito diferentes doses de B (0, 2, 4, 8, 12, 16, 24 e 32 mig mL-1) preparadas em CaCl2.2H2O 0,01 mol L-1, com ácido bórico como fonte. Os teores de B na solução de equilíbrio foram determinados pelo método da Azometina-H. Os resultados mostraram que alto teor de matéria orgânica confere ao solo Glei Húmico maior capacidade de adsorver boro. A matéria orgânica, a superfície específica, caulinita e alumínio trocável foram os atributos dos solos que se correlacionaram diretamente com a capacidade máxima de adsorção de B (CMAB). A calagem proporcionou diminuição da CMAB em todos os solos.

Adsorption of glyphosate in chilean soils and its relationship with unoccupied phosphate binding sites

The objective of this work was to investigate glyphosate adsorption by soils and its relationship with unoccupied binding sites for phosphate adsorption. Soil samples of three Chilean soils series - Valdivia (Andisol), Clarillo (Inceptisol) and Chicureo (Vertisol) - were incubated with different herbicide concentrations. Glyphosate remaining in solution was determined by adjusting a HPLC method with a UV detector. Experimental maximum adsorption capacity were 15,000, 14,300 and 4,700 mg g¹ for Valdivia, Clarillo, and Chicureo soils, respectively. Linear, Freundlich, and Langmuir models were used to describe glyphosate adsorption. Isotherms describing glyphosate adsorption differed among soils. Maximum adjusted adsorption capacity with the Langmuir model was 231,884, 17,874 and 5,670 mg g-1 for Valdivia, Clarillo, and Chicureo soils, respectively. Glyphosate adsorption on the Valdivia soil showed a linear behavior at the range of concentrations used and none of the adjusted models became asymptotic. The high glyphosate adsorption capacity of the Valdivia soil was probably a result of its high exchangeable Al, extractable Fe, and alophan and imogolite clay type. Adsorption was very much related to phosphate dynamics in the Valdivia soil, which showed the larger unoccupied phosphate binding sites. However relationship between unoccupied phosphate binding sites and glyphosate adsorption in the other two soils (Clarillo and Chicureo) was not clear.

Zinc adsorption in highly weathered soils

The objective of this work was to assess the effects of pH and ionic strength upon zinc adsorption, in three highly weathered variable charge soils. Adsorption isotherms were elaborated from batch adsorption experiments, with increasing Zn concentrations (0-80 mg L-1), and adsorption envelopes were constructed through soil samples reactions with 0.01, 0.1 and 1 mol L-1 Ca(NO3)2 solutions containing 5 mg L-1 of Zn, with an increasing pH value from 3 to 8. Driving force of reaction was quantified by Gibbs free energy and separation factor. Isotherms were C-, H- and L-type and experimental results were fitted to nonlinear Langmuir model. Maximum adsorption ranged from 59-810 mg kg-1, and Zn affinity was greater in subsoil (0.13-0.81 L kg-1) than in the topsoil samples (0.01-0.34 L kg-1). Zinc adsorption was favorable and spontaneous, and showed sharply increase (20-90%) in the 4-6 pH range. No effect of ionic strength was observed at pH values below 5, because specific adsorption mechanisms predominated in the 3-5 pH range. Above pH 5, and in subsoil samples, Zn was adsorbed by electrostatic mechanisms, since ionic strength effect was observed. Despite depth and ionic strength effects, Zn adsorption depends mainly on the pH.

Adsorção de cádmio e chumbo em solos tropicais altamente intemperizados

O objetivo deste trabalho foi determinar a capacidade de adsorção de cádmio e de chumbo e avaliar a influência das propriedades dos solos sobre os parâmetros de adsorção desses elementos em solos tropicais altamente intemperizados. Foram utilizados quatro Latossolos e um Argissolo. Amostras de 1 g de solo foram agitadas por 16 horas, com soluções de CaCl2 0,01 mol L-1, às quais foram adicionadas 0, 10, 20, 30, 40, 60 e 80 µg mL-1 de cádmio e 0, 10, 20, 40, 60, 80, 100 e 120 µg mL-1 de chumbo na forma de nitrato. As quantidades adsorvidas foram determinadas mediante análise dos elementos no sobrenadante, e os dados foram ajustados às isotermas de Langmuir e de Freundlich. Os resultados experimentais ajustaram-se aos modelos estudados. A adsorção máxima de cádmio variou de 136 a 1.604 µg g-1 e a de chumbo, de 988 a 1.660 µg g-1. As energias de ligação variaram de 0,0036 a 0,0403 µg mL-1 e de 0,0282 a 1,0425 µg mL-1 para cádmio e chumbo, respectivamente. Os atributos dos solos correlacionados à adsorção de cádmio foram o pH e a capacidade de troca de cátions, e à adsorção de chumbo foram o pH e os níveis de óxidos de ferro e de alumínio.

