Solid-phase reactors in sequential injection analysis. Determination of manganese (II) in tap water and effluent streams using a solid-phase lead(IV) dioxide reactor in a sequential injection system

The determination of manganese(II) in tap water and effluent streams, using a solid-phase reactor incorporated into a sequential injection system was investigated. Mn2+-ions in samples injected into a carrier stream, were oxidised by solid lead(IV) dioxide suspended on silica gel beads to form MnO4- -ions which were detected spectrophotometrically at 526 nm. The linear range of the system is from 1 to 7 mg L(-1) with a detection limit of 0.62 mg L(-1). The proposed system is suitable for the determination of manganese(II) in tap and effluent streams at a rate of approximately 50 samples per hour with a relative standard deviation of better than 3%. Statistical comparison between the proposed sequential injection system and a standard ICP method revealed that there is no significant difference between the two methods at the 95% confidence level for effluent streams and at 99.9% for tap water.     

On-line monitoring of phosphate in natural water and effluent streams using sequential injection analysis

Automation of the molybdenum blue method by sequential injection (SIA) for the on-line monitoring of phosphate in natural waters is presented. Although sequential injection analysis runs at one fifth the speed of conventional FIA, it presents many advantages such as simplicity of the manifold, robustness and computer compatibility. A reduction in reagent and sample consumption is also observed. Flow detector fouling does not occur in SIA manifolds as the detector is in contact with water between analysis. The proposed SIA analyser is able to monitor phosphate in the range 0–70 mg l^–1 with a standard deviation of 0.9%. The detection limit is 0.5 mg l^–1 PO ₄ ^3– .     

Determination of sulphuric acid in process effluent streams using sequential injection titration

Sulphuric acid in process effluent streams from an electrorefining copper plant was analysed with a sequential injection (SI) titration system using sodium hydroxide as titrant. In the proposed SI titration system a base titrant, acid analyte and base titrant zone were injected sequentially into a distilled water carrier stream in a holding coil and swept by flow reversal through a reaction coil to the detector. The base zones contained bromothymol blue as indicator and the endpoint was monitored spectrophotometrically at 620 nm. The influence of carrier stream flow rate, acid and base zone volumes and titrant concentration on the linear range of the method was studied to obtain an optimum. A linear relationship between peak width and logarithm of the acid concentration was obtained in the range 0.006-0.178 mol l(-1) of H(2)SO(4) for a NaOH concentration of 0.002 mol l(-1). The results obtained for the SI titration of process samples were in good agreement with a standard potentiometric method with an RSD<0.75% and a sample frequency of 23 samples h(-1).     

Determination of mercury(II) traces in drinking water by inhibition of an urease reactor in a flow injection analysis (FIA) system

 The integration of an urease reactor into a gas diffusion flow injection system was investigated for the determination of urease inhibitors. The enzyme was immobilized by entrapping in polyacrylamide gel. Besides copper and silver ions mercury ions inhibit the conversion of urea to carbon dioxide and ammonia catalysed by urease. The pH change of the carrier solution caused by the ammonia released was measured potentiometrically with a pH electrode. The inhibition behaviour of Hg(II) ions was investigated. A linear range from 2 to 20 μg L^-1 Hg(II) was obtained after a 90 s inhibition, with a correlation coefficient of r=0.9997. The relative standard deviation was 1.4% for five measurements of 2 μg L^-1Hg(II). A sample frequency of 7 h^-1 was achieved. The inhibited enzyme can be reactivated. The method was applied to the determination of Hg(II) in two drinking water samples. Received: 16 April 1996/Revised: 3 June 1996/Accepted: 11 June 1996     

Selective solid-phase extraction of lead(II) from biological and natural water samples using surface-grafted lead(II)-imprinted polymers

