Determinação de fósforo em aços por espectrometria de absorção atômica no forno de grafite

A method for the determination of phosphorus in steel samples by graphite furnace atomic absorption spectrometry, using the Zeeman effect background correction and the STPF conditions is proposed. The effect of iron (III) on the phosphorus signal was studied. It was verified, through the pyrolysis temperature curves, that iron (III) is an efficient chemical modifier, thermically stabilizing phosphorus up to 1400ºC. The phosphorus signal increases with the iron (III) concentration, but in the range, which corresponds to the usual concentrations of iron in the sample solutions, the increase is small. Phosphorus was determined in three standard reference materials, after its dissolution in a mixture of hydrochloric and perchloric acids in a PTFE bomb. The agreement with the certified concentration values was excellent. Iron (III) was added to the reference analytical solutions prepared in the blank of the dissolution, while the sample solutions were measured directly, since they already contained the modifier. The detection limit (k = 2) was 0.0042% of phosphorus in the steel sample.

Determinação de fósforo orgânico em águas de produção petrolífera por ICP- AES e ICP- MS após pré-concentração em coluna de sílica-C18

Results on the optimization of analytical methods for the determination of phosphorus in phosphino-polycarboxylate (PPCA), used frequently as scale inhibitor during oil production, by ICP-AES and ICP-MS are presented. Due to the complex matrix of production waters (brines) and their high concentration in inorganic phosphorus, the separation of organic phosphorus prior to its determination is necessary. In this work, minicolumns of silica immobilized C18 were used. Optimization of the separation step resulted in the following working conditions: (1) prewashing of the column with methanol (80% v/v); (2) use of a flow rate of 5 mL/min and 10 mL/min, respectively, for the preconditioning step and for percolation of the water sample; (3) final elution of organic phosphorus with 7 mL of buffer of H3BO3/NaOH (0.05 M, pH 9) with a flow rate of 1 mL/min. Sample detection limits (3s) for different combinations of nebulizers and spectrometric methods, based on 10 mL water aliquots, are: ICP-AES -Cross flow (47 mg/L) and Ultrasonic (18 mug/L); ICP-MS -Cross flow (1.2 mug/L), Cyclonic (0.7 mug/L) and Ultrasonic (0.5 mug/L). Typical recoveries of organic phosphorus are between 90 and 95% and the repeatability of the whole procedure is better than 10%. The developed methodology was applied successfully to samples from the oil-well NA 46, platform PNA 2, Campos basin, Brazil. Assessment of the PPCA inhibitor was possible at lower concentrations than achieved by current analytical methods, resulting in benefits such as reduced cost of chemicals, postponed oil production and lower environmental impacts.

Reações de Cp'(CO)2MnPPH2H com CH3COCl e CH3S(O)2Cl em THF/trietilamina: evidências da primeira estabilização por complexação de um fósforo-homólogo das sulfonamidas

Cp'Mn(CO)3 (Cp'=h5-C5H4-CH 3) reacts with P(C6H5)2H in THF to give Cp'(CO)2MnPPh2H (Ph = Phenyl) (1), by substitution of one CO ligand. The reaction of 1 with CH3COCl and CH3S(O)2Cl in the presence of triethylamine occurs under electrophilic substitution on the diphenylphosphan ligand to yield the acetyl- and sulfonylphosphane complexes of manganese(I) Cp'(CO)2MnPPh2COCH3 (2) and Cp'(CO)2MnPPh2S(O)2 CH3 (3). The complex stabilisation of these molecules, wich are hitherto unknown in the free state, is only accomplished by blocking the free electron pair on phosphorus by coordination. The new complexes 1, 2 and 3 were analysed by IR, ¹H-NMR and 31P-MNR spectroscopy and their similar structures are discusssed.

Híbridos inorgânico-orgânicos derivados da reação de filossicatos com organossilanos

Silylation reactions involving hydroxylated surfaces are an important route for synthesis of new materials that could present selected properties, for application in different areas such as catalysis, chromatography, adsorption and electrochemistry. An overview of many synthetic routes, comprising organosilanes to yield phyllosilicates is now presented.

Otimização da preparação de eletrodo de pasta de carbono contendo riboflavina imobilizada em suporte inorgânico

The aim of this work was to optimize the preparation of electrodes with riboflavin (RF) immobilized on a silica surface modified with niobium oxide and carbon paste. Electrode preparation was optimized employing a factorial design consisting of two levels and three factors. The electrochemical properties of immobilized RF were investigated by cyclic voltammetry. The factorial analysis was carried out analysing the current intensity (Ipa). It was possible to optimize the electrode to get the best reversibility in the redox process, i. e. the lowest separation between anodic and cathodic peak potentials and a current ratio close to unity. The concentration of supporting electrolyte has a small effect. The proportion has the highest effect and the interaction factor between proportion and mixture has also a significant effect on the current intensity.

Estudo dos efeitos do silício e do fósforo na redução da disponibilidade de metais pesados em área de mineração

This study was developed with a soil contaminated by heavy metals, with the purpose of evaluating the action of silicon and phosphorus as protection agents through simple extractions by DTPA. The collected samples were prepared and incubated with five doses of silicon and five doses of phosphorus, with four replicates, amounting to 100 experimental units. After 30 and 60 days, samples of each treatment were collected, submitted to pH analyses and simple extraction by DTPA. The amounts of DTPA-extracted metals depended on the doses of silicon and phosphorus and on the pH. Treatments with silicon and phosphorus was efficient in decreasing the availability of heavy metals in soil.

