An Environmental Friendly Procedure for Photometric Determination of Hypochlorite in Tap Water Employing a Miniaturized Multicommuted Flow Analysis Setup

A photometric procedure for the determination of ClO(-) in tap water employing a miniaturized multicommuted flow analysis setup and an LED-based photometer is described. The analytical procedure was implemented using leucocrystal violet (LCV; 4,4', 4 ''-methylidynetris (N, N-dimethylaniline), C(25)H(31)N(3)) as a chromogenic reagent. Solenoid micropumps employed for solutions propelling were assembled together with the photometer in order to compose a compact unit of small dimensions. After control variables optimization, the system was applied for the determination of ClO(-) in samples of tap water, and aiming accuracy assessment samples were also analyzed using an independent method. Applying the paired t-test between results obtained using both methods, no significant difference at the 95% confidence level was observed. Other useful features include low reagent consumption, 2.4 mu g of LCV per determination, a linear response ranging from 0.02 up to 2.0 mg L(-1) ClO(-), a relative standard deviation of 1.0% (n = 11) for samples containing 0.2 mg L(-1) ClO(-), a detection limit of 6.0 mu g L(-1) ClO(-), a sampling throughput of 84 determinations per hour, and a waste generation of 432 mu L per determination.

Exploiting Pulsed Flows for Heating Improvement: Application to Determination of Total Reducing Sugars in Molasses and Sugar-Cane Juices

Laminar and pulsed flows typical of multi-commuted and multi-pumping flow systems, were evaluated in relation to analytical procedures carried out at high temperatures. As application, the spectrophotometric determination of total reducing sugars (TRS, hydrolyzed sucrose plus reducing sugars) in sugar-cane juice and molasses was selected. The method involves in-line hydrolysis of sucrose and alkaline degradation of the reducing sugars at about 98 degrees C. Better results were obtained with pulsed flows, due to the efficient radial mass transport inherent to the multi-pumping flow system. The proposed system presents favorable characteristics of ruggedness, analytical precision (r.s.d. < 0.013 for typical samples), stability (no measurable baseline drift during 4-h working periods), linearity of the analytical curve (r > 0.992, n = 5, 0.05-0.50% w/v TRS) and sampling rate (65 h(-1)). Results are in agreement with ion chromatography.

The reduction of Cu(II)/neocuproine complexes by some polyphenols: Total polyphenols determination in wine samples

A new method is presented for spectrophotometric determination of total polyphenols content in wine. The procedure is a modified CUPRAC method based on the reduction of Cu(II), in hydroethanolic medium (pH 7.0) in the presence of neocuproine (2,9-dimethyl-1,10-phenanthroline), by polyphenols, yielding a Cu(I) complexes with maximum absorption peak at 450 nm. The absorbance values are linear (r = 0.998, n = 6) with tannic acid concentrations from 0.4 to 3.6 mu mol L(-1). The limit of detection obtained was 0.41 mu mol L(-1) and relative standard deviation 1.2% (1 mu mol L(-1); n = 8). Recoveries between 80% and 110% (mean value of 95%) were calculated for total polyphenols determination in 14 commercials and 2 synthetic wine samples (with and without sulphite). The proposed procedure is about 1.5 more sensitive than the official Folin-Ciocalteu method. The sensitivities of both methods were compared by the analytical responses of several polyphenols tested in each method. (C) 2010 Elsevier Ltd. All rights reserved.

FIA determination of ascorbic acid at low potential using a ruthenium oxide hexacyanoferrate modified carbon electrode

The anodic oxidation of ascorbic acid on a ruthenium oxide hexacyanoferrate modified electrode was characterized by cyclic voltammetry. On this modified surface, the electrocatalytic process allows the determination of ascorbic acid to be performed at 0.0 V and pH 6.9 with a limit of detection of 2.2 mu M in a flow injection configuration. Under this experimental condition, no interference from glucose, nitrite and uric acid was noticed. Lower detection limit values were obtained by measuring flow injection analysis (FIA) responses at 0.4 V (0.14 mu M), but a concurrent loss of selectivity is expected at this more positive potential. Under optimal FIA operating conditions, the linear response of the method was extended up to 1 mM ascorbic acid. The repeatability of the method for injections of a 1.0 mM ascorbic acid solution was 2.0% (n=10). The usefulness of the method was demonstrated by an addition-recovery experiment with urine samples and the recovered values were in the 98-104% range. (c) 2007 Elsevier B.V. All rights reserved.