A new Pb(II)-imprinted amino-functionalized silica gel sorbent was synthesized by an easy one-step reaction by combining a surface imprinting technique for selective solid-phase extraction of trace Pb(II) prior to its determination by inductively coupled plasma optical emission spectrometry. The Pb(II)-imprinted amino-functionalized silica gel sorbent was characterized by Fourier transform infrared spectroscopy. Compared to non-imprinted polymer particles, the ion-imprinted polymers had higher selectivity and adsorption capacity for Pb(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Pb(II) was 19.66 and 6.20 mg g^?1, respectively. The largest selectivity coefficient of the Pb(II)-imprinted sorbent for Pb(II) in the presence of Cd(II) was over 450. The relative selectivity (α _r) values of Pb(II)/Cd(II) were 49.3 and 46.3, which were greater than 1. The distribution ratio (D) values of Pb(II)-imprinted polymers for Pb(II) were much larger than that for Cd(II). The detection limit (3σ) was 0.20 μg L^?1. The relative standard deviation was 2.0% for 11 replicate determinations. The method was validated for the analysis three certified reference materials (GBW 08301, GBW 08504, GBW 08511), and the results are in good agreement with standard values. The method was also successfully applied to the determination of trace lead in plants and water samples with satisfactory results.     

Determination of salbutamol using on-line solid-phase extraction and sequential injection analysis. Comparison of chemiluminescence and fluorescence detection

Determination of salbutamol using sequential injection analysis (SIA) with chemiluminescence and fluorescence detection has been devised. The chemiluminescence signal was emitted during the oxidation of salbutamol by potassium permanganate in sulfuric acid medium. Sodium polyphosphate was used as chemiluminescence enhancer. The fluorescence signal (excitation wavelength 230 nm) was also measured in sulfuric acid medium. Both detection techniques were compared with respect to the application of the methods to the determination of salbutamol in biological materials. The sample pre-treatment takes place directly in the SIA system, when salbutamol is adsorbed on the solid-phase (Baker-carboxylic acid) microcolumn integrated into the system. Sulfuric acid serves both as the reagent and the eluent. The lab-made SIA system consisted of a 2.5-mL Cavro syringe pump, ten-port Vici Valco selection valve and Spectra-Physics FS 970 fluorescence detector, which was lab-modified for chemiluminescence detection. The system was controlled by a PC using originally compiled LabVIEW-supported software. Concentrations, volumes of reagents and flow rates were optimised by a simplex method. Salbutamol was determined in the linear range 0.05-10 microg mL(-1) (RSD 1.53%), with the detection limit (3 sigma) 0.03 microg mL(-1) and sample throughput of 42 samples per hour with chemiluminescence detection in standard solutions. The fluorescence detection enabled the determination of salbutamol in standard solutions in the linear range 0.5-100 microg mL(-1) (RSD 2.69%), with the detection limit 0.2 microg mL(-1) and sample throughput of 24 h(-1). The proposed methods were applied to the determination of salbutamol in human serum and urine. However, serum is a very complicated matrix and the SIA-SPE analysis did not provide satisfactory results. It was possible to determine salbutamol in human urine using this technique. Better recovery was achieved with fluorescence detection.     

Determination of tetramethylthiuram disulfide (thiram) for residual analysis in food using spectrophotometry coupled with a solid-phase reactor (SPR) in a flow system

An analytical method was developed for quantification of the fungicide thiram (tetramethylthiuram disulfide), based on its capacity to complex Cu²⁺ ions. A solid-phase reactor (SPR) was coupled in a flow system containing a spectrophotometer as detector. The SPR consisted of a tube filled with finely ground resin, in which copper(II) phosphate was immobilised prior to polymerisation. Contact of thiram with the Cu²⁺ ions immobilised in the resin resulted in the formation of a strongly coloured Cu²⁺/thiram complex. Maximum absorbance of the Cu²⁺/thiram complex was obtained at a wavelength of 439 nm. The usefulness of the methodology has been evidenced by the determination of thiram residues in corn and bean grains. Previously, a variety of transition metal cations which would form coloured complexes with tetramethylthiuram disulfide were tested.     

