A bench arc-furnace facility for fullerene and single-wall nanotubes synthesis

A metallic-sample arc-furnace was modified to synthesize fullerenes and nanotubes. The (reversible) changes and the process for producing single-wall nanotubes (SWNTs) are described.

Determination of Cd and Pb in fuel ethanol by filter furnace electrothermal atomic absorption spectrometry

A method was developed for quantification of Cd and Pb in ethanol fuel by filter furnace atomic absorption spectrometry. Filter furnace was used to eliminate the need for chemical modification, to stabilize volatile analytes and to allow the application of short pyrolysis step. The determinations in samples were carried out against calibration solutions prepared in ethanol. Recovery tests were made in seven commercial ethanol fuel samples with values between 90 and 120%. Limits of detection were 0.1 µg L-1 for Cd and 0.3 µg L-1 for Pb. Certified water samples (APS 1071, APS 1033, NIST 1643d, NIST 1640) were also used to evaluate accuracy and recoveries from 86.8% to115% were obtained.

RAPID AND SENSITIVE DETERMINATION OF PALLADIUM USING HOMOGENEOUS LIQUID-LIQUID MICROEXTRACTION VIA FLOTATION ASSISTANCE FOLLOWED BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

A method for the determination of trace amounts of palladium was developed using homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA) followed by graphite furnace atomic absorption spectrometry (GFAAS). Ammonium pyrrolidine dithiocarbamate (APDC) was used as a complexing agent. This was applied to determine palladium in three types of water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added to the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting extraction efficiency were investigated and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0-200 µg L-1 with a limit of detection of 0.3 µg L-1. The performance of the method was evaluated for the extraction and determination of palladium in water samples and satisfactory results were obtained. In order to verify the accuracy of the approach, the standard addition method was applied for the determination of palladium in spiked synthetic samples and satisfactory results were obtained.

Optimization and validation of a methodology to determine total arsenic, As(III) and As(V), in water samples, through graphite furnace atomic absorption spectrometry

The Graphite furnace atomic absorption spectrometry (GF AAS) was the technique chosen by the inorganic contamination laboratory (INCQ/ FIOCRUZ) to be validated and applied in routine analysis for arsenic detection and quantification. The selectivity, linearity, sensibility, detection, and quantification limits besides accuracy and precision parameters were studied and optimized under Stabilized Temperature Platform Furnace (STPF) conditions. The limit of detection obtained was 0.13 µg.L-1 and the limit of quantification was 1.04 µg.L-1, with an average precision, for total arsenic, less than 15% and an accuracy of 96%. To quantify the chemical species As(III) and As(V), an ion-exchange resin (Dowex 1X8, Cl- form) was used and the physical-chemical parameters were optimized resulting in a recuperation of 98% of As(III) and of 90% of As(V). The method was applied to groundwater, mineral water, and hemodialysis purified water samples. All results obtained were lower than the maximum limit values established by the legal Brazilian regulations, in effect, 50, 10, and 5 µg.L-1 para As total, As(III) e As(V), respectively. All results were statistically evaluated.

Association of dental enamel lead levels with risk factors for environmental exposure

OBJECTIVE: To analyze household risk factors associated with high lead levels in surface dental enamel. METHODS: A cross-sectional study was conducted with 160 Brazilian adolescents aged 14-18 years living in poor neighborhoods in the city of Bauru, southeastern Brazil, from August to December 2008. Body lead concentrations were assessed in surface dental enamel acid-etch microbiopsies. Dental enamel lead levels were measured by graphite furnace atomic absorption spectrometry and phosphorus levels were measured by inductively coupled plasma optical emission spectrometry. The parents answered a questionnaire about their children's potential early (05 years old) exposure to well-known lead sources. Logistic regression was used to identify associations between dental enamel lead levels and each environmental risk factor studied. Social and familial covariables were included in the models. RESULTS: The results suggest that the adolescents studied were exposed to lead sources during their first years of life. Risk factors associated with high dental enamel lead levels were living in or close to a contaminated area (OR = 4.49; 95% CI: 1.69;11.97); and member of the household worked in the manufacturing of paints, paint pigments, ceramics or batteries (OR = 3.43; 95% CI: 1.31;9.00). Home-based use of lead-glazed ceramics, low-quality pirated toys, anticorrosive paint on gates and/or sale of used car batteries (OR = 1.31; 95% CI: 0.56;3.03) and smoking (OR = 1.66; 95% CI: 0.52;5.28) were not found to be associated with high dental enamel lead levels. CONCLUSIONS: Surface dental enamel can be used as a marker of past environmental exposure to lead and lead concentrations detected are associated to well-known sources of lead contamination.