A multicommuted flow-system for spectrophotometric determination of tannin exploiting the Cu(I)/BCA complex formation

A flow system exploiting the multicommutation approach is proposed for spectrophotometric determination of tannin in beverages. The procedure is based on the reduction of Cu(II) in the presence of 4,4`-dicarboxy-2,2`-biquinoline, yielding a complex with maximum absorption at 558 nm. Calibration graph was linear (r=0.999) for tannic acid concentrations up to 5.00 mu mol L-1. The detection limit and coefficient of variation were estimated as 10 nmol L-1 (99.7% confidence level) and 1% (1.78 mu mol L-1 tannic acid, n=10), respectively. The sampling rate was 50 determinations per hour. The proposed procedure is more sensitive and selective than the official Folin-Denis method, also minimizing drastically waste generation. Recoveries within 91.8 and 115% were estimated for total tannin determination in tea and wine samples. (C) 2007 Elsevier B.V. All rights reserved.

A Graphite-Polyurethane Composite Electrode for the Analysis of Furosemide

A graphite-polyurethane composite electrode has been used for the determination of furosemide, a antihypertensive drug, in pharmaceutical samples by anodic oxidation. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrooxidation process at +1.0 V vs. SCE over a wide pH range, with the result that no adsorption of analyte or products occurs, unlike at other carbon-based electrode materials. Quantification was carried out using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry. Linear ranges were determined (up to 21 mu mol L-1 with cyclic voltammetry) as well as limits of detection (0.15 mu mol L-1 by differential pulse voltammetry). Four different types of commercial samples were successfully analyzed. Recovery tests were performed which agreed with those obtained by spectrophotometric evaluation. The advantages of this electrode material for repetitive analyzes, due to the fact that no electrode surface renewal is needed owing to the lack of adsorption, are highlighted.

Determination of picloram in waters by sequential injection chromatography with UV detection

This paper describes a sequential injection chromatography procedure for determination of picloram in waters exploring the low backpressure of a 2.5 cm long monolithic C18 column. Separation of the analyte from the matrix was achieved in less than 60 s using a mobile phase composed by 20:80 (v v-1) acetonitrile:5.0 mmol L-1 H3PO4 and flow rate of 30 μL s-1. Detection was made at 223 nm with a 40 mm optical path length cell. The limits of detection and quantification were 33 and 137 μg L-1, respectively. The proposed method is sensitive enough to monitor the maximum concentration level for picloram in drinking water (500 μg L-1). The sampling frequency is 60 analyses per hour, consuming only 300 μL of acetonitrile per analysis. The proposed methodology was applied to spiked river water samples and no statistically significant differences were observed in comparison to a conventional HPLC-UV method.

A flow injection procedure based on solenoid micro-pumps for spectrophotometric determination of free glycerol in biodiesel

A flow system designed with solenoid micro-pumps is proposed for fast and greener spectrophotometric determination of free glycerol in biodiesel. Glycerol was extracted from samples without using organic solvents. The determination involves glycerol oxidation by periodate, yielding formaldehyde followed by formation of the colored (3,5-diacetil-1,4-dihidrolutidine) product upon reaction with acetylacetone. The coefficient of variation, sampling rate and detection limit were estimated as 1.5% (20.0 mg L(-1) glycerol, n =10), 34 h(-1), and 1.0 mg L(-1) (99.7% confidence level), respectively. A linear response was observed from 5 to 50 mg L(-1), with reagent consumption estimated as 345 mu g of KIO(4) and 15 mg of acetylacetone per determination. The procedure was successfully applied to the analysis of biodiesel samples and the results agreed with the batch reference method at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

Downscaling a multicommuted flow injection analysis system for the photometric determination of iodate in table salt

In this work a downscaled multicommuted flow injection analysis setup for photometric determination is described. The setup consists of a flow system module and a LED based photometer, with a total internal volume of about 170 mu L The system was tested by developing an analytical procedure for the photometric determination of iodate in table salt using N,N-diethyl-henylenediamine (DPD) as the chromogenic reagent. Accuracy was accessed by applying the paired r-test between results obtained using the proposed procedure and a reference method, and no significant difference at the 95% confidence level was observed. Other profitable features, such as a low reagent consumption of 7.3 mu g DPD per determination: a linear response ranging from 0.1 up to 3.0 m IO(3)(-), a relative standard deviation of 0.9% (n = 11) for samples containing 0.5 m IO(3)(-), a detection limit of 17 mu g L(-1) IO(3)(-), a sampling throughput of 117 determination per hour, and a waste generation 600 mu L per determination, were also achieved. (C) 2010 Elsevier B.V. All rights reserved.

