Effect of pH on the characteristics of potassium permanganate–luminol CL reaction in the presence of trace aluminum(III) and its analytical application

At pHs ≥ 11.45, trace Al was found to enhance the CL from luminol–KMnO₄ system. However, at pHs ≤ 10.42, it was found to inhibit strongly the CL from luminol–KMnO₄ system. The effect of pH, luminol and potassium permanganate concentrations on the kinetic characteristics of CL system was investigated in the presence of trace Al. On this basis, a flow injection inhibition chemiluminescence method was established for the determination of trace Al in this study. Under optimized conditions, the CL decreased linearly with Al(III) concentration in the range of 8–500 μg L⁻¹ and the detection limit (3σ) of 2 μg L⁻¹. The relative standard deviation (R.S.D.) is 3.6% for 100 μg L⁻¹ Al(III) (n = 11). The method has been applied to the determination of trace Al in real water samples with satisfactory results without the pretreatment of samples. The results given by the proposed method are in good agreement with those given by ICP-AES detection method.     

Preliminary results on the determination of ultratrace amounts of cadmium in tea samples using a flow injection on-line solid phase extraction separation and preconcentration technique to couple with a sequential injection hydride generation atomic fluorescence spectrometry

In this work, a method was developed for determination of ultra-trace levels of Cd in tea samples by atomic fluorescence spectrometry (AFS). A flow injection solid phase extraction (FI-SPE) separation and preconcentration technique, to on-line couple with a sequential injection hydride generation (SI-HG) technique is employed in this study. Cd was preconcentrated on the SPE column, which was made from a neutral extractant named Cyanex 923, while other matrix ions or interfering ions were completely or mostly separated off. Conditions for the SPE separation and preconcentration, as well as conditions for the HG technique, were studied. Due to the separation of interfering elements, Cd hydride generation efficiency could be greatly enhanced with the sole presence of Co²⁺ with a concentration of 200 μg L⁻¹, which is much lower than those in other works previously reported. Interferences on both the Cd separation and preconcentration, and Cd hydride generation (HG) were investigated; it showed that both the separation and preconcentration system, and the HG system had a strong anti-interference ability. The SPE column could be repeatedly used at least 400 times, a R.S.D. of 0.97% was obtained for 6 measurements of Cd with 0.2 μg L⁻¹ and a correlation coefficiency of 1.0000 was obtained for the measurement of a series of solutions with Cd concentrations from 0.1 to 2 μg L⁻¹. The method has a low detection limit of 10.8 ng L⁻¹ for a 25 mL solution and was successfully validated by using two tea standard reference materials (GBW08513 and GBW07605).     

Flow injection hydride generation electrothermal atomic absorption spectrometric determination of toxicologically relevant arsenic in urine

Analytical procedure for the determination of toxicologically relevant arsenic (the sum of arsenite, arsenate, monomethylarsonate and dimethylarsinate) in urine by flow injection hydride generation and collection of generated inorganic and methylated hydrides on an integrated platform of a transverse-heated graphite atomizer for electrothermal atomic absorption spectrometric determination (ETAAS) is elaborated. Platforms are pre-treated with 2.7 μmol of zirconium and then with 0.10 μmol of iridium which serve both as an efficient hydride sequestration medium and permanent chemical modifier. Arsine, monomethylarsine and dimethylarsine are generated from diluted urine samples (10–25-fold) in the presence of 50 mmol L⁻¹ hydrochloric acid and 70 mmol L⁻¹ l-cysteine. Collection, pyrolysis and atomization temperatures are 450, 500, 2100 and 2150 °C, respectively. The characteristic mass, characteristic concentration and limit of detection (3σ) are 39 pg, 0.078 μg L⁻¹ and 0.038 μg L⁻¹ As, respectively. The limits of detection in urine are ca. 0.4 and 1 μg L⁻¹ with 10- and 25-fold dilutions. The sample throughput rate is 25 h⁻¹. Applications to several urine CRMs are given.     

