Determination and multivariate evaluation of the mineral composition of red jambo (Syzygium malaccense (L.)).

This work aimed to evaluate the mineral composition of twelve samples of red jambo (Syzygium malaccensis) collected in 10 cities in the state of Bahia. The samples were digested in a digester block with a reflux system and cold finger, and the analytes were determined by optical emission spectrometry with inductively coupled plasma. The accuracy of the method was confirmed by analyzing NIST 1570a certified reference material (spinach leaves) at a 95% confidence level. The results were evaluated through Principal Component Analysis and Hierarchical Cluster Analysis, which allowed the identification of outliers in the results of the city of Jaguaquara. The analyte concentrations in the samples (mg 100 g -1) comprised a range of: Ca (3.0-28.9), Fe (0.035-0.125), K (134.8-197.5), Mg (2.7-19.8), Mn (0.012-0.131), Na (0.5-10.8), P (0.24-13.5), Sr (0.010-0.314), and Zn (0.026-0.129). This demonstrates that the fruit can be indicated as a potential nutritional supplement in human nutrition.

Doehlert design in the optimization of procedures aiming food analysis - A review.

In the present paper is presented a review on the application of Doehlert design in the optimization of some of the steps of analytical procedures aimed the analysis of food samples. The theoretical principles and the main characteristics of this type of design are described. In addition, the main advantages and limitations of Doehlert design over other designs (Central Composite Design and Box-Behnken) and its application in the area of food analysis are discussed. Finally, to illustrate its potential, some examples of Doehlert design application in other areas of food chemistry without the purpose of analytical determination will be briefly presented.

Assessment of toxicity of metals in river sediments for human supply: Distribution, evaluation of pollution and sources identification.

Ten surface sediments collected from Joanes River, Bahia, Brazil in rainy and drought periods in 2019 were evaluated according to the enrichment factor (EF), potential ecological risk index (RI), potential contamination index (PCI), pollution load index (PLI), and index of geoaccumulation (Igeo). Initially the dry sediment was subjected to granulometric analysis and determination of the concentration of organic matter. Then, the samples were digested in HNO3 and analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) to determine the metals cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb) and zinc (Zn). Zn and Cu were classified in that order as the most contaminated elements in most sediment. Comparison of the total metal concentrations with the threshold (TELs) and probable (PELs) effect levels in sediment quality guidelines suggested a more worrisome situation for Zn (648.83-1415.90 µg g-1; PELZn = 315 µg g-1), of which concentrations were occasionally associated with adverse biological effects in four sediments, followed by Cu in five sediments during dry and rainy periods; while adverse effects were rarely associated with Cd, Cr, Ni, and Pb. In another evaluation, Cd, Cu, Cr, and Zn could be considered the most dangerous in the entire river, as they were classified in the high levels of contamination by the PCI, associated with serious adverse effects in most samples. In an assessment regarding the ecological risks in the study environment, the sediment samples remained below the limit established by the risk index (IR). The Zn presented moderately severe enrichment (6.78-11.83) in all the collection stations in the dry and rainy periods, followed by the Cd that presented moderate enrichment (2.23-4.17), whose values exceeded almost 1000 times the background at one site. Through the PCA it was possible to evidence the existing correlation between metals, organic matter, and silt and clay fraction. The results obtained in the PCA represented more than 80% of the variance between the data. The environmental risk assessment revealed a significant increase in the risk associated with metals during the rainy season. This is probably due to the greater supply of organic matter from the leaching of the margins.

Evaluation of the bioavailability of potentially toxic metals in surface sediments collected from a tropical river near an urban area.

