Atomic spectrometric detectors for flow-injection analysis

The distinction between liquid chromatography and flow injection analysis is discussed in terms of the underlying concepts, the performance characteristics and the hardware involved. For the last aspect, attention is focused on the role of the detector and the development of spectroscopic detectors for these techniques is discussed. The limitations of atomic spectrometric detectors are discussed for the three most widely used techniques, flame atomic absorption spectrometry, plasma spectrometry and electrothermal atomisation atomic absorption spectrometry, and the recent literature concerned with the use of these techniques for chromatographic detectors is summarized. The use of flow-injection methods to extend the capabilities of the techniques, particularly as far as detection limits and matrix interferences are concerned, is discussed. These topics are illustrated by a detailed review of relevant papers from 1988 and 1989. It is concluded that there is a considerable sustained research effort in this field.     

Bio-field-effect transistors as detectors in flow-injection analysis

The development of enzyme-modified bio-field-effect transistors (BioFETs) for the determination of glucose, urea, penicillin G, penicillin V and cephalosporin C is reported. BioFETs are produced by covering the pH-sensitive gate areas of ion-selective field-effect transistors with enzyme membranes. The characteristics of the resulting BioFETs and the influence of several parameters, e.g., pH and buffer capacity, are described. The measuring range covers 1–2 orders of magnitude of substrate concentration, and the BioFETs are applicable for 3–12 weeks, depending on the enzyme. They show a short response time and are well suited for detection in flow systems. The frequency of determination with BioFETs in flow systems is high (15–20 measurements per hour). The application of a BioFET in on-line bioprocess control is described. A glucose oxidase FET monitors the glucose concentration during cultivation of Escherichia coli. The results correspond well with off-line liquid chromatographic determinations.     

Impulse-response functions of several detectors used in flow-injection analysis

A procedure for the determination of the impulse-response function of a detector is given. Its application to photometers, ion-sensitive field effect transistors, a potentiometric detector at constant current and a voltammetric detector shows that the impulse-response function can be used to obtain specific information about the performance of the detector in the manifold. This function clearly shows the contribution of the detector to the peak broadening and how the detector generates the final signal from the presented concentration profile. From this information one could derive improvements to the detector, such as changing the construction of the detector cell, minimizing the influence of other parts of the manifold or adapting the attached electronics.     

Speciation studies by flow-injection analysis

A survey of the use of flow-injection analysis for speciation studies is presented. Comments are made about the future potential of the technique, and suggestions are made for further research.     

Metal speciation by flow-injection analysis

A two-channel switching valve is incorporated in the flow-injection manifold for on-line control of the metal speciation of Fe(II)/Fe(III) and Cr(III)/Cr(VI). 1,10-Phenanthroline is used for the iron determinations and diphenylcarbazide for chromium. The absorbances are measured at 512 and 540 nm, respectively. When a 30-mul injection loop is used, the response is linear for 0.5-30.0 ppm Fe and 0.5-40.0 ppm Cr. The relative standard deviation in each case is approximately 1%. The method allows at least 180 injections per hour.     

Fluorimetric determination of aflatoxins by flow-injection analysis

Summary A fast and inexpensive fluorimetric method for the determination of total aflatoxins (B₁, B₂, G₁, and G₂) in food of use in screening numerous samples suspectedly containing these substances is proposed. The sensitivity of the method (determination range between 0.5 and 200.0 ng ml^–1) allows these analytes to be detected at concentrations well below legal limits; hence, separation-detection techniques such as HPLC need only be used with samples in which these compounds are found to occur. The method has been applied to maize, peanut and tapioca samples, obtaining average recoveries of 100.9 with deviations of ±5% with respect to 100% recovery.

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Fluorometrische Bestimmung von Aflatoxinen durch Fließinjektionsanalyse

     

流动注射化学发光法测定片剂中阿昔洛韦含量

在碱性介质中,低浓度的阿昔洛韦会增强鲁米诺-H2O2体系的化学发光,据此建立了测定阿昔洛韦的新方法.该法的化学发光增强值ΔICL与阿昔洛韦的浓度在9.00×10-8～3.00×10-6mol/L范围内呈良好的线性关系,相关系数r为0.9957,检出限为7.71×10 -8mol/L.对1.00×10-6 mol/L的阿...     

