Extension of the dynamic range of flame atomic absorption spectrometry using flow injection analysis with variable-volume dilution chambers

A simple and inexpensive procedure is proposed for the extension of the dynamic range of flame atomic absorption spectrometry measurements using on-line dilution. The proposed methodology is based on the use of a manifold with two coupled dilution chambers and a zone injection system. The samples are prediluted in a closed system which includes a variable-volume mixing chamber (10–120 ml) and two injection valves. The samples are injected through one of these valves, and the other is employed to take 100 μl of prediluted samples which are then passed through a new dilution chamber (volume 1–10 ml) and aspirated by the nebulizer of the instrument. A third injection valve mounted in the last part of the manifold is used for the direct injection of diluted standard solutions. Various dilution factors are obtained, ranging from 2 to 130 000 times, thus extending the analytical range of copper determination to more than 100 000 mg l⁻¹.     

On-line microwave oven digestion flame atomic absorption analysis of solid samples

A manifold has been developed for on-line microwave oven digestion and flame atomic absorption spectrometric (FAAS) determination of metallic elements in solid samples. The use of a closed flow system permits sample treatment before analysis by FAAS, the direct injection of slurries avoids a filtration step and the interconnection of two conventional rotary injection valves allows the rapid introduction of samples and standards. The determination of lead in sewage sludge was employed as a test system for the proposed on-line sample digestion manifold. The procedure has a limit of detection of 0.2 μg Pb g^?1.     

Fast microwave-assisted free sugars washing and hydrolysis pre-treatment for the flow injection determination of starch in food

The approach used consists of a flow injection (FI) manifold assisted by a focused microwave digestor for both fast washing of free sugars and acceleration of the hydrolysis step prior to the determination of starch in food. The action of microwaves reduces both the times for removal of free sugars to a 5 min single washing cycle with ethanol/water and that of the subsequent starch hydrolysis to a 10 min step. The sugars formed in the starch hydrolysis are in-line derivatised and photometrically monitored at λ=460 nm. In this way, automation of pre-treatment and determination is achieved with the minimum of both cost and time. The precision of the overall method, expressed as relative standard deviation, is 3.75% and the total analysis time is 38 min. Comparison of the results, obtained in applying the method to flour and bread, is in agreement with those provided by the manual method.     

Automated flow-injection procedures for the determination of hydrolytic enzymes in bioreactor preparations

Summary Automated spectrophotometric flow-injection (FI) procedures for the quantitative determination of the hydrolytic enzymes amylase, xylanase, polygalacturonase and protease, acting on macromolecular substrates, are described. The peptides produced by the protease are derivatized with trinitrobenzene sulphonic acid. For the other enzymes, the reducing sugars produced are derivatized with p-aminobenzoylhydrazide (PABH). The FI manifold design allows the choice of any required detetion, range between 0.1 U ml^–1 and several hundred U ml^–1. Two FI manifold designs are proposed; one optimizes, sample throughput at a high sensitivity level by incorporating several parallel incubation coils, the other minimizes sample volume at a low sensitivity level and facilitates, automation. The instrumentation is largely based on commercial HPLC equipment.     

On-line dynamic fractionation and automatic determination of inorganic phosphorus in environmental solid substrates exploiting sequential injection microcolumn extraction and flow injection analysis

Sequential injection microcolumn extraction (SI-MCE) based on the implementation of a soil-containing microcartridge as external reactor in a sequential injection network is, for the first time, proposed for dynamic fractionation of macronutrients in environmental solids, as exemplified by the partitioning of inorganic phosphorus in agricultural soils. The on-line fractionation method capitalises on the accurate metering and sequential exposure of the various extractants to the solid sample by application of programmable flow as precisely coordinated by a syringe pump.

Three different soil phase associations for phosphorus, that is, exchangeable, Al- and Fe-bound, and Ca-bound fractions, were elucidated by accommodation in the flow manifold of the three steps of the Hieltjes–Lijklema (HL) scheme involving the use of 1.0 M NH₄Cl, 0.1 M NaOH and 0.5 M HCl, respectively, as sequential leaching reagents. The precise timing and versatility of SI for tailoring various operational extraction modes were utilized for investigating the extractability and the extent of phosphorus re-distribution for variable partitioning times.

