Inorganic As speciation and bioavailability in estuarine sediments of Todos os Santos Bay, BA, Brazil.

The spatial distribution of As (total As, As (III) and As (V)) in estuarine sediments from the main tributaries of Todos os Santos Bay, BA, Brazil, was evaluated under high and low flow conditions. The concentrations of As were determined using a slurry sampling procedure with hydride generation atomic absorption spectrometry (HG-AAS). The highest concentrations were observed at estuary mouths, and exceeded conservative lower threshold value (Threshold Effects Level; TEL). Due to the oxic conditions and abundance of Mn and Fe (oxyhydr)oxides in the sediments, most inorganic arsenic in the Subaé and Paraguaçu estuaries was present as As (V). Nevertheless, the concentration of As (III) at several locations along the Jaguaripe River were also above the TEL value, suggesting that As may be toxic to biota. In the Subaé estuary, antropogenic activities are the main source of As. At the Jaguaripe and at Paraguaçu estuaries, nevertheless, natural sources of As need to be considered to explain the distribution patterns.

Statistical mixture design development of digestion methods for Oyster tissue using inductively coupled plasma optical emission spectrometry for the determination of metallic ions.

The quantitative determination of chemical elements in organic or biological samples is an important analytical problem. Normally the elements to be determined in the organic matrix must be transformed into a simple inorganic form. A digestion method by heating on a block digestor has been developed for the determination of Al, As, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, V and Zn in Oyster tissue by ICP OES. A simplex centroid statistical mixture design has been used to study the effects of changing HNO(3), HCl and H(2)O(2) reagent proportions on the digestion of these samples. Response surface and principal component analyses show that the species Ca, Cd, Cu, Fe, Mg, Mn and Zn have very similar analytical tendencies under this experiment. By means of mixture modeling maximum recoveries for these ions were predicted using 19%, 18% and 63% of the HCl, HNO(3) and H(2)O(2) pseudocomponent mixtures, respectively. This corresponds to 21.4%, 30.8% and 47.8% of the HCl, HNO(3) and H(2)O(2) commercial solutions. Furthermore the As, Co and V ions present large recoveries for these mixtures as well. The Al and Ba ion recoveries are seen to be independent of the mixture proportions. The analysis of Oyster tissue reference material (SRM 1566b - NIST) under optimized conditions at the selected wavelengths resulted in ion recoveries between 90% and 100%.

Box-Behnken design: an alternative for the optimization of analytical methods.

The present paper describes fundamentals, advantages and limitations of the Box-Behnken design (BBD) for the optimization of analytical methods. It establishes also a comparison between this design and composite central, three-level full factorial and Doehlert designs. A detailed study on factors and responses involved during the optimization of analytical systems is also presented. Functions developed for calculation of multiple responses are discussed, including the desirability function, which was proposed by Derringer and Suich in 1980. Concept and evaluation of robustness of analytical methods are also discussed. Finally, descriptions of applications of this technique for optimization of analytical methods are presented.

A pre-concentration procedure using coprecipitation for determination of lead and iron in several samples using flame atomic absorption spectrometry.

The present paper proposes a pre-concentration procedure for determination of lead and iron in several samples by flame atomic absorption spectrometry. In it, lead(II) and iron(III) ions are coprecipitated using the violuric acid-copper(II) system as collector. Afterwards, the precipitate is dissolved with 1M HNO3 solution and the metal ions are determined. The optimization step was performed using factorial design involving the variables: pH, violuric acid mass (VA) and copper concentration (Cu). Using the optimized experimental conditions, the proposed procedure allows the determination these metals with detection limits of 0.18 microg L(-1) for iron and 0.16 microg L(-1) for lead. The effects of foreign ions on the pre-concentration procedure were also evaluated and the results demonstrated that this method could be applied for determination of iron and lead in several real samples. The proposed method was successfully applied to the analysis of seawater, urine, mineral water, soil and physiological solution samples. The concentrations of lead and iron achieved in these samples agree well with others data reported in the literature.

Optimization of the preconcentration system of cadmium with 1(2-thiazolylazo)-p-cresol using a knotted reactor and flame atomic absorption spectrometric detection.