The objective of this study was to evaluate the bioavailability of the metals cadmium, copper, lead, nickel, and zinc from sediment samples collected in the Paraguaçu river between the cities of Cachoeira and São Félix in the state of Bahia in Brazil. The method used was the acid extraction of volatile sulfides and metals extracted simultaneously (AVS-SEM) as described in the literature. For the extraction of sulfide, an argon drag system was used after acidification of the samples with HCl, releasing the volatile sulfides collected in the basic solution. Its determination was made by molecular absorption spectrophotometry using the methylene blue method. For quantification of the metals, the sediment with acid was filtered and the residual solution was analyzed by inductively coupled plasma mass spectrometry (ICP MS) in which the elements that were associated with the sulfide were released in solution. The bioavailability evaluation was done by the relation between the sum of the concentrations of the metals in solution (SEM) and the concentration of sulfide in each sample (AVS). When the ∑SEM/AVS ratio is >1, the medium is considered contaminated by the high bioavailability of the metals to other environmental compartments. In the samples collected in the Paraguaçu river in two campaigns, with an ∑SEM/AVS ratio of 0.007 to 1.082, the last value being the only critical>1, while the other quantities in the metallic phase were not available for a biota. By comparing the metal concentration data with the internationally established tolerance limits, all the values found were below the critical values, presenting no toxic risks to the surrounding ecosystem.

Simultaneous optimization of multiple responses and its application in Analytical Chemistry - A review.

This manuscript covers the application of the main techniques for simultaneous optimization of multiple responses generated by the application of multivariate designs (two-factor factorial, Central Composite, Doehlert, etc.) or by chromatographic runs in the development of analytical methods. Special attention will be given to the graphical method, desirability function, multiple response function and chromatographic response functions, since they are more frequently used in the analytical area. The advantages, disadvantages, limitations, and potentialities of these methods will also be addressed, as well as some of their applications, commenting on real examples from the literature. Some less usual methods in multiple response optimization in Analytical Chemistry will also be commented.

Mineral content in mustard leaves according to the cooking method.

This work evaluated the influence of the cooking methods (cooked in a water bath, in a stove, and in a microwave oven) on the mineral composition of mustard leaves (Sinapis alba). So, raw and cooked samples were digested and afterward the elements calcium, magnesium, potassium, sodium, iron, zinc, phosphor, barium and sulfur were determined using inductively coupled plasma optical emission spectrometry (ICP OES). The experimental work involved a set of five samples from different locations, processed in triplicates. The results were evaluated employing Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA) and Linear Discriminate Analysis (LDA). All techniques showed that the mineral content of the raw and cooked samples in a water bath is different from the samples cooked in stove and microwave oven. Especially for potassium, whose content is strictly controlled for chronic renal patients, this study showed that cooking using microwave oven has the greatest efficiency for reduction.

Speciation analysis of inorganic antimony in sediment samples from São Paulo Estuary, Bahia State, Brazil.

This paper proposes an extraction procedure for the speciation analysis of inorganic antimony in sediment samples using slurry sampling and hydride generation atomic absorption spectrometry. The optimization step of extraction of the species was performed employing a full two-level factorial design (2(3)) and a Box-Behnken matrix where the studied factors in both experiments were: extraction temperature, ultrasonic radiation time, and hydrochloric acid concentration. Using the optimized conditions, antimony species can be extracted in closed system using a 6.0 M hydrochloric acid solution at temperature of 70 °C and an ultrasonic radiation time of 20 min. The determination of antimony is performed in presence of 2.0 M hydrochloric acid solution using HG AAS by external calibration technique with limits of detection and quantification of 5.6 and 19.0 ng L(-1) and a precision expressed as relative standard deviation of 5.6 % for an antimony solution with concentration of 6.0 µg L(-1). The accuracy of the method was confirmed by analysis of two certified reference materials of sediments. For a sample mass of sediment of 0.20 g, the limits of detection and quantification obtained were 0.70 and 2.34 ng g(-1), respectively. During speciation analysis, antimony(III) is determined in presence of citrate, while total antimony is quantified after reduction of antimony(V) to antimony(III) using potassium iodide and ascorbic acid. The method was applied for analysis of six sediment samples collected in São Paulo Estuary (Bahia State, Brazil). The antimony contents obtained varied from 45.3 to 89.1 ng g(-1) for total antimony and of 17.7 to 31.4 ng g(-1) for antimony(III). These values are agreeing with other data reported by the literature for this element in uncontaminated sediment samples.