Time measurement-visual analysis of nickel(II) using autocatalytic reaction with sodium sulfite/hydrogen peroxide system and its application to the length detection-flow analysis

Trace amounts of nickel(II) can function as a trigger (=reaction initiator) in an autocatalytic reaction with the sodium sulfite/hydrogen peroxide system. Based on this finding, sub-μg L⁻¹ levels of nickel(II) were determined by a time measurement using the autocatalytic reaction. The detection range using the above method was 10⁻⁹–10⁻⁵ M, the detection limit (3σ) was 8.1 × 10⁻¹⁰ M (0.047 μg L⁻¹), and the relative standard deviation was 2.66% at nickel(II) concentration of 10⁻⁷ M (n = 7). This method was applied to length detection-flow injection analysis. The detection range for the flow injection analysis was 2 × 10⁻⁹–2 × 10⁻³ M. The detection limit (3σ) was 1.4 × 10⁻⁹ M (0.082 μg L⁻¹), and the relative standard deviation was 1.86 at initial nickel(II) concentration of 10⁻⁶ M (n = 7).     

Automatic in-tube SPME and fast liquid chromatography: a cost-effective method for the estimation of dibuthyl and di-2-ethylhexyl phthalates in environmental water samples

A 80-cm length commercially available capillary coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane (TBR-5) was employed to carry out on-line extraction and preconcentration of dibuthyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) in the chromatographic system. The coated capillary was placed between the sample injection loop and the injection needle of an autosampler. Variables affecting the automatic in-tube solid-phase microextraction (SPME) were optimized. A Genesis C₁₈ (5 cm × 4.6 mm i.d., 4 μm particle size) was employed as analytical column. The achieved limits of detection by use of diode array detection were 1 and 2.5 μg L⁻¹, respectively. The proposed conditions have been applied to determine those compounds at low ppb levels (≤250 μg L⁻¹) in aqueous samples. No matrix effect was found, and recoveries between 85 and 115% were obtained. The precision of the method was good, and the achieved intra- and inter-day variation coefficients were between 5 and 20%. The analysis time per sample was 20 min and any off-line pre-treatment of the samples was needed. The taken sample volume was 100 μL. Data on the application of the described method to the analysis of different water samples are presented.     

Method development for the determination of lead in wine using electrothermal atomic absorption spectrometry comparing platform and filter furnace atomizers and different chemical modifiers

A method has been developed for the determination of lead in wine by electrothermal atomic absorption spectrometry without any sample preparation and calibration against aqueous standards, using 7.5 μg Pd as a chemical modifier. The results obtained for seven wines using the proposed method and an acid digestion procedure did not show any significant difference using a Student's t-test. Atomization in a transversally heated filter atomizer (THFA) was compared with atomization in a conventional transversally heated platform furnace. The former provided a 2.6-fold higher sensitivity, improving the characteristic mass from 34 to 12 pg and a 1.6-fold better limit of detection (0.3 μg L⁻¹ compared to 0.5 μg L⁻¹) for aqueous solutions using the same injection volume of 20 μL. However, the average precision, expressed as the relative standard deviation for the determination of lead in wine under routine conditions was improved from 4.6% with platform atomization to 0.6% in the THFA. The lead content found in seven arbitrarily chosen white and red wines, five from Brazil, one from Chile and one from Spain, ranged from 6 to 60 μg L⁻¹ Pb with an average content of 11.4 μg L⁻¹ Pb for the wines from South America.     

Hydrogen peroxide in basic media for whole blood sample dissolution for determination of its lead content by electrothermal atomization atomic absorption spectrometry

Hydrogen peroxide in basic media is proposed as a means for dissolving whole blood samples to be analyzed by electrothermal atomization atomic absorption spectrometry, ET AAS. Approximately 2 g of the whole blood sample were directly weighed in a 150 mL volumetric flask; 3 mL of a NaOH 0.2 mol L⁻¹ solution, two drops of 1-octanol, as an antifoaming agent, and 1 mL of 30% volume hydrogen peroxide were added to the flask to promote oxidation. The solution was then manually shaken and after approximately three minutes of shaking, a clear solution, with no apparent suspended solids or greasy layers, was obtained. Distilled-deionized water was used to complete the volume. Ten μL of the resulting solution along with 10 μL of a solution containing 5000 mg L⁻¹ of NH₄H₂PO₄ and 300 mg L⁻¹ of Mg(NO₃)₂ as a modifier, were injected into transversely heated graphite tubes for lead determination. Both aqueous standards and standard addition calibration curves produced results not significantly different at a 95% confidence limit level. Accuracy of the measurements was assessed by analysis of the IAEA A-13 (concentration of trace and minor elements in freeze dried animal blood) standard reference material containing 0.18 mg L⁻¹ lead on a dry basis and by means of recovery tests. Analysis of the IAEA A-13 standard produced 0.17 ± 0.02 mg L⁻¹ lead on a dry basis; recovery tests afforded values from 95 to 105%. Ten consecutive measurements of a 5 ppb lead solution gave a characteristic mass of 47.2 pg and a (3S) detection limit of 1.77 μg L⁻¹ Pb. Results obtained from analysis of whole blood samples of volunteer donors covered a lead concentration range between 8 and 21 μg L⁻¹ with a mean value of 11.9 ± 4.7 μg L⁻¹.     

