Cadmium Determination in Sedimented Dust by Atomic Emission Spectrometry With a New Radiofrequency Capacitively Coupled Plasma Source

ABSTRACT

A new radiofrequency capacitively coupled plasma source (r.f.CCP) was used for Cd determination in dust samples by atomic emission spectrometry. The plasma torch consists of a molybdenum tube electrode and one or two ring electrodes situated outside the quartz tube. Plasma was operated at 27.12 MHz, at low power (275 W) and low gas consumption (0.4 1 min^? argon flow). The choice of the optimum operating conditions for Cd determination in dust samples dissolved in acids and pneumatically nebulized is presented. The results obtained in such samples were compared with those obtained by flame atomic absorption spectrometry (FAAS). The matrix effect of NaCl and CaCl₂ on Cd emission was also studied depending of the plasma coupling system. The true limit of detection for Cd in dust sample by r.f.CCP-AES is 3 μg g^?1. Concentration of Cd higher than 10 μg g^?1 can be determined by the proposed method with a relative standard deviation within the range 5 - 10%. The recovery is 100 ± 10%.     

Determination of inorganic and total mercury by vapor generation atomic absorption spectrometry using different temperatures of the measurement cell

A simple and inexpensive laboratory-built flow injection vapor generation system coupled to atomic absorption spectrometry (FI-VG AAS) for inorganic and total mercury determination has been developed. It is based on the vapor generation of total mercury and a selective detection of Hg^2 + or total mercury by varying the temperature of the measurement cell. Only the inorganic mercury is measured when the quartz cell is at room temperature, and when the cell is heated to 650 °C or higher the total Hg concentration is measured. The organic Hg concentration in the sample is calculated from the difference between the total Hg and Hg^2 + concentrations. Parameters such as the type of acid (HCl or HNO₃) and its concentration, reductant (NaBH₄) concentration, carrier solution (HCl) flow rate, carrier gas flow rate, sample volume and quartz cell temperature, which influence FI-VG AAS system performance, were systematically investigated. The optimized conditions for Hg^2 + and total Hg determinations were: 1.0 mol l^− 1 HCl as carrier solution, carrier flow rate of 3.5 ml min^− 1, 0.1% (m/v) NaBH₄, reductant flow rate of 1.0 ml min^− 1 and carrier gas flow rate of 200 ml min^− 1. The relative standard deviation (RSD) is lower than 5.0% for a 1.0 μg l^− 1 Hg solution and the limit of quantification (LOQ, 10 s) is 55 ng g^− 1. Certified samples of dogfish muscle (DORM-1 and DORM-2) and non-certified fish samples were analyzed, using a 6.0 mol l^− 1 HCl solution for analyte extraction. The Hg^2 + and CH₃Hg⁺ concentrations found were in agreement with certified ones.     

Electrocatalytic Application of Girard's Reagent T to Simultaneous Determination of Furaldehydes in Pharmaceutical and Food Matrices by Highly Sensitive Voltammetric Methods

Sensitive and precise voltammetric methods for the determination of trace amounts of furaldehydes, mainly as furfural (F) and 5‐hydroxymethyl‐2‐furaldehyde (HMF), in foods, pharmaceutical and other matrices is described. Determination of total furaldehyde at <μg g^?1 levels in alkaline buffered aqueous media was individually investigated. By the use of ordinary SWV and adsorptive square wave stripping voltammetry (Ad‐SWSV), the detection limits for determination of F and HMF found to be 400 and 10 ng g^?1, respectively. At a 1.0 μg g^?1 level of furfural in sample, the relative standard deviation (n=4) was 2.79%. The application of Ad‐SWSV to the determination of F and HMF, after their in situ derivatization with trimethylaminoacetohydrazide chloride (Girard's reagent T) at a static mercury drop electrode (SMDE) in NH₃‐NH₄Cl buffer of pH 9.5, resulted in a limit of detection of 10 ng g^?1 for the resolved peaks of HMF and F. The results obtained by the proposed method for the real samples were compared with the corresponding results from UV‐spectrophotometry and HPLC experiments in various matrices.     