Application of manganese(IV) dioxide microcolumn for determination and speciation of nitrite and nitrate using a flow injection analysis-flame atomic absorption spectrometry system

A flow injection (FI) method with flame atomic absorption spectrometry (FAAS) detection was developed for the determination and speciation of nitrite and nitrate in foodstuffs and wastewaters. The method is based on the oxidation of nitrite to nitrate using a manganese(IV) dioxide oxidant microcolumn where the flow of the sample through the microcolumn reduces the MnO₂ solid phase reagent to Mn(II), which is measured by FAAS. The absorbance of Mn(II) are proportional to the concentration of nitrite in the samples. The injected sample volume was 400 μL with a sampling rate of analyses was 90 h⁻¹ with a relative standard deviation better than 1.0% in a repeatability study. Nitrate is reduced to nitrite in proposed FI-FAAS system using a copperized cadmium microcolumn and analyzed as nitrite. The calibration curves were linear up to 20 mg L⁻¹ and 30 mg L⁻¹ with a detection limit of 0.07 mg L⁻¹ and 0.14 mg L⁻¹ for nitrite and nitrate, respectively. The results exhibit no interference from the presence of large amounts of ions. The method was successfully applied to the speciation of nitrite and nitrate in spiked natural water, wastewater and foodstuff samples. The precision and accuracy of the proposed method were comparable to those of the reference spectrophotometric method.     

Determination of paracetamol in pharmaceutical formulations using a sequential injection system

A simple method for the rapid determination of paracetamol in pharmaceutical formulations is described. The method involves oxidation of paracetamol by potassium hexacyanoferrate(III) and a subsequent reaction with phenol in the presence of ammonia. The blue complex formed is measured at 630 nm. The system has a sample frequency of 27 samples per h with a detection limit of 0.2 mg l⁻¹. The calibration curve is linear up to 60 mg l⁻¹ with a relative standard deviation of 1.2% (n=10).     

Determination of cadmium and lead in river water by sequential metal vapor elution analysis using a step-heated column

Determination of cadmium and lead in river water by sequential metal vapor elution analysis (SMVEA, column temperature; >1210 K) with argon carrier gas and an atomic absorption detector (AA) is reported. The column was a molybdenum tube inserted a tungsten coil. The flow rate of carrier gas was 1.8 ml min^–1. Cadmium and lead were separated from Ca, Fe, K, Na, and Zn metal vapours by SMVEA with the step-heated column (1210–1520 K) at an atomization temperature of 1830 K. Under the optimal experimental conditions, the recoveries of spiked-cadmium and lead in river waters were in the range of 91 to 106%. It is to determine cadmium and lead in river water without the interferences by matrix elements observed by electrothermal AAS, after only the addition of hydrochloric acid to the sample.     

Comparison of soluble manganese(IV) and acidic potassium permanganate chemiluminescence detection using flow injection and sequential injection analysis for the determination of ascorbic acid in Vitamin C tablets

The limits of detection (3s) for ascorbic acid were 5×10⁻⁸ M with acidic potassium permanganate using both flow injection analysis (FIA) and sequential injection analysis (SIA) whereas the soluble manganese(IV) afforded 1×10⁻⁸ M and 5×10⁻⁹ M for FIA and SIA, respectively. Determinations of ascorbic acid in Vitamin C tablets were achieved with minimal sample pretreatment using a standard additions calibration and gave good agreement with those of iodimetric titration.     

Flow injection analysis of chloride in tap and sewage water using ion-selective electrode detection

Summary The application of a chloride-selective electrode in flow injection analysis of chloride in tap and sewage water samples is described. With an extremely simple experimental set-up, from 60 to 120 samples per hour can be analysed. The standard deviation lies at 5%, when the chloride content is above 100 ppm, and 10%, if 10 ppm are present. Using a AgCl single crystal ion-selective electrode and high carrier solution flow rates, interfering anions like iodide, bromide, etc. are kinetically discriminated against and interfere only at orders of magnitude less than usual.