Automatic spectrophotometric determination of soluble reactive phosphorus in soil extracts was performed by a flow injection (FI) analyser based on the Molybdenum Blue (MB) chemistry. The 3σ detection limit was 0.02 mg P L⁻¹ while the linear dynamic range extended up to 20 mg P L⁻¹ regardless of the extracting media. Despite the variable chemical composition of the HL extracts, a single FI set-up was assembled with no need for either manifold re-configuration or modification of chemical composition of reagents.

The mobilization of trace elements, such as Cd, often present in grazed pastures as a result of the application of phosphate fertilizers, was also explored in the HL fractions by electrothermal atomic absorption spectrometry.     

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II)

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.     

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II)

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.     

Spectrophotometric determination of phenol and resorcinol by reaction with p-aminophenol

Based on the reaction with p-aminophenol, a series of procedures have been developed for the spectrophotometric determination of phenol and resorcinol. Three basic approaches have been studied: (i) a batch procedure, using the dissolved oxygen as oxidant, (ii) a stopped-flow procedure by use of KIO(4) as oxidant and (iii) a flow injection (FI) procedure developed in the presence of KIO(4). Phenol can be accurately determined at 626 nm, in the stopped-flow mode, after a reaction time of 45 min in 0.005M NaOH, 0.004M KIO(4) and 500 mug/ml of PAP. The development of a manifold, which incorporates a sample parking, is a convenient approach which makes it possible to measure, in the stopped-flow mode, four solutions in one hour. The limit of detection of this method corresponds to 64 ng/ml of phenol Resorcinol can be determined by FI at 540 nm in 0.006M NaOH, 0.0002M KIO(4) and 50 mug/ml PAP with a limit of detection of 6.6 ng/ml and a sample throughput of 300 injections per hour. A combination between the FI procedure for the determination of resorcinol and the stopped-flow procedure for phenol determination provides accurate results in the analysis of spiked samples containing both phenol and resorcinol.     

Triple-channel portable capillary electrophoresis instrument with individual background electrolytes for the concurrent separations of anionic and cationic species

The portable capillary electrophoresis instrument is automated and features three independent channels with different background electrolytes to allow the concurrent optimized determination of three different categories of charged analytes. The fluidic system is based on a miniature manifold which is based on mechanically milled channels for injection of samples and buffers. The planar manifold pattern was designed to minimize the number of electronic valves required for each channel. The system utilizes pneumatic pressurization to transport solutions at the grounded as well as the high voltage side of the separation capillaries. The instrument has a compact design, with all components arranged in a briefcase with dimensions of 45 (w) × 35 (d) × 15 cm (h) and a weight of about 15 kg. It can operate continuously for 8 h in the battery-powered mode if only one electrophoresis channel is in use, or for about 2.5 h in the case of simultaneous employment of all three channels. The different operations, i.e. capillary flushing, rinsing of the interfaces at both capillary ends, sample injection and electrophoretic separation, are activated automatically with a control program featuring a graphical user interface. For demonstration, the system was employed successfully for the concurrent separation of different inorganic cations and anions, organic preservatives, additives and artificial sweeteners in various beverage and food matrices.     

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 injection differential potentiometric determination of lysine by using a lysine biosensor

This paper describes a method for the determination of lysine based on a flow injection (FI) differential potentiometry system. The flow injection manifold is composed of a support electrolyte solution channel and a water channel acting as a carrier into which the sample solution is injected. The lysine biosensor was consisted of lysine oxidase chemically immobilized on a nylon membrane and attached to an all-solid-state ammonium electrode. A circular ammonium electrode was used as a reference. Hence, the possible interference of endogenous ammonium can be partly corrected by differential potentiometry. In order to increase the sensitivity of the response, the reaction was kinetically developed following a stopped-flow method. As a result, the sensitivity increased from 20 to 40 mV per decade when comparing the FI and the stopped-flow values. Furthermore, the peak-to-peak stopped-flow signals generated can be used as a more selective analytical response for lysine. The quantification of lysine in mixture samples containing small amounts of ammonium can be achieved with an acceptable accuracy, with prediction errors lower than 4%. However, when the ammonium concentration exceeded the lysine concentration, multivariate calibration with non-linear partial least squares (PLS) regression was needed to improve the lysine quantification, with an overall prediction error around 10%.     