Kinetic spectrophotometric method for rapid determination of trace formaldehyde in foods

A simple and sensitive kinetic-spectrophotometric method was developed for the determination of ultra trace amount of formaldehyde in food samples. The method was based on the oxidation of rhodamine B (RhB) by potassium bromate in sulfuric acid medium (formaldehyde as catalyst). The reaction was monitored by measuring the decrease in absorbance of the dye at 515 nm after 6 min. The developed method allowed the determination of formaldehyde in the range of 10–100 μg L⁻¹ with good precision, accuracy and the detection limit was down to 2.90 μg L⁻¹. The relative standard deviations for the determination of 10 and 60 μg L⁻¹ of formaldehyde were 3.0% and 1.9% (n = 10), respectively. The method was found to be sensitive, selective and was applied to the determination of formaldehyde in foods with satisfactory results.     

Dithiocarbamate functionalized or surface sorbed Merrifield resin beads as column materials for on line flow injection-flame atomic absorption spectrometry determination of lead

This article describes the preparation of dithiocarbamate immobilized/functionalized and diethylammonium dithiocarbamate (DDTC) sorbed Merrifield Chloromethylated Resin (MCR) beads and comparison of these materials for on-line flow injection (FI)–flame atomic absorption spectrometry (FAAS) determination of lead. The above two materials enrich lead quantitatively over an identical optimal pH range (8.0–9.0), a preconcentration/loading time (up to 4 min) and elution with acidified methanol (a minimum of 0.01 mol L⁻¹ HNO₃ in methanol). However, the detection limit for lead using dithiocarbamate functionalized MCR beads is 1.3 μg L⁻¹ compared to 3 μg L⁻¹ for DDTC sorbed MCR beads. Again, the sensitivity enhancement over direct FAAS signal is 48- and 27-fold, respectively. In addition, dithiocarbamate functionalized MCR beads offers better precision compared to DDTC sorbed MCR beads as the corresponding relative standard deviation (R.S.D.) values for five successive determinations of 0.20 μg mL⁻¹ are 1.44 and 4.36%, respectively. The accuracy of the developed on-line FI–FAAS procedure employing dithiocarbamate functionalized MCR beads as column material was tested by analyzing Certified Reference Material (CRM) of soil (IAEA soil-7) and marine sediment reference material (MESS-3) supplied by International Atomic Energy Agency (IAEA), Vienna and National Research Council (NRC), Canada, respectively. Furthermore, the developed procedure has been successfully tested for the analysis of surface, pond, ground and effluent water and soil samples collected from the vicinity of lead acid battery industry in India.     

Cloud point extraction for the determination of As(III) in water samples by electrothermal atomic absorption spectrometry

Cloud point extraction was applied as a preconcentration step for electrothermal atomic absorption spectrometry (ETAAS) determination of As(III) in aqueous solutions. After complexation with ammonium pyrrolidinedithiocarbamate, the analyte was quantitatively extracted to the surfactant-rich phase in the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. 0.1 mol L⁻¹ HNO₃ in methanol was added to the surfactant-rich phase before ETAAS determination. The precision (R.S.D.) for 11 replicate determinations of 5.0 μg L⁻¹ of As(III) was 3.0%. The concentration factor, which is defined as the concentration ratio of the analyte in the final diluted surfactant-rich extract ready for ETAAS determination and in the initial solution, was 36 for As(III). The linear concentration range was from 0.1 to 20 μg L⁻¹. The developed method was applied to the determination of As(III) in lake water and river water.     

Diagnosis of copper ions in vascular tracts using a fluorine-doped carbon nanotube sensor

The voltammetric assay of Cu(II) was investigated using a carbon nanotube electrode (CNE) and fluorine immobilized onto a carbon nanotube electrode (FCNE) in cyclic voltammetry (CV), square-wave (SW) stripping voltammetry, and chronoamperometry. Optimum SW conditions were attained at working ranges of 0.01–0.11 ng L⁻¹ Cu(II) (11 points), and a relative standard deviation of 1.68% (RSD, n = 15) was observed at 10.0 μg L⁻¹ Cu(II). Within a 200 s accumulation time, detection limit of 0.006 μg L⁻¹ was attained. The life span of each electrode was more than 1 month. The sensor was applied to tap water, blood, and rat tail vascular (in vivo). It was found that the sensor could be used with an interface system in the assay of live cells and non-treated blood.     