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Fließinjektionsanalyse von Chlorid in Leitungs- und Abwasser mit Hilfe der Detektion durch eine ionen-selektive Elektrode

Zusammenfassung Es wird der Einsatz einer ionenselektiven Chloridelektrode in Verbindung mit der Fließinjektionsanalyse von Chlorid in Leitungs- und Abwasserproben beschrieben. Mittels einer extrem einfachen Anordnung lassen sich so zwischen 60 und 120 Proben stündlich analysieren. Die Standardabweichung beträgt bei Chloridgehalten >100 ppm ca. 5% und bei Gehalten um 10 ppm ca. 10%. Wenn eine AgCl-Einkristallmembranelektrode in Verbindung mit einer hohen Flußrate benutzt wird, stören die üblichen Störionen, wie Iodid, Bromid usw., um Größenordnungen weniger als üblich.

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Dedicated to Prof. Dr. H. Monien on the occasion of his 60th birthday

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1983 on leave from Analytical Chemistry Department, Higher Chemical Technological Institute, 8, Kliment-Ochridsky-Str., Sofia 1156, Bulgaria     

Determination of sources of lead in tap water by inductively coupled plasma mass spectrometry (ICP-MS)

We measured the concentrations of Pb and its isotope ratios in coconmittantly obtained tap water and plumbing materials by inductively coupled mass spectrometry (ICP-MS). The Pb concentrations were determined by external calibration with²⁰⁹Bi as an internal standard. Isotope ratios were measured and mass discrimination corrected by normalization to NIST SRM-981 (common lead isotopic standard). Student/s t-test was used to compare the isotopic ratios of²⁰⁶Pb/²⁰⁷Pb,²⁰⁶Pb/²⁰⁸Pb, and²⁰⁷Pb/²⁰⁸Pb in the tap water with those in various plumbing materials. The comparisons revealed that the source of Pb in most of the tap water samples was derived from copper pipe or solder.     

An electrochemical assay for the determination of Se (IV) in a sequential injection lab-on-valve system

A sequential injection lab-on-valve (LOV) unit, integrating a miniaturized electrochemical flow cell (EFC), has been constructed for the determination of trace amounts of Se (IV) by employing cathodic stripping voltammetry (CSV) technique. The procedure is carried out on a mercury film coated glassy carbon electrode. The analyte solution and electrolyte solution were continuously aspirated and merged in the holding coil (HC) by using a single syringe pump, which were afterwards pushed into the EFC, where the peak current was generated during the subsequent deposition/stripping procedure and measured as the basis of quantification. Assay parameters were optimized in order to achieve the best analytical performance, including mercury film preparation, supporting electrolyte composition, deposition potential and deposition time, and flow variables in the LOV. By loading a sample volume of 500 μL, a linear calibration graph was derived within 1-600 μg L⁻¹, and a detection limit (3б) of 0.11 μg L⁻¹ was achieved along with a sampling frequency of 20 h⁻¹. By integrating the EFC into the LOV unit, the assembling system not only minimized the sample/reagent consumption and waste generation, but also enhanced the sampling frequency. The work itself extended the applications of electrochemical detection techniques and provided a good platform for Se (IV) electrochemical analysis.     

Potentiometric flow injection determination of manganese(II) by using a hexacyanoferrate(III)-hexacyanoferrate(II) potential buffer

A highly sensitive potentiometric flow injection analysis method for the determination of manganese(II), utilizing a redox reaction with hexacyanoferrate(III) in near neutral media containing ammonium citrate is described. The analytical method is based on the detection of the change in potential of a flow-through type redox electrode detector, resulting from the composition change of an [Fe(CN)₆]³⁻-[Fe(CN)₆]⁴⁻ potential buffer solution. A linear relationship between the potential change (peak height) and the concentration of manganese(II) was found. Manganese(II) in a wide concentration range from 10⁻⁴ to 10⁻⁷ M could be determined by appropriately altering the concentration of the potential buffer from 10⁻³ to 10⁻⁵ M. The lower detection limit of manganese(II) was determined to be 1×10⁻⁷ M. The sampling rate and relative standard deviation were 20 h⁻¹ and 1.9% (n=8) for 6×10⁻⁶ M manganese(II), respectively. The proposed method was successfully applied to the determination of manganese(II) in actual soil samples obtained from tea fields. Analytical results obtained by the proposed method were in good agreement with those obtained by an atomic absorption spectrophotometric method.     