A simple flow injection spectrophotometric procedure for the determination of diazepam in pharmaceutical formulation.

A single-channel flow injection (FI) manifold with spectrophotometric detection has been designed and fabricated for diazepam determination. A 100 microl sample and/or standard solution containing diazepam was injected into a flowing stream of 0.1 mol L(-1) hydrochloric acid with the optimum flow rate of 6.8 mL min(-1). As soon as the sample reached the detector, the FI signal as a peak was recorded at 360 nm. The optimum conditions for microg amounts of diazepam were achieved. A linear calibration graph over the range of 2-110 mg L(-1) diazepam was obtained with the regression equation Y = 0.2926X + 0.5896 (r2 = 0.9929). The method was very sensitive, since as little as 0.60 mg L(-1) could be detected; very reproducible with an RSD of 3.3% (n=11); and very rapid with a sampling rate of 100 h(-1). The limit of quantitation (10 sigma) was 2.0 mg L(-1). The proposed FI procedure has been satisfactorily applied to the quantitation of diazepam in commercial pharmaceutical formulations. The obtained results were in excellent agreement with those obtained by the conventional spectrophotometric method, verified by the student t-test at the 95% confidence level.     

Ultrasound-assisted continuous liquid-liquid extraction without phase separation and hydrolysis of paracetamol in suppositories

An automated flow injection (FI) manifold based on iterative change of the flow direction has been designed to carry out continuous liquid-liquid extraction without phase separation and hydrolysis both with ultrasound-assistance. The dynamic approach has been applied to suppositories from which paracetamol has been extracted in this way into an aqueous phase and hydrolysed prior to reaction with o-cresol in the alkaline medium used as extractant. The three linked reactions, extraction-hydrolysis-derivatisation, cause displacement of the balance to completeness. The strategic location of the photometric flow-cell in the flow-injection manifold enables monitoring of the overall process and the obtaining of a characteristic multipeak recording. The influence of ultrasounds on the different steps was investigated. The indophenol blue dye formed was monitored at 620 nm. The limits of detection (LOD) and quantification (LOQ) of the method are 0.38 and 0.64 μg ml⁻¹, respectively, with a linear range from 0.64 to 50 μg ml⁻¹; a within-laboratory reproducibility between 2.07 and 4.66% and repeatability from 2.01 to 4.63%, both expressed as relative standard deviation. The results obtained with the proposed method are in excellent agreement with those provided by the official method, but with a shorter analysis time, lower sample and reagent consumption and less analyst involvement.     

Application of flow injection on-line electrothermal atomic absorption spectrometry to the determination of rhodium

A fully automated procedure for the determination of rhodium has been developed using flow injection (FI) on-line microcolumn preconcentration coupled with electrothermal atomic absorption spectrometry (ETAAS). The proposed FI manifold and its operation make possible the introduction of the total eluate volume into the graphite atomizer, avoiding the necessity for optimisation of subsampling the eluate. Rhodium is adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). Under the optimum conditions, using a 60 s preconcentration time, a sample flow rate of 3.5 mL min(-1) and an injection volume of eluent of 50 microL, a linear calibration graph was obtained from 1 to at least 40 ng mL(-1) and the detection limit was 1 ng mL(-1). The proposed method has been successfully applied to the analysis of samples. Its performance was investigated against certified reference catalyst sample SRM-2557 and by recovery measurements on spiked samples (soil, foods and beverages).     

Screening method for linear alkylbenzene sulfonates in sediments based on water Soxhlet extraction assisted by focused microwaves with on-line preconcentration/derivatization/detection

A screening method for linear alkylbenzene sulfonates (LAS) in sediments has been developed. Soxhlet extraction with water assisted by focused microwaves provides recoveries better (>90%) than obtained by conventional Soxhlet extraction (70-80%). Coupling of the extractor with an on-line preconcentration/derivatization/detection manifold through a flow injection (FI) interface allows a fully automated screening approach. A yes/no answer can be obtained in less than 2 h (for the whole analytical process), a short time compared with the at least 24 h of Soxhlet extraction (without final detection). Due to the use of water as leaching agent, the proposed method is environmentally friendly.     