Determination of the mineral composition of Caigua (Cyclanthera pedata) and evaluation using multivariate analysis.

Caigua (in Brazil "maxixe do reino") is a fruit that is generally consumed either cooked or even raw as salad. This fruit has been used as a food and also in folk medicine. In this work, the mineral composition of Caigua was determined for the first time. Twenty-nine samples from five farms located in the southwestern region of Bahia, Brazil were acquired and analyzed using inductively coupled plasma optical emission spectrometry. The elements determined in this fruit included calcium, magnesium, sodium, potassium, phosphorus, manganese, iron, zinc, copper and vanadium. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to evaluate the obtained results. The average concentrations of the determined elements (expressed as mg 100 g(-1)) were as follows: 0.91 for sodium, 152 for potassium, 19.4 for phosphorus, 11.9 for calcium, 8.4 for magnesium, 0.074 for manganese, 0.21 for iron, 0.013 for copper, 0.13 for zinc and 0.015 for vanadium.

Synthesis of a new solid-phase extractor and its application to preconcentration and determination of lead in water samples.

A procedure for preconcentration and determination of lead in water is described. The method is based on the sorption of Pb(II) in a minicolumn packed with a functionalized sorbent and subsequent elution with acidic solution. The determination of lead content in the eluate was carried out using flame atomic absorption spectrometry. The sorbent was prepared by immobilization of the ligand 4-(5'-bromo-2'-thiazolylazo)orcinol on polystyrene-divinylbenzene through an azo spacer. Diazotization and coupling reactions were used for synthesis of the sorbent. Some variables affecting the preconcentration were optimized using a full factorial design. Under optimized conditions, the method presented a detection limit of 0.5 microg/L and enrichment factor of 36 for a sample volume of 25 mL. The accuracy of the method was tested by the determination of lead in a standard reference material (National Institute of Standards and Technology 1643d Fresh Water). The proposed procedure was applied to the determination of lead in samples of natural and drinking waters.

Application of pyridylazo and thiazolylazo reagents in flow injection preconcentration systems for determination of metals.

Pyridylazo and thiazolylazo reagents are synthetic dyes widely used in analytical chemistry. These reagents are also very attractive for use in preconcentration systems. This paper covers the application of pyridylazo and thiazolylazo reagents in flow injection systems for the determination of metals. The article discusses flow injection preconcentration systems with solid-phase extraction, precipitation and cloud point extraction. The use of pyridylazo and thiazolylazo reagents in flow injection detection systems is also presented. The relative advantages and drawbacks of these systems are discussed. The application of pyridylazo and thiazolylazo reagents in new systems is presented in the concluding part of this review article.

Multivariate optimization of a solid phase microextraction-headspace procedure for the determination of benzene, toluene, ethylbenzene and xylenes in effluent samples from a waste treatment plant.

A method based on solid-phase microextraction (SPME) and gas chromatography with flame ionization detection (GC-FID) has been optimized for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in water released from a waste treatment plant. The extraction step was optimized using fractional factorial and central composite designs including the following experimental factors: saline concentration; extraction time; desorption time; agitation velocity; headspace volume. A multiple function was used to describe the experimental conditions for simultaneous extraction of the compounds. The procedure, based on direct SPME at 50 degrees C, using a polydimethylsiloxane fiber, showed good linearity (r>0.997 over a concentration range 2-200 microg L(-1)) and repeatability (relative standard deviation (RSD)<4.23%) for all compounds, with limits of detection ranging from 0.05 to 0.28 microg L(-1), and limits of quantification ranging from 0.14 to 0.84 microg L(-1). Concentrations of the target compounds in these samples were between 145.8 and 1891 microg L(-1).

Optimization of microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry.

The present paper describes the development of a microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry (FAAS). The optimization step was performed using a full factorial design (2(3)) involving the factors: composition of the acid mixture (CMA), microwave power (MP) and radiation time (RT). The experiments of this factorial were carried out using a certified reference material of tea GBW 07605 furnished by National Research Centre for Certified Reference Materials, China, being the metal recoveries considered as response. The relative standard deviations of the method were found below 8% for the three elements. The procedure proposed was used for the determination of copper, zinc and nickel in several samples of tea from Turkey. For 10 tea samples analyzed, the concentration achieved for copper, zinc and nickel varied at 6.4-13.1, 7.0-16.5 and 3.1-5.7 (microg g(-1)), respectively.