The present paper proposes an on-line preconcentration procedure for cadmium determination in drinking water samples. It is based on the precipitation of cadmium(II) ions on a knotted reactor (KR) using 1(2-thiazolylazo)-p-cresol (TAC) as complexing reagent. The optimization step was performed using a full factorial design involving the variables: pH, eluent concentration (nitric acid) and TAC concentration. The results of this experiment demonstrated that these variables at chosen levels are not statistically significant. Under optimized experimental established conditions, analytical parameters for the preconcentration method were: a detection limit of 40.0 ng/l, precision as relative standard deviation (RSD) of 1.2 and 1.0%, for cadmium concentration of 2.5 and 20.0 microg/l, respectively. The preconcentration factor considering the slopes of the analytical curves with and without preconcentration is 23 for a sample volume of 10 ml. This system shows a sampling frequency of 25 h(-1). In order to check the accuracy, the standard reference material, NIST SRM 1643d trace elements in water was analyzed. A comparison, using t-test demonstrates that there is not significant difference among the achieved results with proposed method and the certified values. The addition/recovery experiments in the samples analyzed demonstrated the accuracy and applicability of the system developed for cadmium determination in water samples.

Factorial design for multivariate optimization of an on-line preconcentration system for platinum determination by ultrasonic nebulization coupled to inductively coupled plasma optical emission spectrometry.

A system for on-line preconcentration and determination of platinum by ultrasonic nebulization (USN) coupled to inductively coupled plasma optical emission spectrometry (ICP-OES) was studied. It is based on the chemical sorption of platinum on a column packed with polyurethane foam loaded with thiocyanate reagent. The optimization step was carried out using two level full factorial design. Three variables (pH, loading flow rate (LFR) and eluent concentration) were regarded as factors in the optimization. Results of the two level factorial design 2(3) with three replicates of the central point for platinum preconcentration, based on the variance analysis (ANOVA), demonstrated that the factors and their interactions are not statistically significant. The proposed procedure allowed the determination of platinum with a detection limit of 0.28mugl(-1). The precision for 10 replicate determinations at 10.0mugl(-1) Pt level was 3.8% relative standard deviation (R.S.D.), calculated from the peak heights obtained. A total enhancement factor of 100 was obtained with respect to ICP-OES using pneumatic nebulization (10 for USN and 10 for preconcentration). A sampling frequency of 50 samples per hour was obtained. The effect of other ions in concentrations agreeing with water samples was studied. The addition/recovery experiments in the samples analyzed demonstrated the accuracy and applicability of the system developed for platinum determination in spiked water samples.

Use of factorial design and Doehlert matrix for multivariate optimisation of an on-line preconcentration system for lead determination by flame atomic absorption spectrometry.

A system for on-line preconcentration and determination of lead by flame atomic absorption spectrometry (FAAS) was proposed. It was based on the sorption of lead(II) ions on a minicolumn of polyurethane foam loaded with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM). The optimisation step was carried out using two-level full factorial and Doehlert designs for the determination of the optimum conditions for lead preconcentration. The proposed procedure allowed the determination of lead with a detection limit of 2.2 microg L(-1), and a precision, calculated as relative standard deviation (RSD), of 2.4 and 6.8 for a lead concentration of 50.0 and 10.0 microg L(-1), respectively. A preconcentration factor of 45 and a sampling frequency of 27 samples per hour were obtained. The recovery achieved for lead determination in the presence of several cations demonstrated that this procedure has enough selectivity for analysis of environmental samples. The validation was carried out by analysis of certified reference material. This procedure was applied to lead determination in natural food.

Use of tissue conditioner in pediatric dentistry: a clinical case report.

This report intends to show the use of tissue conditioners on esthetic and functional removable partial dentures, placed by the technique of direct relining immediately after surgery to protect the surgical wound and aid the cicatrization.

Molybdenum determination in iron matrices by ICP-AES after separation and preconcentration using polyurethane foam.