Influência das variáveis nitrogênio, fósforo e ºBrix na produção dos metabólicos secundários contaminantes totais da fermentação alcoólica

The present study evaluated the influence of nitrogen, phosphorus and ºBrix on the production of MSCT through a factorial design methodology and analysis of response surface. The objective was to propose a statistically significant probabilistic model for the alcoholic fermentation. In order to obtain less MSCT, the medium under fermentation needs to present low sugar concentration. It was observed that phosphorus and nitrogen, even with no significant individual effects, presented interactions with each other decreasing the production of MSCT, which improves alcohol quality.

Estudo das diferentes formas de fósforo nas águas da plataforma continental do Amazonas

Hydrological samples were collected on the continental shelf of the Amazon river to determine particulate organic and inorganic matter, dissolved organic phosphorus (DOP), phosphate, total particulate phosphorus (TPP), chlorophyll a, temperature, salinity, pH, water transparency, dissolved oxygen (DO) and saturation rate. The objective was to study the forms of DOP, phosphate and TPP. In the euphotic layer, the fluvial discharge from the Amazon river favored the distribution of phosphate, TPP and DOP. In the aphotic layer, the phosphate concentration increased due to the decomposition of DOP and TPP. This increase is due to the absence of photosynthetic processes.

Geoquímica de fósforo como indicadora da qualidade ambiental e dos processos estuarinos do Rio Jaguaribe - costa nordeste oriental brasileira

Phosphorus geochemistry as a proxy of environmental estuarine processes at the Jaguaribe River, Northeastern Brazil. Sedimentation of different phosphorus geochemical fractions can characterize the natural or anthropogenic processes dominant in the watershed. Selective chemical extraction of different phosphorus geochemical forms in estuarine sediments showed the predominance of inorganic over organic forms suggesting an increase in inorganic phosphorus input from anthropogenic sources. Local hydrochemistry favors the dominance of inorganic ferric and carbonatic phosphorus. Ongoing changes in the estuarine throphy, from mesothrophic to euthrophic, may decrease the immobilization of these forms, increasing dissolved phosphorus and favoring euthrophy. Detritic phosphorus suggests a fluvial origin of this fraction and acts as a tracer of river influence upon the estuary.

Espectroscopia Mössbauer na caracterização de compostos ferrosos em solos e sua relação com retenção de fósforo

The chemical role of iron-bearing compounds on the dynamics of phosphorus in selected Brazilian latosols was investigated. The iron oxides were characterized in an attempt to assess their main chemical-mineralogical properties influencing the ion sorption mechanisms in those pedosystems. It was found that increasing total iron contents tend to increase the phosphorus adsorption capacity in the selected soils. 110 K-Mössbauer data reveal that the dominant iron oxides are hematite and goethite. Particularly for the yellower soil samples some prominent doublets, more certainly due to superparamagnetic relaxation, may be assigned to corresponding fractions of relatively small-sized particles.

Determinação de fósforo biodisponível em rações de peixes utilizando extração assistida por ultra-som e espectrofotometria no visível

The aim of the present work was to develop and optimize a method for determination of bioavailable phosphorus in samples of feces and fish feed using ultrasound extraction and subsequent quantification by visible spectrophotometry. Using as extractor solution HNO3 0.50 mol L-1, the great conditions of extraction established were: sample mass - 100 mg, samples granulometry - < 60 µm, sonification time - five cycles of 40 s and ultrasound potency - 136 W. The proposed method was applied in studies of digestibility of this nutrient in different feeds used in diets of juvenile of Nile tilapia.

Estudo da especiação de arsênio inorgânico e determinação de arsênio total no monitoramento ambiental da qualidade de águas subterrâneas

This work reports an alternative, fast and robust method, for the determination of total As, As(III) and As(V) by HG-AAS without the use of prereductants. The method is based on the different rates of arsine formation of the inorganic As species and the effect of As(III) in the signal obtained for total As. Groundwater and mineral spiked waters were used to sample preservation evaluation. The method was validated by the determination of As in SRM 1640 and used in the determination of total As and its inorganic species in groundwater samples collected from mines in the Iron Quadrangle - MG.

Comparação entre um trocador aniônico de sal de amônio quaternário de quitosana e um trocador comercial na extração de fósforo disponível em solos

The present work aimed modify chemically the chitosan (QTS) surface to obtain a reticulate chitosan quaternary ammonium salt (SAQQR), and compare this anionic exchanger with an commercial ion exchanger in the extraction of available phosphorus in soils. The results showed that the two exchangers are identical, extracting similar and proportional quantities of available phosphorus in the studied soils, and the anionic exchanger of SAQQR provides a high chemical stability, not affected by the pH difference of soils.

Utilização de planejamento fatorial no preparo de amostras de detergente em pó para a determinação de fósforo por análise em fluxo

The decomposition of detergent powder samples in a microwave oven and autoclave was evaluated. To establish the best experimental conditions a 2(5) factorial design was performed, varying the conditions in autoclave and microwave digestion and flow system parameters for the determination of phosphorus. The best composition was: 0.2 mL sulfuric acid; 500 W power and a 2 min time interval; 6 mmol L-1 of ascorbic acid and 16 mmol L-1 of molybdate to flow system. This factor levels use less reagents than the reference method. No statistically significant differences were found between the autoclave and microwave oven responses at the 95% confidence level.

Aplicação de fósforo para imobilização química do cádmio em solo contaminado

The objective of the study was to evaluate the effect of phosphorus on the Cd availability to plants of a contaminated soil using 109Cd isotope and chemical extractants. The experiment was set in a randomized block design and the soil was labeled with 222 KBq of 109Cd per pot and received 5 rates of P as triple superphosphate, growing lettuce plants as test crop. The use of phosphorus reduced pH of soil which altered the Cd availability in DTPA and Mehlich extractants. The lettuce Cd content decreased but its accumulation and L value increased in all treatments compared to the control, demonstrating the inefficiency of phosphorus in reducing the Cd availability.