Statistical designs and response surface techniques for the optimization of chromatographic systems.

This paper describes fundamentals and applications of multivariate statistical techniques for the optimization of chromatographic systems. The surface response methodologies: central composite design, Doehlert matrix and Box-Behnken design are discussed and applications of these techniques for optimization of sample preparation steps (extractions) and determination of experimental conditions for chromatographic separations are presented. The use of mixture design for optimization of mobile phases is also related. An optimization example involving a real separation process is exhaustively described. A discussion about model validation is presented. Some applications of other multivariate techniques for optimization of chromatographic methods are also summarized.

Atomic spectrometric methods for the determination of metals and metalloids in automotive fuels--a review.

Gasoline, diesel, ethanol and more recently also biodiesel are the four types of fuel used for automobile, truck and other transportation vehicle. The presence of metallic and metalloid species in automotive fuels is undesirable, except in the form of additives in order to improve specific characteristics of the fuel. Metallic or metalloid elements may derive from the raw product, such as nickel and vanadium in petroleum-based fuel or phosphorus in biodiesel, or they may be introduced during production and storage, such as copper, iron, nickel and zinc in case of petroleum-based fuel and alcohol or sodium and potassium in the case of biodiesel. The most famous additive to fuel is undoubtedly lead, the use of which has been banned or drastically reduced now in many countries of the world. The problems related to the trace element content may be economic, such as fuel degradation and poisoning of automotive catalysts, and/or environmental, such as the emission of metal compounds to the atmosphere. The analytical methods that have been developed for metal and metalloid quantification in automotive fuel are reviewed in this article. The main atomic spectrometric techniques used for trace metal and metalloid determination in fuels, particularly atomic absorption spectrometry with flames, graphite furnaces and with chemical vapor generation, and inductively coupled plasma coupled with optical emission and mass spectrometry are presented, including the different sample preparation procedures proposed for these techniques.

Multivariate technique for optimization of digestion procedure by focussed microwave system for determination of Mn, Zn and Fe in food samples using FAAS.

This article describes the development by response surface methodology (RSM) of a procedure for iron, zinc and manganese determination by flame atomic absorption spectrometry (FAAS) in food samples after digestion employing a focussed microwave system. A Doehlert matrix was used to find optimal conditions for the procedure through response surface study. Three variables (irradiation power and time and composition of oxidant solution-HNO(3)+H(2)O(2)) were regarded as factors in the optimization study. The working conditions were established as a compromise between optimum values found for each analyte taking into consideration the robustness of the procedure. These values were 12min, 260W and 42% (v/v) for irradiation time, irradiation power and percent of H(2)O(2) in solution, respectively. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials and by comparison with a well-established closed vessel microwave dissolution methodology.

Factorial design in the optimization of preconcentration procedure for lead determination by FAAS.

The present paper proposes a preconcentration procedure for lead determination using flame atomic absorption spectrometry (FAAS). It is based on lead(II) ions extraction as brilliant cresyl blue (BCB) complex and its sorption onto Diaion HP-2MG, a methacrylic ester copolymer. The optimization step was carried out using factorial design and the variables studied were pH, shaking time and reagent concentration. In the established experimental conditions, lead can be determinate with a limit of detection of 3.7mugL(-1) lead (N = 20) and a relative standard deviation of 7% for a lead concentration of 100mugL(-1). The accuracy was confirmed by analysis of a certified reference material, the stream sediment furnished by National Research Centre for Certified Reference Materials (NRCCRM), China (GBW 07310). Effect of other ions in the procedure proposed was also studied. The method was applied for lead determination in real samples of water, tea, soil and dust. Tests of addition/recovery in the experiments for lead determination in water samples revealed that the proposed procedure could be applied satisfactorily for analysis of these samples.