ABSTRACT Introduction: One of the most critical complications in myelodysplastic syndromes (MDS) is the progression to acute myeloid leukemia (AML). The dynamics of clonal evolution in MDS and how acquired mutations can be used as biomarkers to track disease progression remains under investigation. Objective and method: Herein, we investigated the frequency of common myeloid clonal mutations (FLT3, NPM1, JAK2, IDH1 and IDH2) in 88 patients with MDS and 35 AML patients with myelodysplasia-related changes, followed at a single reference center in northeastern Brazil. Results: Overall, 9/88 (10%) ofthe MDSpatients and 9/35 (26%) of the secondary AML patients had at least one mutation. While the JAK2 V617F mutation was the most frequent in the MDS patients, the FLT3, NPM1, IDH1 and IDH2 mutations were more frequently found in the secondary AML group. Furthermore, there was a higher frequency of FLT3, NPM1, IDH1 and IDH2 mutations in MDS patients classified as high-risk subtypes than in those of lower risk. Conclusion: Despite the limited sample size, our data suggest that mutations in FLT3, NPM1, IDH1 and IDH2 genes could be potential biomarkers to detect early disease progression in MDS.

Abstract Introduction: Sickle cell anemia (SCA) is a Mendelian disorder with a heterogeneous clinical course. The reasons for this phenotypic diversity are not entirely established, but it is known that high fetal hemoglobin levels lead to a milder course of the disease. Additionally, genetic variants in the intergenic region HBS1L-MYB promote high levels of fetal hemoglobin into adulthood. Objective: In the present study, we investigated the HMIP1 C-839A (rs9376092) polymorphism, located at the HBS1L-MYB intergenic region block 1, in SCA patients. Method: We analyzed 299 SCA patients followed in two reference centers in Brazil. The HMIP1 C-839A (rs9376092) genotypes were determined by allele specific polymerase chain reactions. Clinical and laboratory data were obtained from patient interviews and medical records. Results: The median fetal hemoglobin levels were higher in patients with the HMIP1 C-839A (rs9376092) AA genotype (CC = 6.4%, CA = 5.6% and AA = 8.6%), but this difference did not reach significance (p = 0.194). No association between HMIP1 C-839A (rs9376092) genotypes and other clinical and laboratorial features was detected (p > 0.05). Conclusion: In summary, our data could not support the previously related association between the HMIP1 C-893A (rs9376092) polymorphism and differential fetal hemoglobin levels.

A simple analytical procedure is proposed for the direct analysis of guarana-based beverages in order to determine nutrient elements by inductively coupled plasma optical emission spectrometry (ICP OES). A Box-Behnken design, combined with Derringer’s desirability function, was applied to the simultaneous optimization of the ICP OES radiofrequency (RF), sample volume and nitric acid concentration. Using this approach, optimal conditions were established as RF power of 1.40 kW, and 5.0 mL of sample diluted twice with 0.5 mol L-1 HNO3. The optimized procedure allowed the determination of Cu, Fe, Mn, Zn, K, Ca, S, P and Mg with limits of quantification of 10.0, 2.0, 0.6, 6.0, 66.0, 65.0, 235, 40.0 and 20.0 µg L-1, respectively. Accuracy of the method was evaluated through analysis of water standard reference material (SRM NIST 1643f) and by addition-recovery experiments, in which satisfactory recoveries were obtained. The procedure was applied for the analysis of guarana-based soft and energy drinks. The concentration ranges (mg L-1) were: 0.36-43.3 (Ca), 4.04-192 (K), 0.36-44.8 (Mg), 10.1-1,073 (S), 0.04-92.4 (P), < 0.010-0.0174 (Cu), < 0.002-0.294 (Fe), < 0.006-0.06 (Zn) and < 0.0006-0.168 (Mn).