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20–200 mg L⁻¹, described by the equation S = −0.0767 + 0.00438C (mg L⁻¹), r = 0.999. The detection limit was estimated as 3 mg L⁻¹ at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7–16 mg L⁻¹, described by the equation S = −0.865 + 0.132C (mg L⁻¹), r = 0.999. The detection limit was estimated as 150 μg L⁻¹ at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level.     

The effect of signal suppression and mobile phase composition on the simultaneous analysis of multiple classes of acidic/neutral pharmaceuticals and personal care products in surface water by solid-phase extraction and ultra performance liquid chromatography-negative electrospray tandem mass spectrometry

A new multi-residue method for the determination of 25 acidic/neutral pharmaceuticals (antibiotics, anti-inflammatory/analgesics, lipid regulating agents, diuretics, triazides, H2-receptor antagonists, cardiac glicozides and angiotensin II antagonists) and personal care products (sunscreen agents and preservatives) in surface water with the usage of a new technique: ultra performance liquid chromatography–negative electrospray tandem mass spectrometry (UPLC–MS/MS) was developed and validated. The novel UPLC system with 1.7 μm particle-packed column allowed for good resolution of analytes with the application of low mobile phase flow rates (0.05 mL min⁻¹) and short retention times (from 4.7 min to 13.3 min) delivering a fast and cost-effective multi-residue method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile-phase composition, matrix assisted ion suppression and SPE recovery on the sensitivity of the method was identified and quantified. The instrumental limits of quantification varied from 0.2 μg L⁻¹ to 30 μg L⁻¹. The method limits of quantification were at low nanogram per litre levels and ranged from 0.3 ng L⁻¹ to 30 ng L⁻¹. The instrumental and method intra-day and inter-day repeatabilities were on average less than 5%. The method was successfully applied for the determination of PPCPs in River Taff. Thirteen compounds were determined in river water at levels ranging from a single to a few hundred nanograms per litre. Among them were ten pharmaceuticals (aspirin, salicylic acid, ketoprofen, naproxen, diclofenac, ibuprofen, mefenamic acid, furosemide, sulfasalazine and valsartan) and three personal care products (methyl- and ethylparaben and 4-benzophenone).     

Development of a luminol-based chemiluminescence flow-injection method for the determination of dichlorvos pesticide

A simple, fast chemiluminescence (CL) flow-injection method based on the reaction of luminol with H₂O₂ in the presence of a cationic surfactant (cyltrimethylammonium bromide, CTMAB) has been described for the direct determination of dichlorvos pesticide (DDVP). Under the optimal conditions, the CL intensity was linear to the DDVP concentration in the range of 0.02–3.1 μg ml⁻¹ (r=0.9998, n=10). The relative standard deviation was 3.4% at 0.35 μg ml⁻¹ (n=10), with a detection limit (3σ) of 0.008 μg ml⁻¹ DDVP. The possible reaction mechanism was also discussed. This method has been successfully applied to the determination of trace DDVP residue in vegetable sample and results have been compared with that of the UV method.     

Multiple square wave voltammetry for analytical determination of paraquat in natural water, food, and beverages using microelectrodes

This paper reports on the use of multiple square wave voltammetry (MSWV) for analytical determination of paraquat herbicide at gold microelectrode (Au-ME) in different samples of natural water, food, and beverages. In this work, the MSWV consisted in a sequence of four pairs of potential pulse in the same step and the interval potential evaluated was of the 0.0 V at −1.2 V versus Ag/AgCl 3.0 mol L⁻¹. The paraquat herbicide presented two reduction peaks, in −0.69 V and −0.99 V, with profile of the redox process totally reversible, and the use of multiple pulses allowed a detection of nanomolar levels after the optimization of experimental and voltammetric conditions. Analytical curves were constructed for pulse potential frequency of 250 s⁻¹, pulse amplitude of 50 mV, scan increment of 2 mV and pulse number of 8 pulses in a same step. The two reduction peaks showed that the peak currents were found to be directly proportional to the pesticide concentration in the range comprised between 5.0 × 10⁻⁷ mol L⁻¹ and 1.04 × 10⁻⁵ mol L⁻¹. With this, it was possible to determine detection limits (DL), which resulted in 0.044 μg L⁻¹ (0.044 ppb) and 0.146 μg L⁻¹ (0.146 ppb), respectively, for peak 1 and peak 2. DL results, obtained using MSWV, were 2–3 orders of magnitude lower (10⁻² to 10⁻³) less than those observed for traditional square wave voltammetry or published in literature, clearly pointing to the advantages arising from the possibility of using a MSWV for analytical purposes in contaminated matrices. In addition, the proposed methodology was applied in different samples of natural water, food and beverages without pre-treatment or pre-concentration step, where a recovery measurement indicated that the methodology could be employed to analyze paraquat in such matrices.     