Determination of total and inorganic mercury in biological and environmental samples with on-line oxidation coupled to flow injection-cold vapor atomic absorption spectrometry

A method for determination of inorganic and total mercury by flow injection-cold vapor atomic absorption spectrometry (FI-CVAAS) with on-line oxidation was developed. Potassium peroxodisulphate and sulphuric acid were used as oxidizing agents so that decomposition of organomercury compounds could be achieved. Depending on the temperature selected, inorganic or total mercury could be determined with the same FI manifold. In order to assess the method performance, synthetic wastewater, wastewater, urine and saline water samples were spiked with inorganic mercury, methylmercury and phenylmercury. Quantitative recoveries were obtained for the three mercury species, except with the synthetic wastewater when the chemical oxygen demand value was higher than 1000 mg l⁻¹. In most cases, the standard addition method was usually needed for calibration. LODs calculated as 3 σ/m were 0.47 μg l⁻¹ for inorganic mercury and 0.45 μg l⁻¹ for total mercury. R.S.D. values corresponding to peak height measurements were 1.5 and 2.2% for inorganic mercury and total mercury, respectively. The accuracy of the method was tested by analyzing 5 mol l⁻¹ hydrochloric acid extracts of seven biological and environmental CRMs. LODs in the solid CRMs ranged from 0.032 to 0.074 μg g⁻¹.     

Indirect Mercury Speciation in Biological Tissues by Closed‐Vessel Microwave‐Assisted Digestion and Flow‐Injection Cold‐Vapor Atomic Fluorescence Detection

Abstract

A simple and rapid method based on closed vessel microwave‐assisted extraction was developed to determine total, inorganic mercury and organomercury in biological tissues. Total mercury was extracted using HNO₃:H₂O₂ (4:1) mixture. In a separate subsample, extraction of mercury species was carried out with tetramethylammonium hydroxide (TMAH). The total and inorganic mercury analyses were carried out by flow‐injection cold‐vapor atomic fluorescence spectrometry (FI‐CV‐AFS). The organomercury concentration was calculated by difference. Considering a sample amount of 0.2 g, the detection limits were 4 and 26 ng/g for total and inorganic mercury, respectively. The accuracy of the procedures was checked by analyzing certified reference materials and recovery studies of spiked fish tissues.     

Determination of Arsenic,Mercury and Barium in Herbarium Mount Paper Using Dynamic Ultrasound-Assisted Extraction Prior to Atomic Fluorescence and Absorption Spectrometry

A dynamic ultrasound-assisted extraction method using Atomic Absorption and Atomic Fluorescence spectrometers as detectors was developed to analyze mercury, arsenic, and barium from herbarium mount paper originating from the herbarium collection of the National Museum of Wales. The variables influencing extraction were optimized by a multivariate approach. The optimal conditions were found to be 1% HNO₃ extractant solution used at a flow rate of 1 mL min^?1. The duty cycle and amplitude of the ultrasonic probe was found to be 50% in both cases with an ultrasound power of 400 W. The optimal distance between the probe and the top face of the extraction chamber was found to be 0 cm. Under these conditions the time required for complete extraction of the three analytes was 25 min. Cold vapor and hydride generation coupled to atomic fluorescence spectrometry was utilized to determine mercury and arsenic, respectively. The chemical and instrumental conditions were optimized to provide detection limits of 0.01 ng g^?1 and 1.25 ng g^?1 for mercury and arsenic, respectively. Barium was determined by graphite-furnace atomic absorption spectrometry, with a detection limit of 25 ng g^?1. By using 0.5 g of sample, the concentrations of the target analytes varied for the different types of paper and ranged between 0.4–2.55 µg g^?1 for Ba, 0.035–10.47 µg g^?1 for As, and 0.0046–2.37 µg g^?1 for Hg.     

Sample treatment selection for routine mercury speciation in seafood by gas chromatography–atomic fluorescence spectroscopy

A general analytical strategy for mercury speciation in seafood samples has been proposed to increase sample throughput. This consists of the initial determination of total mercury content, and then mercury speciation using gas chromatography coupled to atomic fluorescence spectroscopy. The appropriate sample treatment for mercury speciation is selected between a method based on aqueous ethylation with sodium tetraethylborate (Approach A: a rapid methodology for samples with methylmercury concentrations between 150 and 2000 ng g^?1) and another one based on the determination of organomercury chlorides (Approach B: a much more time‐consuming methodology, applicable to samples with methylmercury at 1.2–200 ng g^?1). Both procedures have been used together for the analysis of bivalves and fish samples. Copyright © 2005 John Wiley & Sons, Ltd.     