A procedure is proposed for the separation and determination of molybdenum in iron matrices by a batch process. It is based on the solid-phase extraction of the molybdenum(V) ion as thiocyanate complex on polyurethane (PU) foam. The extraction parameters were optimized. Using 0.20 mol L-1 hydrochloric acid, a thiocyanate concentration of 0.10 mol L-1, 100 mg of polyurethane foam and shaking time of 10 min, molybdenum (5-400 micrograms) can be separated and preconcentrated from large amounts of iron (10 mg). Desorption was carried out instantaneously by conc. nitric acid or acetone. Distribution coefficients, sorption capacity of the PU foam and coefficients of variation were also evaluated. The effect of some ions on the separation procedure was assessed. Iron(III) should be reduced to iron(II). The proposed procedure was used to determine molybdenum in standard iron matrices such as steel and pure iron. The achieved results did not show significant differences with certified values.

Flow injection determination of cobalt after its sorption onto polyurethane foam loaded with 2-(2-thiazolylazo)-p-cresol (TAC).

This paper reports the development of a new methodology for determination of cobalt in water samples by using a flow injection system with loaded PUF as solid phase to preconcentrate analytes. Procedure is based on on-line retention of Co(III) ions (generated in alkaline medium by Co(II) oxidation) in a minicolumn packed with a polyether type polyurethane foam loaded with TAC (2-(2-thiazolylazo)-p-cresol) and elution with 2 mol l(-1) HCl directly to the flame atomic absorption spectrometer nebulizer. Several chemical and flow variables that could affect the performance of this system were investigated as well as the possible interferents. For 2 min of preconcentration time (10.0 ml of sample volume) the system achieved a detection limit 3.2 mug l(-1), a R.S.D. 5% at 20 mug l(-1) and an analytical throughput 24 h(-1). Whereas for 3 min of preconcentration time (15.0 ml of sample volume) a detection limit 2.4 mug l(-1), a R.S.D. under 8% at 10 mug l(-1) and a sampling frequency 17 h(-1) were reported.

[Impact of spouse violence on the decision to have an abortion]. / Influência da violência conjugal sobre a decisão de abortar.

Studies on marital violence against women have contributed to a better understanding of the health problems to which this population is exposed to, especially those related to reproduction. The need to investigate more deeply connections between home violence and provoked abortion has elicited questions like: "Does the decision to abort occur during the violence cycle as a moment of autonomy for the woman or is she forced to do it? The purpose of this qualitative study is to describe manifestations of marital violence among women admitted to the hospital due to provoked abortions, analyzing the influence of such violence on their decision to have an abortion. With the results, the study intends to broaden the discussion on home violence and abortion, giving visibility to these problems in the context of health services.

Copper determination in natural water samples by using FAAS after preconcentration onto amberlite XAD-2 loaded with calmagite.

A procedure for separation and preconcentration of trace amounts of copper in natural water samples, has been proposed. It is based on the adsorption of copper(II) ions onto a column of Amberlite XAD-2 resin loaded with calmagite reagent. This way amounts of copper within the range from 0.0125 to 25.0 microg, in a sample volume of 25 to 250 ml, and pH from 3.7 to 10.0 was concentrated as calmagite complex in a column of 0.50 g of Amberlite XAD-2 resin. Copper (II) ion was desorpted by using 5.0 ml of 2 mol l(-1) hydrochloric acid. Detection and determination limits of the proposed procedure for 250 ml sample volume were 0.15 and 0.50 microg l(-1), respectively. Selectivity test showed that (in the indicated concentration), calcium(II) (500 mg l(-1)), magnesium(II) (500 mg l(-1)), strontium(II) (50 mg l(-1)), iron(III) (10 mg l(-1)), nickel(II) (10 mg l(-1)), cobalt(II) (10 mg l(-1)), cadmium(II) (10 mg l(-1)) and lead(II) (10 mg l(-1)) did not interfere in copper determination by this procedure. Precision of the method, evaluated as the relative standard deviation by analyzing a series of seven replicates, was 2.42% for a copper mass of 1.0 microg in a sample volume of 100 ml. The accuracy of the proposed procedure was evaluated by means of copper determination in reference biological samples. The achieved results were in good agreement with certified values. The extractor system had a sorption capacity of 1.59 mumol of copper per gram of resin loaded with calmagite. The proposed procedure was applied for copper determination by FAAS in natural water samples. Samples were collected from different places of Salvador city, Bahia, Brazil. The achieved recovery, measured by the standard addition technique, showed that the proposed procedure had good accuracy. A good enrichment factor (50x) and simplicity are the main advantages in this analytical procedure.