Analysis of acrylamide in coffee and dietary exposure to acrylamide from coffee

An analytical method for analysing acrylamide in coffee was validated. The analysis of prepared coffee includes a comprehensive clean-up using multimode solid-phase extraction (SPE) by automatic SPE equipment and detection by liquid chromatography tandem mass spectrometry using electrospray in the positive mode. The recoveries of acrylamide in ready-to-drink coffee spiked with 5 and 10 μg l⁻¹ were 96±14% and 100±8%, respectively. Within laboratory reproducibility for the same spiking levels were 14% and 9%, respectively. Coffee samples (n = 25) prepared twice by coffee machines and twice by a French Press Cafetière coffee maker contained 8±3 μg l⁻¹ and 9±3 μg l⁻¹ acrylamide. Five ready-to-drink instant coffee prepared twice contained 8±2 μg l⁻¹. Hence, the results do not show significant differences in the acrylamide contents in ready-to-drink coffee prepared by coffee machine, French Press or from instant coffee. Medium roasted coffee contained more acrylamide (10 μg l⁻¹) than dark roasted coffee (5 μg l⁻¹). Males aged 35–45 years, drinking on average 1.1 l coffee per day are exposed to the highest doses of acrylamide from coffee. The dietary intake of acrylamide from coffee comprises, on an average, 10 μg day⁻¹ for males and 9 μg day⁻¹ for females aged 35–45 years. Probabilistic modelling of the exposure of Danish consumers (all adults) to acrylamide from coffee shows a mean exposure of 6.5 μg day⁻¹ and a 95 percentile of 18 μg day⁻¹.     

Continuous flow system for lead determination by faas in spirituous beverages with solid phase extraction and on-line copper removal

A continuous flow system for the determination of lead in home made spirituous beverages was developed. The determination was based on the formation of a neutral chelate of the element with ammonium pyrrolidine dithiocarbamate, its adsorption onto a minicolumn packed with sodium faujasite type Y synthetic zeolite, followed by elution with methyl isobutyl ketone and determination by flame atomic absorption spectrometry. Ethanol and copper interfere strongly in the determination and therefore, must be separated prior to the analysis. Copper is removed by precipitation with rubeanic acid, while ethanol is eliminated by rotaevaporation. Sample solutions containing Pb²⁺ in the concentration range from 5 to 120 μg l⁻¹ at pH 2.5 could be analyzed, by using a preconcentration time of 3 min. Preconcentration factors from 80 to 140 were achieved for a sample volume of 6 ml and the detection limit varied from 1.4 to 3.5 μg l⁻¹, depending on the matrix composition. The relative standard deviations for 60 μg l⁻¹ Pb was 3.2% (n = 10) and the recovery of spikes (20, 40, 60 and 80 μg l⁻¹) added to the samples was estimated within 92–105% range, suggesting that lead can be quantitatively determined in such samples. Determining lead in several samples by an alternative technique further checked the accuracy. Finally, the concentrations of Pb²⁺ determined in 28 samples of Venezuelan spirituous beverages were in 12.6–370.0 μg l⁻¹ range, depending on the fermenting material based on different mixtures of agave, raw sugar cane and white sugar.     