Spectrophotometric Determination of Furosemide Based on Its Complexation with Fe(III) in Ethanolic Medium Using a Flow Injection Procedure

Abstract

A fast flow injection procedure with spectrophotometric detection based on the furosemide complexation with Fe(III) ions in ethanolic media is described. As carrier the flow single line system configuration used an ethanolic 10^?2 mol L^?1 Fe(III) solution flowing at 1.0 mL min^?1, a 50 cm sample loop (250 µL total sample injection), and a 50 cm long reactor coil, at room temperature. The detection at 513 nm presented a linear dynamic range from 1.00×10^?4 to 1.00×10^?2 mol L^?1, obeying the linear equation Abs=8.9×10^?3+22.3×[furosemide] (r=0.998, n=7). The limit of detection (3σ/slope) was 3.00×10^?5 mol L^?1. The proposed method was applied to four commercial samples from different suppliers, as tablets and ampoules, and a synthetic urine sample spiked with the analyte without an effect from the other substances present in the formulation. The proposed procedure presented an analytical frequency of 95 measurements per hour. The results agreed with those from both the label and those determined by a spectrophotometric comparative procedure. Recoveries close to 100% were found in the commercial formulations and synthetic urine matrixes.     

Simple mercury fractionation in biological samples by CV AAS following microwave-assisted acid digestion or TMAH pre-treatment

A simple and reliable method to determine total and inorganic mercury in biological certified reference material (CRM) by cold vapor atomic absorption spectrometry (CV AAS) is proposed. After the CRM treatment at room temperature with tetramethylammonium hydroxide (TMAH), inorganic mercury is determined by CV AAS. Total mercury is measured by the same technique, after sample acid digestion in a microwave oven. Organic mercury, basically methylmercury, is obtained by difference. In both procedures, the quartz tube is kept at room temperature. By means of analysis of the following reference materials: pig kidney, lobster hepatopancreas, dogfish liver and mussel tissue, it was clear that the difference between the total and inorganic mercury concentrations agrees with the methylmercury concentration. Only one calibration curve against aqueous standards in acidic medium was carried out for both procedures. The concentrations obtained by both procedures are in agreement with the certified values according to the t-test at a 95% confidence level. The relative standard deviations were lower than 3.0% for digested CRM and 6.0% for CRM treated with TMAH for most of the samples. The limits of detection in the samples were 0.02 µg g^− 1 and 0.04 µg g^− 1 for inorganic and total Hg, respectively, since the sample mass for total mercury was half of that for inorganic mercury determination. Simplicity and high efficiency without using chromatographic techniques are some of the qualities of the proposed method, being adequate for fractionation analysis of mercury in biological samples.     

Application of ion-selective electrodes in environmental analysis : Determination of Acid and Fluoride concentrations in Rain-water with a Flow-Injection System

A flow-injection method is described for the measurement of acid and fluoride concentrations. The conditions were optimized to ensure small sample and reagent consumption, low detection limit and the highest rate of analysis allowed by the potentiometric sensor. With a microcapillary pH-sensitive glass electrode, 20-μl sample volumes and 1.0–1.5 ml min^?1 carrier flow rates, strong acids were determined at concentrations as low as 10^?5 M (0.2 nmol of acid in 20 μ1). The relative standard deviation was about 1% at 10?4 M strong acid concentration at an injection rate of 500–550 h^?1. With a flow- through fluoride-selective electrode, 250-μl sample volumes and a 1 ml min^?1 carrier flow rates, fluoride concentrations as low as 10^?7 M were measured (ca. 0.5 ng of fluoride in 250 μ1). The injection rate was 40 h^?1 at concentrations below 10^?6 M, but 60 h^?1 above 10^?5 M. The methods were used successfully for determining the acid and fluoride concentrations in rain-waters.     

Flow injection determination of hydrogen peroxide by means of a solid-state-peroxyoxalate chemiluminescence reactor

A solid-state reactor for detection of hydrogen peroxide in aqueous samples by peroxyoxalate chemiluminescence is described. Bis(2,4,6-trichlorophenyl)oxalate in solid form is packed into a bed reactor, which eliminates mixing problems and facilitates the instrumental development. Perylene is added as a sensitizer to a water/acetonitrile (20:80) carrier stream into which the samples (200–600 μl) are injected. Detection limits of 6 × 10^?9 M H₂O₂ (0.2 μg l^?1) are obtained with both a commercial and a home-made luminescence detector. Calibration graphs are linear up to 10^?5 M. The r.s.d. for 2 × 10^?7 M (6.7 μg^?1) hydrogen peroxide (n = 10) is 2.8%. Sample throughput is ca. 120 h^?1.     