The development of a method based on extraction induced by emulsion breaking (EIEB) aiming copper determination in gasohol using graphite furnace atomic absorption spectrometry (GF AAS) is reported. Emulsification of the gasohol samples was carried out using nitric acid solution, (1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol surfactant (Triton X-114), and ultrasound energy. The variables related to the extraction efficiency were optimized by multivariate approaches (two-level factorial fractional design and Doehlert design). The best results were obtained when the emulsion was formed with 5.0 mL of the sample, 0.200 mL of 2.4 mol L-1 HNO3, 0.100 mL of 10% Triton X-114 and 10 min of sonication. A fast and efficient emulsion breaking was performed at 90 ºC. A volume of 6.65 mL of the copper-rich hydroalcoholic phase was extracted, separated from the organic phase and analyzed. Under these conditions, the following analytical characteristics were obtained: 0.61 and 2.0 µg L-1 for limits of detection and quantification, respectively; precision (percentage of relative standard deviation, 10 µg L-1) of 2.8%; and analytical sensitivity of 0.011 L µg -1. Accuracy was assessed by spike tests, and values in the range of 95-110% were achieved. The method was applied in the determination of copper in Brazilian gasoline samples (gasohol with 27% ethanol).

An infection of the fungus Moniliophthora perniciosa in cocoa trees reduces productivity of the plant. In this study, the concentrations of mineral nutrients in healthy leaves and in leaves of vegetative broom of the cocoa plant were determined, and the relationship between the disease and the nutritional composition of the leaves was assessed. The samples were analyzed using the wet digestion method and the concentrations were determined by inductively coupled plasma optical emission spectrometry and the Kjeldahl method. Results indicate that leaves of vegetative broom have lower concentrations of Ca, Mg, S, Fe, Mn, and Ni than healthy leaves. Concentrations of P and Cu were lower in healthy leaves and higher in leaves of vegetative broom. In contrast, concentrations of K, N, and Zn were the same for both types of leaves. In short, plant-fungal interaction was reflected in the nutritional composition of the leaves, demonstrated by the differences in nutrient concentrations between healthy and infected leaf tissue.

Plant litter has several functions in a forest ecosystem. Studies about plant litter are of great importance to better understand and conserve ecological environments. The objective of this study was to investigate the concentration of metals (Fe, Co, Ca, Cu, Ni, Mg, Mn and Zn) in Caatinga plant litter in the southwest region of Bahia. Plant litter was collected in summer (January/2017) and winter (August/2017). Concentrations were determined by flame atomic absorption spectrometry (FAAS). The results were submitted to multivariate analysis, principal component analysis (PCA), and hierarchical cluster analysis (HCA). The average amount of plant litter found in January and August was 1190 and 1329 kg ha-1, respectively. The twigs fraction provided the largest amount of biomass to the plant litter since this deposition occurred in greater quantity in August, a period of drought. Metal concentrations (g kg-1) in the analyzed samples ranged from 1.39-257 (Fe), < limit of quantification (LOQ)-0.269 (Co), 0.0036-0.61 (Cu), 1.39-8.76 (Ca), 0.0022-0.56 (Ni), 0.137-1.52 (Mg), 0.033-1.91 (Mn) and 0.0022-0.8 (Zn). The multivariate analysis showed that the composition of plant litter is altered seasonally.

Cloud point extraction (CPE) in association with graphite furnace atomic absorption spectrometry (GF AAS) was proposed for preconcentration and quantification of trace amounts of copper and cadmium in samples of saline produced formation water from petroleum exploration. The procedure was based on the formation of hydrophobic complexes of the analytes with 1,5-diphenylthiocarbazone (dithizone) in a micellar media of the surfactant (1,1,3,3-tetramethyl butyl) phenyl-polyethylene glycol (Triton X-114). Constrained mixture design was performed for the optimization of the proportions of the three solutions employed in the CPE: Triton X-114, dithizone, and buffer solution. Under the recommended conditions, the CPE GF AAS procedure allowed to obtain enrichment factors of 18 and 11 times, limits of quantification of 0.030 and 0.12 µg L-1 and precision, expressed as relative standard deviation (RSD, n = 8, 2.0 µg L-1), of 1.1 and 4.3% for copper and cadmium, respectively. The CPE GF AAS method was applied to the determination of copper and cadmium in samples of saline produced formation water from petroleum exploration, and its accuracy was accessed by analyzing certified reference material CASS-5 (Nearshore Seawater Reference Material for Trace Metals) from National Research Council (Canada).