Development of the continuously variable volume reactor for flow injection analysis: Part 1. Design, capabilities and testing

A new apparatus for mixing sample and reagent in flow injection analysis (FIA) is described. The continuously variable volume reactor (CVVR) replaces the conventional mixing coil in a flow injection (FI) manifold to provide mixing and dilution. A linear actuator motor allows control of the chamber volume via LabVIEW software. The chamber volume can be incremented in steps of 1 μl over the range 68-1704 μl. In addition, the chamber has an integral variable-speed stirring unit that is also under computer control. Experiments were performed to evaluate the dispersion characteristics of this new device, evaluate the volume reproducibility, and understand the mixing characteristics. Use of the chamber is shown in the determination of iron(II) in pond water, and in NIST SRM 1643d with excellent results and a detection limit of 3.7 μg/l iron(II). Advantages of the CVVR and future research activities using the device are discussed.     

Two-parameter determination in vinegar by a flow injection-pervaporation system

A flow injection method (FI) for the sequential determination of ethanol and acetic acid in vinegar is reported. The determination of ethanol is based on the oxidation of the pervaporated ethanol by K2Cr2O7. The acetic acid is determined by an acid-base reaction with Thymol Blue as the indicator. Both reactions are monitored photometrically at 600 nm using a single detector. Optimisation studies and assessment of the sequential Fl method are also reported. The linear determination range is 0-12% v/v for ethanol and 0-10% (grams of acetic acid in 100 ml) for acetic acid. The sample throughput of the sequential manifold is seven per hour. The new method was applied to vinegar samples and the results obtained were in excellent agreement with those from reference methods used in Spain.     

Speciation with unsegmented continuous systems

Speciation applications of the flow-injection technique are discussed in relation to the hydrodynamic manifold components that are adapted for this purpose. Alterations include double halting of the propulsion system, coupling of injection valves, modifications of the transport-reaction zone, use of switching valves, and merging and splitting points. Detector remodelling, the use of sensors and special detectors, and data processing methodologies are also reviewed in connection with the flow-injection/chromatography coupling. Finally, foreseeable trends and desirable advances are outlined.     

Design and fabrication of a low-cost flow-through cell for the determination of acetaminophen in pharmaceutical formulations by flow injection cyclic voltammetry

A low-cost electrochemical flow-through cell is designed and fabricated to use in conjunction with a flow injection (FI) system. This detector cell used a centrosymmetric radial flow thin-layer geometry with a stainless steel auxiliary electrode and a reference electrode (Ag/AgCl) without a salt bridge. The 5H pencil lead electrode used as a working electrode in the home-made cell is an extremely inexpensive electrode which performs as well as the expensive commercial glassy carbon electrode. Optimum conditions for determining acetaminophen using the proposed FI manifold was investigated. Appropriate volume of sample and/or standard solution containing acetaminophen in pH 2.2 Mcllvaine buffer solution was injected into the proposed FI system and mixed with the flowing stream of supporting electrolyte (pH 2.2 Mcllvaine buffer solution) at an optimum flow rate of 1 ml min⁻¹. The cyclic voltammograms were recorded over the potential range from −0.5 to +2.0 V with a scan rate of 40 mV s⁻¹. Linear calibration curve over the range of 0.1–5 mM acetaminophen was established with the regression equation Y=3.68X+1.0157 (r²=0.9964). The recommended method has been applied to the determination of acetaminophen in 8 commercial pharmaceutical preparations. The percentage recoveries of the spiked acetaminophen in four tablet samples were ranging from 103 to 112 with the relative standard deviation in the range of 0.1–1.3%.     

A new microdialysis unit for flow injection analysis

Summary A new dialysis unit optimized for FIA is described. It contains both a dialysis cell and a manifold for reagent addition. Both parts are included in the same module. For test purposes, a colorimetric determination of chloride — both with and without dialysis — has been carried out. For the conditions given in the experimental setup, the dialyzing efficiency was ca. 11 %. The dilution loss factor, i.e., dilution caused by the dialysis cell, was ca. 9. The dispersion coefficient (D) for the manifold — excluding the dispersion caused by dialysis — was calculated to 2.2. The analytical performance expressed as repeatability is around 1.3% r.s.d., and the sample throughput is around 80 – 90 samples/h. Potential application areas cover a wide range of possibilities, e.g., foods and feeds, dairy products, soils and plants, water and waste water analysis and fermentation products.

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Neue Mikrodialyseeinheit für die Fließinjektionsanalyse