Miniature flow-injection analysis manifold created by micromilling

The miniature flow injection analysis (μFIA) system is based on a mechanically engraved manifold in a PMMA-substrate. The channels have a trapezoidal cross-section with a depth of 150 μm and a width between 180 and 360 μm and the reactor volume is 3.75 μl. A light-emitting diode (LED) is used as radiation source for absorbance detection and optical fibres are used for transmitting light to and from the manifold. Computer controlled valves are used for directing the liquid flows maintained with syringe pumps. A sampling rate of approximately five determinations per minute was achieved with a reagent consumption of 10 μl min⁻¹. Four applications were implemented and tested; the performance was found to be comparable to that obtained with conventional FIA-set-ups despite the drastically reduced optical pathlength. Electrokinetic pumping was extensively evaluated but found to generally be very restricted in scope because the reagent solutions cannot usually be adapted to the requirements for generating the flow.     

Flow-reversal flow-injection analysis. Enhancement of flow-injection titrations

Most FIA applications involve simple unidirectional continuous-flow regimes. This paper continues the development of the flow-reversal (frFIA) approach and its applications. Flow-reversal flow programming achieves flexibility in operation without requiring manifolds to be refitted. The sensitivity of FIA titrations can be increased by use of frFIA.     

流动注射化学发光法测定己内酰胺

使用己内酰胺增强Ce(Ⅳ) SO32-化学发光体系,结合流动注射分析技术进行了己内酰胺的测定。己内酰胺的质量浓度在4.0×10-7～1.0×10-5g/mL范围内与化学发光分析信号呈线性关系,其检出限为1×10-7g/mL。对4.0×10-7g/mL的己内酰胺溶液进行11次连续测定,相对标准偏差为2.1%。方法已应用于层析用聚己内酰胺中的己内酰胺测定。     

Fluorometric determination of diphenhydramine by flow-injection analysis

A sensitive, rapid and simple flow injection procedure for the determination of diphenhydramine has been designed based on a fluorometric approach. An aqueous solution of diphenhydramine is injected into a carrierreagent stream containing Ce(IV) in dilute sulphuric acid and the fluorescence intensity of the Ce(III) produced is monitored. Chemical, FIA and instrumental variables were optimized. Analytical features of the method are: linear range 0.2–2 ppm, precision 0.7%, sample throughput 80/h. The influence of some foreign substances which can be found in typical pharmaceutical samples containing diphenhydramine was also investigated. The diphenhydramine content of a pharmaceutical preparation was determined.     

Radiometric flow-injection analysis

The initiation, present status and future trends of radiometric flow-injection analysis is described.     

Determination of nitrate in natural waters by flow-injection analysis

Summary Nitrate was determined in natural water samples by flow-injection spectrophotometry. It was reduced to nitrite with copperized cadmium and the nitrite thus produced reacted with p-aminoacetophenone and m-phenylenediamine. The limit of detection was about 1.5 g l^–1 for sample injections of 650 l. The sampling rate was about 40 samples h^–1 and the relative standard deviation was above 1% for 0.1–0.3 mg l^–1 nitratenitrogen. Nitrite present in the sample was determined separately and subtracted.

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Nitratbestimmung in natürlichen Wässern mit Hilfe der Fließinjektions-Analyse

Zusammenfassung Nitrat wird bei dieser Methode mit Hilfe einer Cu/Cd-Reduktionssäule zu Nitrit reduziert, das mit p-Aminoacetophenon und m-Phenylendiamin zur Reaktion gebracht wird. Die gebildete Verbindung wird spektral-photometrisch gemessen. Die Nachweisgrenze beträgt etwa 1,5 g/l bei injizierten Probevolumina von 650 l. Der Probendurchsatz beträgt 40/h. Die relative Standardabweichung liegt über 1% bei 0,1–0,3 mg/l Nitrat-Stickstoff. Vorhandenes Nitrit wird gesondert bestimmt und abgezogen.

     

Determination of sulphate in natural water by flow-injection analysis

Summary Sulphate was determined in natural water samples by flow-injection analysis using dimethylsulphonazo-III as reagent. The interference by Ca was eliminated by a cation-exchanger column inserted directly after the sample injection valve. In order to ensure high sensitivity and reproducibility it was necessary to saturate the carrier solution with barium sulphate and to fill the reaction coil with ethanol-water (11) when not in use. Standard deviations were 0.94–1.2% for 6–10mg/l sulphate. The limit of detection was about 0.2mg/l. The calibration graph was linear up to 14mg/l Mg²⁺, NH ₄ ⁺ , Na⁺, K⁺, Cl^–, NO ₃ ^– , PO ₄ ^3– , HCO ₃ ^– and SiO ₃ ^2– did not interfere in the normally occurring concentrations.