Chronic hepatitis C: hepatic iron content does not correlate with response to antiviral therapy

The complex interaction between hepatitis C virus infection, iron homeostasis and the response to antiviral treatment remains controversial. The aim of this study was to evaluate the influence of hepatic iron concentration (HIC) on the sustained virological response (SVR) to antiviral therapy in patients with chronic hepatitis C. A total of 50 patients who underwent pretreatment liver biopsy with assessment of HIC by graphite furnace atomic absorption spectroscopy and were subsequently submitted to antiviral treatment with interferon/peginterferon and ribavirin were included in the study. Patients with alcoholism, history of multiple blood transfusion, chronic kidney disease, hemolytic anemia and parenteral iron therapy were excluded. The iron related markers and HIC were compared between those who achieved an SVR and non-responders (NR) patients. The mean age was 45.7 years and the proportion of patients' gender was not different between SVR and NR patients. The median serum iron was 138 and 134 µg/dL (p = 0.9), the median serum ferritin was 152.5 and 179.5 ng/mL (p = 0.87) and the median HIC was 9.9 and 8.2 µmol/g dry tissue (p = 0.51), for SVR and NR patients, respectively. Thus, hepatic iron concentration, determined by a reliable quantitative method, was not a negative predictive factor of SVR in patients with chronic hepatitis C presenting mild to moderate hepatic iron accumulation.

Potenciais efeitos das mudanças climáticas futuras sobre a distribuiçãode um anuro da Caatinga Rhinella granulosa (Anura, Bufonidae)

Neste estudo, usamos dois tipos de modelagem de distribuição de espécies (correlativo e mecanístico), com o objetivo de avaliar o efeito das mudanças climáticas sob a distribuição geográfica de Rhinella granulosa (Spix, 1824), espécie inserida principalmente no bioma Caatinga. Avaliamos a predição, levantada por outros autores, de que espécies de anfíbios distribuídos em climas quentes terão suas distribuições espaciais restringidas por aumento da temperatura considerando cenários futuros. Na abordagem correlativa, os resultados mostraram que as distribuições espaciais geradas pelo modelo de distância Euclidiana foram mais conservativas, ou seja, as áreas que apresentaram menor distância do nicho ótimo se restringiram às áreas de distribuição real da espécie (Caatinga) e às pequenas regiões que abrangem o bioma Cerrado. A abordagem mecanística apresentou resultados menos conservativos, onde o habitat indicado como adequado para R. granulosa está contido em grande parte da América do Sul, formando uma extensa área contínua. No geral, verificou-se que R. granulosa não sofrerá forte influência climática sobre sua distribuição geográfica no futuro, pelo menos até 2080, provavelmente por apresentar uma fisiologia extremamente tolerante às altas temperaturas e por possuir adaptações para suportar clima quente e seco.

Influence of digestion methods on the recovery of Iron, Zinc, Nickel, Chromium, Cadmium and Lead contents in 11 organic residues

There are currently many devices and techniques to quantify trace elements (TEs) in various matrices, but their efficacy is dependent on the digestion methods (DMs) employed in the opening of such matrices which, although "organic", present inorganic components which are difficult to solubilize. This study was carried out to evaluate the recovery of Fe, Zn, Cr, Ni, Cd and Pb contents in samples of composts and cattle, horse, chicken, quail, and swine manures, as well as in sewage sludges and peat. The DMs employed were acid digestion in microwaves with HNO3 (EPA 3051A); nitric-perchloric digestion with HNO3 + HClO4 in a digestion block (NP); dry ashing in a muffle furnace and solubilization of residual ash in nitric acid (MDA); digestion by using aqua regia solution (HCl:HNO3) in the digestion block (AR); and acid digestion with HCl and HNO3 + H2O2 (EPA 3050). The dry ashing method led to the greatest recovery of Cd in organic residues, but the EPA 3050 protocol can be an alternative method for the same purpose. The dry ashing should not be employed to determine the concentration of Cr, Fe, Ni, Pb and Zn in the residues. Higher Cr and Fe contents are recovered when NP and EPA 3050 are employed in the opening of organic matrices. For most of the residues analyzed, AR is the most effective method for recovering Ni. Microwave-assisted digestion methods (EPA3051 and 3050) led to the highest recovery of Pb. The choice of the DM that provides maximum recovery of Zn depends on the organic residue and trace element analyzed.

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.