Determination of chromium(VI) and lead(II) in drinking water by electrokinetic flow analysis system and graphite furnace atomic absorption spectrometry

An electrokinetic flow analysis system (EKFA) using an electroosmotic pump (Peo) and a bi-directional electrostacking (BDES) unit is introduced in this paper. Large flow range, moderate carrier pressure, low performance voltage and stable flow rate, especially in mulmin(-1) level, are the main specialties of the Peo. Diethanolamine, 0.5 mM, is selected as its carrier to improve the pump efficiency and stability further. Moreover, BDES, a feasibility investigation for the simultaneous separation and pre-concentration of cations and anions, and graphite furnace atomic absorption spectrometry (GFAAS) determination are presented. The calibration series for both of Cr(VI) and Pb(II) are from 0.2 to 40 mugl(-1) with 10 mul pipette volume and GFAAS determination directly. The detection limit of Cr(VI) and Pb(II) with 10 min BDES is 10 and 13 ngl(-1)(3sigma of blank, n=11), respectively. The recovery of Cr(VI) and Pb(II) is (103-105)+/-1% and (95.9-96.9)+/-1.0% with three independent determinations, respectively. The investigated method is also suitable for the simultaneous separation and pre-concentration of trace cations and anions in low conductivity sample solutions with different detection instruments.     

Flow-injection spectrophotometric determination of dipyrone in pharmaceutical formulations using a solid-phase reactor with copper(II) phosphate

In this work, a flow-injection spectrophotometric method for dipyrone determination in pharmaceutical formulations was developed. Dipyrone sample solutions were injected into a carrier stream of deionized water and the reaction was carried out in a solid-phase reactor (12 cm, 2.0 mm i.d.) packed with Cu₃(PO₄)_2(s) entrapped in a matrix of polyester resin. The Cu(II) ions were released from the solid phase reactor by the formation of Cu(II)-(dipyrone)_n complex. When the complex is released, it reacts with 0.02% m/v alizarin red S in deionized water to produce a Cu(VABO₃)₃ complex whose absorbance was monitored at 540 nm. The calibration graph was linear over the range 5.0×10^?5–4.0×10^?4 mol L^?1 with a detection limit of 2.0×10^?5 mol L^?1 and relative standard deviation for 10 successive determinations of 1.5% (2.0×10^?4 mol L^?1 dipyrone solution). The calculated sample throughput was 60 h^?1. The column was stable for at least 8 h of continuous use (500 injections) at 25°C. Pharmaceutical formulations were analyzed and the results from an official procedure measurement were compared with those from the proposed FIA method in order to validate the latter method.      

Determination of boron as boric acid in eye lotions using a sequential injection system

A simple and reliable sequential injection analysis (SIA) system is described for the determination of boron as boric acid in eye lotions. This method is based on the complexation reaction between d-sorbitol and boric acid followed by the acid-base reaction with methyl orange (MO). The colour change reaction is monitored at 520 nm. The system is able to monitor boron at a frequency of 30 samples per h with a relative standard deviation of less than 0.6%. The calibration graph is linear up to 12-mg l(-1). The system has a detection limit of 0.06-mg l(-1). No significant differences (at 95% probability level) were found between the proposed SIA method and the reference method.     

Determination of total iron in ground waters and multivitamin tablets using a solid-phase reactor with tiron immobilised on amberlite ion-exchange resin in a flow injection system

A method is described for the flow injection determination of total iron as Fe(III) using a solid-phase reactor containing disodium-1,2-dihydroxybenzene-3,5-disulphonate (tiron) as substrate. The iron(III) reacted with tiron to form a complex which absorbs strongly at 667 nm, where it was measured spectrophotometrically. The system has a linear range of 1 to 50 mg L^–1 with a detection limit of 0.67 mg L^–1. It is suitable for the determination of total iron in multivitamin tablets and iron-rich ground waters, with a relative standard deviation of better than 1.1%. The results obtained compared favourably with the certified values and a standard ICP-AES method.