Flow Injection Determination of Hydrogen Peroxide Using a Carbon Paste Electrode Modified with a Manganese Dioxide Film

Abstract

A manganese dioxide film modified carbon paste electrode was developed for use as an amperometric sensor for the determination of hydrogen peroxide (H₂O₂) in ammoniacal aqueous solutions. The electrode showed a stable response towards H₂O₂ after electrochemical activation. Effects of flow rate, operating potential, concentration, injection volume and interferences were investigated. A linear response towards H₂O₂ from 5 μg.l^?1 to 450 mg.l^?1 and a detection limit (3 signal-to-noise ratio) of 4.7 μg.l^?1 was found. The method was employed for the determination of H₂O₂ in rain water samples.     

Determination of Tetracyclines in Water Samples Using Liquid Chromatography with Fluorimetric Detection

A liquid chromatographic method with fluorimetric detection is proposed for the determination of trace levels of oxytetracycline, tetracycline, chlortetracycline and doxycycline in water samples. The analytes are preconcentrated by solid phase extraction using reversed phase polymeric cartridges and acetonitrile as eluent. Preconcentration factors up to 125 can be obtained. The chromatographic separation is performed on a polymeric column with a gradient elution program using mobile phases based on mixtures of acetonitrile and 0.01 mol L^?1 oxalic acid aqueous solution at a flow rate of 1.2 mL min^?1. Tetracyclines are post-column derivatized with a reagent solution consisting of 0.1 mol L^?1 Mg(II) at pH 9 at a flow rate of 0.6 mL min^?1. The highly fluorescent Mg(II) chelates are detected at λ _ex = 374 nm and λ _em = 499 nm. The detection limits of the whole process are in the low μg L^?1 level. The proposed method has been applied to the analysis of spiked natural water samples, and recovery rates higher than 80% have been obtained.     

Simple mercury fractionation in biological samples by CV AAS following microwave-assisted acid digestion or TMAH pre-treatment

A simple and reliable method to determine total and inorganic mercury in biological certified reference material (CRM) by cold vapor atomic absorption spectrometry (CV AAS) is proposed. After the CRM treatment at room temperature with tetramethylammonium hydroxide (TMAH), inorganic mercury is determined by CV AAS. Total mercury is measured by the same technique, after sample acid digestion in a microwave oven. Organic mercury, basically methylmercury, is obtained by difference. In both procedures, the quartz tube is kept at room temperature. By means of analysis of the following reference materials: pig kidney, lobster hepatopancreas, dogfish liver and mussel tissue, it was clear that the difference between the total and inorganic mercury concentrations agrees with the methylmercury concentration. Only one calibration curve against aqueous standards in acidic medium was carried out for both procedures. The concentrations obtained by both procedures are in agreement with the certified values according to the t-test at a 95% confidence level. The relative standard deviations were lower than 3.0% for digested CRM and 6.0% for CRM treated with TMAH for most of the samples. The limits of detection in the samples were 0.02 µg g^{− 1} and 0.04 µg g^{− 1} for inorganic and total Hg, respectively, since the sample mass for total mercury was half of that for inorganic mercury determination. Simplicity and high efficiency without using chromatographic techniques are some of the qualities of the proposed method, being adequate for fractionation analysis of mercury in biological samples.     

Determination of nanogram quantities of mercury in water with a gold-plated piezoelectric crystal detector

The use of a gold-coated piezoelectric crystal, coupled with a direct reduction technique, is described for the determination of mercury in water. The linear range is 5–100 ng with a sensitivity of 1.78 Hz ng^-1 of mercury. Reversibility of the detector is achieved by thermal desorption at 170°C. The effect of carrier gas flow rate, sample size and detector cell configuration on the sensitivity are discussed.     

Redox Speciation of Inorganic Arsenic in Water and Saline Samples by Adsorptive Cathodic Stripping Voltammetry in the Presence of Sodium Diethyl Dithiocarbamate

This paper describes a new voltammetric procedure for the inorganic speciation of As(III) and As(V) in water samples. The procedure is based on the chemical reduction of arsenate [As(V)] to arsenite [As(III)] followed by the voltammetric determination of total arsenic as As(III) at the hanging mercury drop electrode (HMDE) by adsorptive cathodic stripping voltammetry (AdCSV) in the presence of sodium diethyl dithiocarbamate (SDDC). The reduction step involved the reaction with a mixture of Na₂S₂O₅ and Na₂S₂O₃ in the concentrations 2.5 and 0.5 mg mL^?1, respectively, and the sample heating at 80 °C for 45 min. The linear range for the determination of total arsenic as As(III) in the presence of SDDC was between 5 and 150 μg L^?1 for a deposition time of 60 s (r=0.992). A detection limit of 1.05 μg L^?1 for total As was calculated for the method in water samples using a deposition time of 60 s. The detection limits of 4.2 μg L^?1 and 15.0 μg L^?1 for total As in seawater and dialysis concentrates, respectively, were calculated using a deposition time of 60 s. The relative standard deviations calculated were 2.5 and 4.0% for five measurements of 20 μg L^?1 As(V) as As(III) in water and dialysis concentrates, respectively, after chemical reduction under optimized conditions. The method was applied for the determination of As(III) and total As in samples of dialysis water, mineral water, seawater and dialysis concentrates. Recovery values between 86.0 and 104.0% for As(III) and As(V) added to the samples prove the satisfactory accuracy and applicability of the procedure for the arsenic monitoring.     