Mapeamento da temperatura da superfície terrestre com uso do sensor AVHRR/NOAA

O objetivo deste trabalho foi avaliar a adequação do uso do sensor AVHRR/NOAA (Advanced Very High Resolution Radiometer/National Oceanic and Atmospheric Administration) para mapeamento da temperatura da superfície terrestre (TST) no Estado do Rio Grande do Sul, por meio da comparação entre três algoritmos clássicos. Foram comparados os métodos de Becker & Li, Sobrino et al. e Kerr et al. para estimativa das TST mínimas, utilizando imagens noturnas e logo após o amanhecer. Os dados de emissividade e TST foram obtidos por meio de combinações matemáticas da radiação detectada nas faixas do visível, infravermelho próximo e termal do sensor AVHRR/NOAA. O sensor AVHRR é adequado para o mapeamento de TST para as condições do tipo de cobertura do solo que predominam no Rio Grande do Sul, visto que a TST estimada pelos três métodos testados foi próxima à temperatura do ar medida nos locais selecionados. O método de Sobrino et al. foi o mais adequado.

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.

Sistema automático para análise direta de ligas metálicas por eletrodissolução anódica e espectrometria de absorção atômica

An automatic system for the direct determination of lead and tin by atomic absorption spectrometry is described. The on-line treatment of the metallic samples was obtained by anodic electrodissolution in a flow injection system. Lead was determined by flame atomic absorption spectrometry (FAAS) and tin by graphite furnace atomic absorption spectrometry (GFAAS). A computer program managed the current source and the solenoid valves that direct the fluids. Good linear correlations between absorbance and current intensity for lead and tin were observed. Results were in agreement with the certified values. Precision was always better than 5%. The recommended procedure allows the direct determination of 60 or 30 elements/h using FAAS or GFAAS, respectively.

Determinação direta de crômio em açúcar e leite por espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

A fast and direct method for the determination of Cr in milk and cane sugar suspensions using graphite furnace atomic absorption spectrometry with Zeeman-effect background correction is described. No sample pre-treatment was necessary, minimizing the risk of contamination. The concentration of chromium in cane sugar was evaluated using Cr reference solutions prepared in 1% v/v HNO3 solution. The milk samples were introduced into the furnace with a mixture of amines for avoiding the autosampler blockage and foaming of milk. Chromium determination in milk was based on the standard additions method (SAM). The limit of detection and characteristic mass for cane sugar sample (30 muL) were 0,13 ng/ml and 4,3 pg, and for milk sample (10 muL) were 0,23 ng/ml and 7,8 pg, respectively. The graphite tube lifetime was 300 firings for sugar-cane sample and 100 firings for milk sample. The heating program was implemented in 68 s.

Determinação direta de selênio em água de coco e em leite de coco utilizando espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

Selenium is both essential and toxic to man and animals, depending on the concentration and the ingested form. Most fruits and vegetables are poor sources of selenium, but coconut can be a good selenium source. Samples were suspended (1 + 4 v/v) in a mixture of tertiary amines soluble in water (10% v/v CFA-C). This simple sample treatment avoided contamination and decreased the analysis time. The standard additions method was adopted for quantification. The action of the autosampler was improved by the presence of the amines mixture in the suspension. A Varian model AA-800 atomic absorption spectrometer equipped with a graphite furnace and a GTA 100 autosampler was used for selenium determination in coconut water and coconut milk. Background correction was performed by means of the Zeeman effect. Pyrolytically coated graphite tubes were employed. Using Pd as chemical modifier, the pyrolysis and the atomization temperatures were set at 1400 and 2200ºC, respectively. For six samples, the selenium concentration in coconut water varied from 6.5 to 21.0 mug L-1 and in coconut milk from 24.2 to 25.1 mug L-1. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values are in the 99.5-102.3% range. The main advantage of the proposed method is that it can be directly applied without sample decomposition.

Avaliacão de programas de aquecimento para espectrometria de absorção atômica com atomizacão eletrotérmica em filamento de tungstênio

A tungsten coil atomizer was used to investigate the effect of heating programs with constant or variable drying temperatures on the atomization of Al, Cd, Cr and Pb. The variation of the surface temperature in the tungsten coil furnace can occur during each heating step due to the design of the power supply, that may apply constant voltages during a programmed time. For volatile elements (Cd), losses in sensitivity were observed when the program with a variable temperature was used. On the other hand, these effects are negligible for less volatile elements (Al and Cr) and any tested program, in different acidic media, could be used without appreciable changes in sensitivities. The results allow the establishment of proper heating programs for elements with different thermochemical behavior in the tungsten coil atomizer.