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Sulfatbestimmung in natürlichem Wasser durch Flow-Injection-Analyse

Zusammenfassung Als Reagens dient Dimethylsulfonazo-III. Die Störung durch Calcium bei dieser Bestimmung wird durch eine Kationenaustauschersäule eliminiert, die direkt nach dem Probeinjektions-Ventil angeordnet ist. Zur Erhöhung der Empfindlichkeit und Reproduzierbarkeit ist es notwendig, die Trägerlösung mit Bariumsulfat zu sättigen sowie bei Nichtbenutzung des Systems den Reaktionsteil mit Ethanol-Wasser (11) zu füllen. Mit dem so modifizierten Verfahren ergaben sich Standardabweichungen von 0,94–1,2% für 6–10 mg/l Sulfat, die Nachweisgrenze liegt bei 0,2 mg/l. Die Eichkurve ist bis 14 mg/l linear. Mg²⁺, NH ₄ ⁺ , Na⁺, K⁺, Cl^–, NO ₃ ^– , PO ₄ ^3– , HCO ₃ ^– und SiO ₃ ^2– stören in den normalerweise vorkommenden Konzentrationen nicht.

     

On-line determination of sulphite in brine by flow-injection analysis

A spectrophotometric flow-injection procedure for the determination of sulphite in aqueous media over the range 0.5–20 mg 1^?1 is described. The reagent used was the organic disulphide 5,5′-dithiobis(2-nitrobenzoic acid). Results are presented for a laboratory-based method for sulphite in water and a potential on-line method for sulphite in high ionic strength potassium chloride brine. The general attractions of flow-injection-based monitors for the on-line analysis of liquid process streams are also discussed.     

Sandwich standardization in flow-injection analysis

The use of internal coupling of valves as an easy and handy way to intersperse calibration and determination is shown. The advantages of derivative over normal recordings are considered.     

Spectrophotometric determination of silicon in silicates by flow-injection analysis

A flow-injection spectrophotometric method has been developed for the accurate, continuous determination of silicon in silicate rocks. A rock sample solution is prepared by fusion with a 1:1 mixture of lithium carbonate and boric acid and subsequent dissolution of the cake in 1 M hydrochloric acid. The preparation technique is the same as that used for the determination of total iron, aluminium, calcium, titanium, and phosphorus in silicate rocks by flow-injection spectrophotometry. Because of the marked polymerization of silicic acid in acid solution, silicic acid is depolymerized in alkaline medium after a simple cation-exchange column filtration of the rock sample solution and then determined by a static or an FIA spectrophotometric method. The FIA system consists of two channels which carry the carrier solution and molybdate reagent, and allows the colour reaction to proceed under controlled conditions. The FIA system permits high throughput of 70 samples per hour. The procedure has been applied to a variety of standard silicate rocks of the U.S. Geological Survey and the Geological Survey of Japan, and gave satisfactory agreement with the recommended values.     

Laminar dispersion in flow-injection analysis

Simple expressions are given for the dispersion and the travel times of samples in simple flow-injection analysis systems. The sum of these two quantities is the total residence time of the sample in the system. The expressions are based on numerical solutions of the diffusion-convection equation. Preliminary experiments are in agreement with the derived simple expressions, as are peak curve shapes. Diffusion coefficients can be obtained in a straightforward manner.     

Chemical speciation by flow-injection analysis. A review

Speciation of elements in natural matrices, especially of trace metals, is one of the predominant development trends of modern inorganic analysis. The main part of the conventional speciation procedures is a suitable combination of separation and chemical conversion steps, for which the most appropriate methodology seems to be the use of flow-injection. A shorter time of performance of these operations in flow-injection manifolds is advantageous in terms of avoiding the shift of chemical equilibria during the speciation measurement. Numerous other advantages are also pointed out in this review based on 58 references. Among flow-injection analysis methods published so far for speciation the determination of different oxidation states predominates, while a much smaller number of papers have been published on the determination of the degree of complexation or the determination of organometallic compounds.