Nickel and zinc determination by flow-injection solid-phase spectrophotometry exploiting different sorption rates.

Flow-injection solid-phase spectrophotometry is applied for sequential determination of nickel and zinc, exploiting their different sorption rates on 1-(2-thiazolylazo)-2-naphthol (TAN) immobilized on C(18)-bonded silica. The Zn(II) sorption rate on the solid support is constant for flow rates ranging from 0.70 to 2.2 ml min(-1), but for Ni(II) the sorption rate decreases with increasing flow rate. A flow system was designed to perform sequential measurements at two different flow rates (0.85 and 1.9 ml min(-1)). The absorbance was measured at 595 nm, where both TAN-immobilized complexes showed maximum absorption. The coefficients of variation were estimated (n=10) as 1.1 and 1.7% (at 1.9 ml min(-1)) and 1.2 and 2.1% (at 0.85 ml min(-1)) for zinc and nickel, respectively. This strategy was applied to determine zinc and nickel in copper-based alloys and the results agreed with certified values at the 95% confidence level. The sample throughput was estimated as 36 h(-1).

Nickel determination in saline matrices by ICP-AES after sorption on Amberlite XAD-2 loaded with PAN.

In the present paper, a solid phase extraction system for separation and preconcentration of nickel (ng g(-1)) in saline matrices is proposed. It is based on the adsorption of nickel(II) ions onto an Amberlite XAD-2 resin loaded with 1-(2-pyridylazo)-2-naphthol (PAN) reagent. Parameters such as the pH effect on the nickel extraction, the effect of flow rate and sample volume on the extraction, the sorption capacity of the loaded resin, the nickel desorption from the resin and the analytical characteristics of the procedure were studied. The results demonstrate that nickel(II) ions, in the concentration range 0.10-275 microg l(-1), and pH 6.0-11.5, contained in a sample volume of 25-250 ml, can be extracted by using 1 g Amberlite XAD-2 resin loaded with PAN reagent. The adsorbed nickel was eluted from the resin by using 5 ml 1 M hydrochloric acid solution. The extractor system has a sorption capacity of 1.87 mumol nickel per g of Amberlite XAD-2 resin loaded with PAN. The precision of the method, evaluated as the R.S.D. obtained after analyzing a series of seven replicates, was 3.9% for nickel in a concentration of 0.20 microg ml(-1). The proposed procedure was used for nickel determination in alkaline salts of analytical grade and table salt, using an inductively coupled plasma atomic emission spectroscopy technique (ICP-AES). The standard addition technique was used and the recoveries obtained revealed that the proposed procedure shows good accuracy.

ICP-AES determination of small amounts of zinc in copper-base alloys after separation by adsorption of the zinc-TAN complex on Sep Pak C18 cartridges.

The use of ICP/AES for the determination of zinc, in low concentration levels, in matrices containing high levels of copper is difficult because copper interferes in the zinc main emission wavelength (213.856 nm). In the present work, a separation of zinc from copper matrices was possible, using the reaction of zinc(II) cation with 1-(2-tiazolylazo)-2-naphthol (TAN), in the pH range of 6.5-8.0, resulting in a stable red complex. Copper also reacts with TAN but its interference was avoided by the addition of ascorbic acid and thiosulphate in the reaction medium. In this way, the aqueous solution was passed through a SEP PAK C18 cartridge, in which the zinc(II)-TAN complex was quantitatively retained, but it did not occur with copper which passes through the cartridge, as [Cu(2)(S(2)O(3))(2)](2-), with the aqueous solution. The cartridge was washed with water and the complex eluted with ethanol. Then, the alcohol was evaporated and the complex decomposed by nitric acid. It results in both zinc pre-concentration and separation from copper. The zinc quantification was carried out by ICP/AES at 213.856 nm. The relative standard deviations, for ten different aliquots, were 5.7% and the average recovery found for zinc was 96%, even when the concentration ratio Cu/Zn was up to 500/1 (mg l(-1):mg l(-1)). Other metals, like nickel, for example, can react with TAN in the same way as zinc but they do not interfere in the emission wavelength 213.856 nm.