In the present paper, an automated online preconcentration system based on the use of two knotted reactors (KR) was developed for Mn determination in tea samples by flame atomic absorption spectrometry (F AAS). The system automation was performed by using four solenoid valves to switch sample streams and reagents. Valves were driven electronically by an integrated Darlington transistor circuit and controlled by an open-source Arduino hardware platform written in C language. The preconcentration was based on the precipitation process of metal ions complexed with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-PADAP) on the inner walls of the reactor, followed by elution with a solution of hydrochloric acid. The optimized system allowed the Mn determination with limit of detection (LOD) of 2.1 mg L-1, precision (relative standard deviation (RSD), 50.0 mg L-1) of 2.6% and enrichment factors of 8. The system presented a sampling frequency of 60 h-1. The method accuracy was evaluated by analysis of the certified reference material (CRM) apple leaves (NIST 1515) and by addition/recovery tests obtaining recoveries between 95.2 to 119%. This method was applied in the Mn determination in commercial tea samples purchased from local trade. Manganese levels were found in a concentration range of 2.95 to 123 µg g-1.

Abstract The Jequiezinho River is a temporary river. In the urban stretch it is impacted, with perennial flow coming from domestic sewage and rainwater. This study evaluated the geochemical distribution and potential mobility of some metals (Pb, Co, Ca, Cr, Mg, Cu, Fe, Mn, Ni and Zn) in sediments of the Jequiezinho River. Sediment samples were collected at ten different sites along the river. The silt/clay fraction was submitted to acid digestion and sequential extraction with analysis by FAAS. The results indicated that, in the more densely populated region, there was an increase in concentrations of Cr, Ni, Cu, Co, Pb, and Zn. The contents found were compared with the guideline values of TEL (Threshold Effect Levels) and PEL (Probable Effect Levels), not exceeding the maximum reference limits. The results indicated that Ca, Mg, Mn and Fe presented greater susceptibility to mobility and bioavailability suggesting the geochemical origin responsible for these high concentrations. The multivariate analysis showed that Cr, Ni, Cu, Co, Pb, and Zn presented a similar behavior, especially in locations with higher population density and the discharge of non-discriminated effluents, reflecting the anthropogenic contributions as responsible for the concentration increase.

In this study, it was developed a method for Ca, Mg, Mn, Fe and Zn determination in palm oil samples by flame atomic absorption spectrometry (FAAS) after ultrasound-assisted emulsification and extraction induced by emulsion breaking (EIEB). Optimization of the method was carried out by a constrained mixture design. The developed method has presented limits of detection (LOD) between 0.012 and 0.057 mg L-1, limits of quantification (LOQ) between 0.039 and 0.19 mg L-1 and precision was expressed as repeatability (%RSD, n = 10) between 1.8 and 3.2% for the five studied metals. Method accuracy was assessed by the application of recovery tests (87 to 113%) and by comparison of concentration values with the dry ashing method, showing good agreement with the standard method. The developed methodology allows operational simplicity, multi-sample treatment, and low cost when compared with some methods based on decomposition. It was applied in palm oil samples collected in the Bahia State (Brazil). The concentrations (in mg L-1) found in the samples were: 3.93-13.9 Ca, 0.37-2.26 Mg, > LOQ-0.32 Mn, 1.77-8.57 Fe and 0.38-2.54 Zn.