Determination of dioxopromethazine hydrochloride by capillary electrophoresis with electrochemiluminescence detection

The paper presents a rapid method for the determination of dioxopromethazine hydrochloride (DPZ), an antihistamine drug, by the capillary electrophoresis with electrochemiluminescene detection (CE–ECL) using tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) reagent. This CE–ECL detection method has high sensitivity, good selectivity and reproducibility for DPZ analysis. Under the optimized conditions: separation capillary, 38 cm length (25 μm i.d.); sample injection, 10 s at 8 kV; separation voltage, 12.5 kV; running buffer, 20 mmol L⁻¹ sodium phosphate of pH 6.0; detection potential, 1.15 V; 50 mmol L⁻¹ of phosphate buffer (pH 7.14) containing 5 mmol L⁻¹ of Ru(bpy)₃²⁺ in ECL detection cell, the detection limit of DPZ was 0.05 μmol L⁻¹ (S/N = 3). The linear range extended from 5 to 100 μmol L⁻¹. The linear curve obtained was Y = 181.62 + 9.28X with a correlation coefficient of 0.9970. The relative standard deviations of the ECL intensity and the migration time for six continuous injections of 5 μmol L⁻¹ DPZ were 3.7% and 0.92%, respectively. The CE–ECL method was applied to analyze DPZ in real samples including tablets, rat serum and human urine, and satisfactory results were obtained without interference from samples matrix. The CE–ECL technique was proved to be a potential method for the detection of DPZ in clinic analysis.     

Preconcentration and decomposition of perfluorinated carboxylic acids on an activated charcoal cartridge with sodium biphenyl reagent and its determination at microg L(-1) level on the basis of flow injection-fluorimetric detection of fluoride ion

Perfluorinated surfactants of heptafluorobutylate and pentadecafluorooctanoate ions were adsorbed on an activated charcoal cartridge and decomposed with sodium biphenyl (SBP) reagent to form inorganic fluoride ion. The fluoride ion thus formed was determined by flow injection analysis (FIA) using quercetin-Zr complex as a fluorimetric reagent, where λ_ex and λ_em were 422 and 491 nm, respectively. The limit of detection for fluoride ion by the FIA system was developed to 1.1 × 10⁻⁶ M (signal to noise ratio of three), when 50% (v/v) tetrahydrofuran (THF) was used as a dissolving solvent for quercetin. The perfluorinated surfactants in the sample solution were quantitatively adsorbed on the cartridge containing 100 mg of activated charcoal and were decomposed with 0.5 mL of sodium biphenyl reagent after drying thoroughly by flowing through dry nitrogen gas. The fluoride ion formed was recovered with 3 mL of purified water as an eluent, and it was determined by the fluorimetric flow injection system. The blank fluorescence signal accompanied during the adsorption/decomposition on the cartridge was reduced by washing the activated charcoal with acetone. The blank signal was also observed from dimethoxyethane, which was used in sodium biphenyl reagent. When 600 mL sample solution was used and 200 times enrichment was applied, the heptafluorobutylate and pentadecafluorooctanoate ions at the concentrations of 2.1 μg L⁻¹ were quantitatively recovered as fluoride ion, and the limit of detections for the perfluorinated surfactants were 0.3 and 0.3 μg L⁻¹ for the two perfluorinated surfactants, respectively (3 sigma of the blank signal).     

Pungency evaluation of onion cultivars from the Venezuelan West-Center region by flow injection analysis-UV-visible spectroscopy pyruvate determination

A flow injection analysis (FIA) method was developed for the determination of pyruvate in onion cultivars (Allium cepa L.) from the West-Center region of Venezuela. The reference Schwimmer and Weston (1961) (J. Agric. Food Chem. 9 (1961) 301) Batch method was modified and adapted to FIA conditions. The formation kinetic of the 2,4-dinitrophenylhydrazine (DNPH)–pyruvate complex was evaluated at room temperature and at 37 °C. It was demonstrated the suitability of the chromopher formation at room temperature. The optimal values for the FIA parameters were: sample injection volume 3 mL, flow rate 6 mL min⁻¹, reactor length 1.5 m, sodium hydroxide concentration 1.0 mol L⁻¹ and hydrochloric acid concentration 0.5 mol L⁻¹. The working calibration range was extended from 80 mg L⁻¹ (Batch method) to 700 mg L⁻¹ with the FIA set up. The sample dilution step is thus avoided, simplifying the whole analysis process. The pungency in representative samples of the cultivars Yellow granex 438, Ultra Hybrid and Red onion “Sangre de Toro” was evaluated by the flow injection analysis (FIA)–pyruvate method and the results were compared to the reference Batch pyruvate method and to the taste panel test. Non-significant differences were found at the 95% of confidence level between the FIA method and the Batch reference method. Correlation coefficient when comparing the FIA results to the taste panel test was r² = 0.8353. Significant differences (P < 0.05) were found in the pungency of the cultivars, the Ultra Hybrid having the highest pungency. The pungency order from minor to major was: Red onion, Texas Grano 438 and Ultra Hybrid.