Quantitative separation of zinc traces from cadmium matrices by solid-phase extraction with polyurethane foam.

A system for separation of zinc traces from large amounts of cadmium is proposed in this paper. It is based on the solid-phase extraction of the zinc in the form of thiocyanate complexes by the polyurethane foam. The following parameters were studied: effect of pH and of the thiocyanate concentration on the zinc extraction, shaking time required for quantitative extraction, amount of PU foam necessary for complete extraction, conditions for the separation of zinc from cadmium, influence of other cations and anions on the zinc sorption by PU foam, and required conditions for back extraction of zinc from the PU foam. The results show that zinc traces can be separated from large amounts of cadmium at pH 3.0+/-0.50, with the range of thiocyanate concentration from 0.15 to 0.20 mol l(-1), and the shaking time of 5 min. The back extraction of zinc can be done by shaking it with water for 10 min. Calcium, barium, strontium, magnesium, aluminum, nickel and iron(II) are efficiently separated. Iron(III), copper(II) and cobalt(II) are extracted simultaneously with zinc, but the iron reduction with ascorbic acid and the use of citrate to mask copper(II) and cobalt(II) increase the selectivity of the zinc extraction. The anions nitrate, chloride, sulfate, acetate, thiosulphate, tartarate, oxalate, fluoride, citrate, and carbonate do not affect the zinc extraction. Phosphate and EDTA must be absent. The method proposed was applied to determine zinc in cadmium salts using 4-(2-pyridylazo)-resorcinol (PAR) as a spectrophotometric reagent. The result achieved did not show significant difference in the accuracy and precision (95% confidence level) with those obtained by ICP-AES analysis.

Spectrophotometric and inductively coupled plasma atomic emission spectrometric determination of titanium in ilmenites after rapid dissolution with phosphoric acid.

The use of 85% phosphoric acid in borosilicate conical flasks for the dissolution of ilmenites at 230 +/- 10 degrees C is reported. The samples were quantitatively dissolved in less than 13 min. Titanium was determined by both spectrophotometry and inductively coupled plasma atomic emission spectrometry ICP-AES. Vanadium and iron were determined by ICP-AES. In several samples of ilmenites analyzed, the TiO(2) concentration was in the range 10.6-57.5% and those of FeO and V(2)O(5) were in the ranges 31.6-51.4% and 0.39-1.32%, respectively. In the spectrophotometric method, vanadium interference occurs only when the Ti V concentration ratio is <4. In all samples analyzed this ratio was around 12, resulting in no interferences due to vanadium. Hence the ilmenite dissolution procedure using phosphoric acid was compatible with titanium quantification by both spectrophotometry and ICP-AES.

Derivative spectrophotometric determination of nickel using Br-PADAP.

A major problem with spectrophotometric methods for nickel is cobalt interference, because many of the reagents for nickel also react with cobalt. In this work, the interference of cobalt in the determination of nickel using 2-(5-bromo-2-pyridylaxo)-5-diethylaminophenol (Br-PADAP) was eliminated by the use of derivative spectrophotometry, using the zero-crossing method for evaluation of the derivative signal. Br-PADAP reacts with nickel(II) in the presence of Triton X-100 to form a red complex with absorption maxima at 530 and 562 nm. The reactions parameters and the conditions for the measurements of the first-derivative signal were studied and the results demonstrated that using the derivative technique, Br-PADAP can be used for nickel determination with a selectivity higher than that of ordinary spectrophotometry and with a limit of detection of 0.2 ng ml(-1). The pH should be in the range 5.0-6.0 using an acetate buffer. The determination of nickel in the presence of cobalt was performed with conventional and derivative procedures, and the results demonstrated that only the derivative method should be used and, of the methods used for evaluation of the derivative signal, the zero-crossing method is the best. The proposed procedure was used for nickel determination in steels standards. The results demonstrated that the procedure has satisfactory accuracy and precision. Cobalt interference can be also eliminated by using dual-wave-length spectroscopy.