Factors affecting the detection limit of a flow- injection spectrophotometric procedure

Design criteria for manifolds to obtain adequated sensitivity and freedom from certain types of noise are discussed. For the determination of chloride by the mercury(II) thiocynate method, the mergin-streams manifold, needed to eliminated negative peaks at low concentrations and refractive index effects, increased the baseline noise because of inefficient mixing at the confluence point. Packed-bed reactors and single-bead-string reactors (SBSR) significantly improved the baseline noise. Refractive index effects caused by sample concentration gradients were eliminated by the injection of large volumes (>500 μl), so that the detector could view a homogeneous central part of the sample zone. This approach maximises the signal because the dispersion is governed only by the relative flow rates of the carrier and reagent streams. The detection limits for chloride were improved to 40 ng l^?1 in aqueous solutions of low ionic strength and to 1.3 mg l^?1 in 5.25% (w/v) potassium sulphate.     

Solid phase extraction and preconcentration of trace mercury(II) from aqueous solution using magnetic nanoparticles doped with 1,5-diphenylcarbazide

A new method for solid-phase extraction and preconcentration of trace mercury(II) from aqueous solution was developed using 1,5-diphenylcarbazide doped magnetic Fe₃O₄ nanoparticles as extractant. The surface treatment did not result in the phase change of Fe₃O₄. Various factors which influenced the recovery of the analyte were investigated using model solutions and batch equilibrium technique. The maximum adsorption occurred at pH?>?6, and equilibrium was achieved within 5 min. Without filtration or centrifugation, these mercury loaded nanoparticles could be separated easily from the aqueous solution by simply applying an external magnetic field. At optimal conditions, the maximum adsorption capacity was 220 μmol g^?1. The mercury ions can be eluted from the composite magnetic particles using 0.5 mol L^?1 HNO₃ as a desorption reagent. The detection limit of the method (3σ) was 0.16 μg L^?1 for cold vapor atomic absorption spectrometry, and the relative standard deviation was 2.2%. The method was validated by the analysis of a certified reference material with the results being in agreement with those quoted by manufactures. The method was applied to the preconcentration and determination of trace inorganic mercury(II) in natural water and plant samples with satisfactory results.     

Isomeric Transformation Of 4-Aminobiphenyl by U.V. Radiation and its Influence on the Determination by Flow Injection Analysis with Amperometric and Spectrophotometric Detection.

Abstract

Two flow-injection methods for the determination of 4-aminobiphenyl by amperometry (glassy carbon electrode) and spectrophotometry are proposed. A sample volume of 200 or 400 μl containing an analyte concentration of 0.1–1.0 μg ml^?1 or 0.8–24.0 μg ml^?1 for amperometric or spectrophotometric detection, respectively, is injected into a carrier stream containing 0.04 or 0.02 M Britton-Robinson buffer at pH 10.0 or 8.0, respectively.

The throughput thus achieved is 200 (amperometry) and 240 samples/h (spectrophotometry) and the relative standard deviation less than 2.5% and 4.2% respectively.

Both methods were applied to the determination of 4-aminobiphenyl in commercially available, legally permitted food colouring additive.     

Kinetic Flow Injection Spectrophotometric Determination of Nitrite by its Catalytic Effect on the Oxidation of Chlorophosphonazo-pN by Bromate

Abstract

A flow injection kinetic method has been developed for the determination of nitrite, based on its catalytic effect on bromate oxidation of chlorophosphonazo-pN in H₂SO₄ medium. The reaction is followed spectrophotometrically by measuring the decrease in the absorbance at 551 nm. The sampling frequency was 83 h^?1. The calibration curve was linear between 0.050 and 1.00 μg/ml, and the detection limit was 0.018 μg/ml. The proposed method was applied to the determination of nitrite in waters and soil with satisfactory results.