Total and inorganic mercury determination in fish tissue by flow injection cold vapour atomic fluorescence spectrometry

A simple and reliable method for Hg determination in fish samples has been developed. Lyophilised fish tissue samples were extracted in a 25% (w/v) tetramethylammonium hydroxide (TMAH) solution; the extracts were then analysed by FI-CVAFS. This method can be used to determine total and inorganic Hg, using the same FI manifold. For total Hg determination, a 0.1% (w/v) KMnO(4) solution was added to the FI manifold at the sample zone, followed by the addition of a 0.5% (w/v) SnCl(2) solution, whereas inorganic Hg was determined by adding a 0.1% (w/v) L-cysteine solution followed by a 1.0% (w/v) SnCl(2) solution to the FI system. The organic fraction was determined as the difference between total and inorganic Hg. Sample preparation, reagent consumption and parameters that can influence the FI-CVAFS performance were also evaluated. The limit of detection for this method is 3.7 ng g(-1) for total Hg and 4.3 ng g(-1) for inorganic Hg. The relative standard deviation for a 1.0 mu gL(-1) CH(3)Hg standard solution (n = 20) was 1.1%, and 1.3% for a 1.0 mu gL(-1) Hg(2+) standard solution (n = 20). Accuracy was assessed by the analysis of Certified Reference Material (dogfish: DORM-2, NRCC). Recoveries of 99.1% for total Hg and 93.9% inorganic Hg were obtained. Mercury losses were not observed when sample solutions were re-analysed after a seven day period of storage at 4 degrees C.

Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10-5000 mu mol L(-1) with detection and quantification limits of 1.7 (S/N = 3) and 5.9 (S/N = 10) mu mol L(-1), respectively. The repeatability of the method was evaluated using a 500 mu mol L(-1) hydrogen peroxide solution, the value obtained being 1.6% (n = 14). A sampling rate of 112 samples h(-1) was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.

Development of a sequential injection chromatography (SIC) method for determination of simazine, atrazine, and propazine

This paper describes the development of a sequential injection chromatography (SIC) procedure for separation and quantification of the herbicides simazine, atrazine, and propazine exploring the low backpressure of a 2.5 cm long monolithic C(18) column. The separation of the three compounds was achieved in less than 90 s with resolution > 1.5 using a mobile phase composed by ACN/1.25 mmol/L acetate buffer (pH 4.5) at the volumetric ratio of 35:65 and flow rate of 40 mu L/s. Detection was made at 223 nm using a flow cell with 40 mm of optical path length. The LOD was 10 mu g/L for the three triazines and the quantification limits were of 30 mu g/L for simazine and propazine and 40 mu g/L for atrazine. The sampling frequency is 27 samples per hour, consuming 1.1 mL of ACN per analysis. The proposed methodology was applied to spiked water samples and no statistically significant differences were observed in comparison to a conventional HPLC-UV method. The major metabolites of atrazine and other herbicides did not interfere in the analysis, being eluted from the column either together with the unretained peak, or at retention times well-resolved from the studied compounds.

Implementing stepwise solvent elution in sequential injection chromatography for fluorimetric determination of intracellular free amino acids in the microalgae Tetraselmis gracilis

The concept of sequential injection chromatography (SIC) was exploited to automate the fluorimetric determination of amino acids after pre-column derivatization with ophthaldialdehyde (OPA) in presence of 2-mercaptoethanol (2MCE) using a reverse phase monolithic C(18) stationary phase. The method is low-priced and based on five steps of isocratic elutions. The first step employs the mixture methanol: tetrahydrofuran: 10 mmol L(-1) phosphate buffer (pH 7.2) at the volumetric ratio of 8:1:91; the other steps use methanol: 10 mmol L-1 phosphate buffer (pH 7.2) at volumetric ratios of 20:80, 35:65, SO:SO and 65:35. At a flow rate of 10 mu L s(-1) a 25 mm long-column was able to separate aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), serine (Ser), glutamine (Gln), glycine (Gly), threonine (Thr), citruline (Ctr), arginine (Arg), alanine (Ala), tyrosine (Tyr), phenylalanine (Phe), ornithine (Orn) and lysine (Lys) with resolution >1.2 as well as methionine (Met) and valine (Val) with resolution of 0.6. Under these conditions isoleucine (Ile) and leucine (Leu) co-eluted. The entire cycle of amino acids derivatization, chromatographic separation and column conditioning at the end of separation lasted 25 min. At a flow rate of 40 mu L s(-1) such time was reduced to 10 min at the cost of resolution worsening for the pairs Ctr/Arg and Orn/Lys. The detection limits varied from 0.092 mu mol L(-1) for Tyr to 0.51 mu mol L(-1) for Orn. The method was successfully applied to the determination of intracellular free amino acids in the green alga Tetraselmis gracilis during a period of seven days of cultivation. Samples spiked with known amounts of amino acids resulted in recoveries between 94 and 112%. (C) 2008 Elsevier B.V. All rights reserved.