In this work, it was developed an alternative analytical strategy for the preparation of vegetal samples extracted with diluted acids and assisted by ultrasound and microwave radiation for the determination of nutrients elements by fast sequential flame atomic absorption spectrometer. The conditions optimized using univariate and multivariate methodologies for the procedure were as follows: 200 mg of sample; extraction solution comprising a mixture of 6.3 mL HNO3, 2.1 mL HCl, and 1.7 mL CH3COOH; extractor with a final concentration of 2.5 mol L-1; a sonication time of 30 min; and a microwave radiation time of 6 s. The accuracy of the procedure was confirmed by analyzing the certified reference material NIST 1515 (apple leaves) and by comparison with the results obtained through microwave-assisted total digestion method. The procedure was applied to determine Ca, Mg, Cu, Mn, Fe, and Zn in several cassava peel samples used in animal nutrition, and proved to be simple, reliable, fast, easy to implement, and inexpensive.

ABSTRACT A method was developed for determination of total antimony in hair samples from patients undergoing chemotherapy against Leishmaniasis based on the administration of pentavalent antimonial drugs. The method is based on microwave assisted digestion of the samples in a pressurized system, reduction of Sb5+ to Sb3+ with KI solution (10% w/v) in ascorbic acid (2%, w/v) and its subsequent determination by hydride generation atomic fluorescence spectrometry (HG-AFS). The proportions of each component (HCl, HNO3 and water) used in the digestion were studied applying a constrained mixtures design. The optimal proportions found were 50% water, 25% HNO3 and 25% HCl. Variables involved in the generation of antimony hydride were optimized using a Doehlert design revealing that good sensitivity is found when using 2.0% w/v NaBH4 and 4.4 mol L-1 HCl. Under the optimum experimental conditions, the method allows the determination of antimony in hair samples with detection and quantification limits of 1.4 and 4.6 ng g-1, respectively, and precision expressed as relative standard deviation (RSD) of 2.8% (n = 10 to 10.0 mg L-1). The developed method was applied in the analysis of hair samples from patients who take medication against Leishmaniasis.

Um simplex de algoritmo modificado foi utilizado na otimização de um sistema de pré-concentração para determinação de cádmio em amostras de sedimentos, cigarros e alimentos por espectrometria de absorção atômica com chama. O sistema de pré-concentração baseia-se na sorção do cádmio em uma minicoluna recheada com uma resina de Amberlite XAD-2 funcionalizada com o ácido 3,4-dihidrixibenzóico (DHB). As variáveis otimizadas foram pH e vazão da amostragem. As condições ótimas encontradas para estas variáveis foram, respectivamente: 8,7 e 8,8 mL min-1. O sistema desenvolvido apresentou fator de pré-concentração de 15,3 vezes, limite de detecção de 0,49 µg L-1, limite de quantificação de 1,65 µg L-1 e precisão expressa pelo desvio padrão relativo (%RSD, n=10) de 5,9. A exatidão do método foi determinada através da aplicação do sistema desenvolvido em material de referência certificado de sedimento de estuário (NIST 1646-1). As concentrações de cádmio encontradas nas amostras de sedimentos variaram entre 1,73 e 1,90 µg g-1. Nas amostras de cigarros os resultados obtidos foram 0,085 e 0,193 µg g-1, e nas amostras de alimentos (coentro e alface) as concentrações encontradas deste metal foram, respectivamente, 0,33 e 0,12 µg g-1.

A modified simplex algorithm was used to optimize a system of preconcentration for cadmium determination in samples of sediments, cigarettes and food using flame atomic absorption spectrometry. The preconcentration system is based on the sorption of cadmium in a minicolumn packed with Amberlite XAD-2 resin functionalized with 3,4-dihydroxybenzoic acid (DHB). The optimized variables were pH and sampling flow rate and the optimum conditions found for these variables were, respectively 8.7 and 8.8 mL min-1. The developed system showed a preconcentration factor of 15.3, detection limit of 0.49 µg L-1, quantification limit of 1.65 µg L-1 and precision expressed as relative standard deviation (% RSD, n=10) of 5.9. The accuracy of the method was checked by analysis of estuary sediment certified reference material (NIST 1646-1). The cadmium concentrations found in sediment samples ranged from 1.73 and 1.90 µg g-1. In cigarette samples the results were 0.085 and 0.193 µg g-1, and in food samples (coriander and lettuce) the concentrations found of this metal were, respectively, 0.33 and 0.12 µg g-1.