Análise das isotermas de adsorção de Cu(II), Cd(II), Ni(II) e Zn(II) pela N-(3,4-dihidroxibenzil) quitosana empregando o método da regressão não linear

Adsorption of Cu(II), Ni(II), Pb(II) and Zn(II) ions from aqueous solutions by N-(3,4-dihydroxybenzyl) chitosan have been carried out. The Langmuir (L), Freundlich (F), Langmuir - Freundlich (LF), Redlich-Peterson (RP) and Tóth (T) adsorption isotherms models have been applied to fit the experimental data. Nonlinear regression computational program "Enzefitte", which is a library of the more commonly used adsorption isotherm equations for obtaining tabular outuput suitable for plotting theoretical of fitted isotherms, has been used to estimate the adsorption parameters. These parameters were used to calculate the amount adsorbed q calc., a function of concentration (C).

Adsorção de íons Cu2+ em latossolo vermelho-amarelo húmico

In environmental studies it is necessary to know the adsorption behavior of metals by soils, since the unfavorable effects of heavy metals and even the micronutrients at high concentrations in the environment are related to these adsorbents' ability to immobilize them. A sample of a humic yellow red oxisol from Araponga region in the State of Minas Gerais, Brazil, was used to verify the adsorption behavior of Cu2+ ions in this substrate. The mathematical model described by Langmuir's adsorption equation in its linearized form was applied and the values of the maximum capacity b and those of the constant related to the bonding energy a were obtained. Aliquots of copper nitrate solutions containing several concentrations of this metal were added to soil samples, the pH being predetermined for developing the adsorption experiments. The chemical and physical characterization of soil sample were performed by determining the organic carbon, nitrogen and phosphorus concentrations, cation exchange capacity (CEC), pH, concentration of metals (Al, Fe, K, Mg, Ca, Zn, Cu, Ni, Cr, Co, Pb, and Cd), granulometric analysis and X-ray diffraction. Langmuir isotherms presented two distinct adsorption regions at both pH 4 and pH 5, showing that the adsorptive phenomenon occurs in two distinct stages. The adsorption sites for the lower part presented greater bonding energy and low adsorption capacity compared with the adsorption sites of the part of the curve corresponding to higher Cu concentrations in the equilibrating solution.

Utilização de modelos físico-químicos de adsorção no estudo do comportamento do cobre em solos argilosos

It was evaluated the applicability of Langmuir, Freundlich and Temkin models to copper adsorption in three classes of soils. Fractions of each soil were added to test tubes containing growing concentrations of the metal in solution. The tubes were shaken and the copper concentrations were determined in the extracts by atomic absorption spectrometry (AAS). The models offered a good fit for the experimental data indicating that presence of silicated clay had high influence on copper sorption. The Langmuir isotherm showed high influence of the organic matter in the absorption phenomenon. It was evidenced the importance of further studies related to Temkin model.

Emprego de monocamadas auto-organizadas no desenvolvimento de sensores eletroquímicos

Self-assembled monolayers (SAMs) modified electrodes exhibit unique behavior that can greatly benefit electrochemical sensing. This brief review highlights the applications of SAM modified electrodes in electroanalytical chemistry. After a general introduction, which includes the approaches for SAM development, different electrochemical systems for detecting inorganic and organic species are described and discussed. Special attention to the coupling of biological sensing element to the SAM is given, which can selectively recognize the analyte. Future prospects are also evaluated.

Desenvolvimento de um sistema automatizado para a fabricação de filmes automontados

In this technical note, we describe the construction of a low-cost computer controlled device for layer-by-layer film fabrication. The software allows to control multiple material deposition, washing and drying steps and the time for each operation. To test the device, we produced and characterized self-assembled films of conductive polymers by alternating poly(o-methoxyaniline) (POMA) and poly(3-thiophene acetic acid) (PTAA) via the layer-by-layer technique.