A simultaneous preconcentration method for cadmium, copper and nickel in samples of sediments and determination by inductively coupled plasma optical emission spectrometry was developed. The method is based on the extraction of the metals as complexes formed with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol (5-Br-PADAP) at cloud point of the nonionic surfactant polyethylene glycol tert-octylphenyl ether (triton X-114). Optimization was performed using a Doehlert design and constrained mixture design. Desirability function was used to provide a simultaneous optimization of the evaluated responses. The developed method presented limits of quantification of 0.066, 0.149 and 0.191 µg g-1 and an enrichment factor of 18.4, 16.8 and 18.2 fold for cadmium, copper and nickel, respectively. The proposed method was applied in sediment samples collected in the urban stretch of the Contas River (Jequié, BA, Brazil). Adequate accuracy was found by analysis of two certified reference materials (NIST 1646a estuarine sediments and NIST 2702 marine sediment).

Este trabalho propõe o uso de degradação por foto-oxidação com radiação ultravioleta e H2O2 como técnica de tratamento de amostras para a determinação de Fe, Zn, Mn, Ni e Co a partir de chorume de aterro sanitário municipal usando espectrometria de absorção atômica com chama (FAAS). Três variáveis (pH, tempo de irradiação e concentração de tampão) foram otimizadas usando planejamento Doehlert e as proporções dos componentes da mistura submetida à irradiação ultravioleta (chorume, solução tampão e H2O2 30% v/v) foram otimizadas usando-se um planejamento de misturas com restrições. Usando as condições experimentais estabelecidas, este procedimento forneceu limites de detecção de 0,075; 0,025; 0,010; 0,075 e 0,041 µg mL-1, e os níveis de precisão, expressos como desvio padrão relativo (%RSD, 0,5 µg mL-1) foram 3,6; 1,8; 1,3; 3,3 e 1,7% pra Fe, Mn, Zn, Ni e Co respectivamente. Testes de recuperação foram realizados para avaliação da exatidão do procedimento e as recuperações encontradas estavam entre 92 e 106% para os metais estudados. Este procedimento foi aplicado nas amostras de chorume coletadas no município de Jequié, região sudoeste da Bahia, Brasil. Os resultados foram comparados com aqueles obtidos pelo procedimento de digestão em meio ácido. Não houve diferenças significativas entre os resultados obtidos nos dois métodos com base no teste t-pareado a um nível de confiança de 95%.

This work proposes the use of photo-oxidation degradation with UV radiation/H2O2 as sample treatment for the determination of Fe, Zn, Mn, Ni and Co in municipal solid waste landfill leachate by flame atomic absorption spectrometry (FAAS). Three variables (pH, irradiation time and buffer concentration) were optimized using Doehlert design and the proportions of mixture components submitted to UV radiation (leachate sample, buffer solution and H2O2 30%, v/v) were optimized using a constrained mixture design. Using the experimental conditions established, this procedure allows limits of detection of 0.075, 0.025, 0.010, 0.075 and 0.041 µg mL-1, and the precision levels expressed as relative standard (%RSD, 0.5 µg mL-1) were 3.6, 1.8, 1.3, 3.3 and 1.7%, for Fe, Mn, Zn, Ni and Co respectively. Recovery tests were carried out for evaluation of the procedure accuracy and recoveries were between 92 and 106% for the studied metals. This procedure has been applied for the analysis of the landfill leachate collected in Jequié, a city of the southwestern region of the State of Bahia, Brazil. The results were compared with those obtained by acid digestion. There was no significant difference between the results obtained by the two methods based on paired t-test at 95% confidence level.