In the present paper, the characteristics (apparatus, manifold design, and operation mode) of multi-syringe flow injection analysis systems are discussed and critically compared to those of flow injection analysis and sequential injection systems. Furthermore, a survey of applications proposed until the present moment is presented, with special emphasis on implementation of in-line sample treatment.

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A micro-reactor system with continual spectrophotometric detection has been operated in Sequential Injection lab-on-valve (SI-LOV) mode and applied to enzyme kinetics and inhibition studies, using acetylcholinesterase (AChE) and angiotensin-converting enzyme (ACE) as model systems. With the advantages of automation, real-time kinetic measurement, and thorough mixing, the SI-LOV micro-reactor system allows for the monitoring of initial reaction rates and determination of reactant concentrations in the reaction mixture, both of which are essential for the determination of kinetic constants for enzymes and inhibitors. Enzyme, substrate, and inhibitor are precisely metered by the syringe pump and delivered to a stirred micro-reactor, followed by a reference scan that establishes the baseline for the following reaction rate measurement. Michaelis constants (K_m) for AChE and ACE were determined to be 0.16 mM and 0.30 mM, respectively, which are consistent with literature values. The type of inhibition (competitive, uncompetitive, or mixed), the dissociation constants for the inhibitors, and the inhibitor dose-response curves were also determined.

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A rapid flow injection (FI) spectrophotometric procedure for tetracycline determination is described. It is based on the injection of a 100 µl sample solution containing tetracycline into merged streams of aluminium(III) chloride (0.01 mol l^-1) and Tris-buffer in the presence of KCl (0.06 mol l^-1), pH 7.0, with the same optimum flow rate of 3.2 ml min^-1. A yellow Al(III)-tetracycline complex was monitored at 376 nm. The flow injection system and the experimental conditions were optimized by means of the univariate method. The procedure was applied to the determination of tetracycline in pharmaceutical preparations with a high sampling rate of at least 165 h^-1. A high precision with a relative standard deviation was obtained less than 0.72 and 0.30% of 5.0 and 10 µg ml^-1 (n = 11), respectively. The detection limit (3 σ) and the quantification limit (10 σ) were 0.07 and 0.72 mg l^-1, respectively. There were no interference effects from traditional excipients in the dosage forms when the method was applied to pharmaceutical preparations. The matrix effect could be reduced by the standard addition method.

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This paper presents the analytical determination of the pesticide Asulam based on its native fluorescence. The method was optimized in either a flow injection analysis (FIA) assembly or in batch. The maximum fluorescence intensity was observed for basic pH solutions and at a λ_ex of 258 nm and a λ_em of 342 nm. The influence of different empirical parameters, such as the pH, the presence of surfactants, solvent polarity or solved oxygen amount, was studied. The calibration range was fitted with a linear equation from 0.01 - 3 mg l^-1 Asulam and 0.005 - 15 mg l^-1 Asulam for batch and continuous-flow, respectively. The RSD for both procedures was 1.0%. After testing the influence of a large series of potential interferents, the method was applied to water samples from different locations.

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A rapid and sensitive chemiluminescence (CL) method using flow injection analysis was described for the determination of three catecholamines: dopamine, adrenaline and dobutamine, based on their greatly enhancing effects on the CL reaction of luminol-potassium periodate in basic solutions. Under the optimized conditions, the calibration graphs relating the increase of CL intensity to the concentration of the analytes were linear. The present method allows for the determination of dopamine, adrenaline, and dobutamine over the range of 1.0 × 10^-10 - 1.0 × 10^-7 g/ml. The relative standard deviations for measurements (n = 11) of dopamine, adrenaline and dobutamine were 2.9, 2.3 and 1.8% when the concentrations of three catecholamines were at 1.0 × 10^-9 g/ml, respectively. The detection limits of the method were 2.0 × 10^-11 g/ml dopamine, 1.0 × 10^-11 g/ml adrenaline and 4.0 × 10^-11 g/ml dobutamine. The method was successfully applied to the determination of three catecholamines in pharmaceutical samples and blood plasma.

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A new, robust and simple method is proposed for the chemiluminescent determination of the pesticide Bromoxynil. The empirical procedure is performed with the aid of a flow-injection manifold provided with an on-line photo-reactor to obtain chemiluminescent photofragments. After a period of 12 s of irradiation with an 8 W low-pressure mercury lamp, a chemiluminescent oxidation was performed with the system potassium permanganate in a polyphosphoric acid medium. The photolysis required a basic medium (KOH 0.014 mol l^-1) with ethanol (1%) as a sensitizer. The method allowed the determination of 134 samples h^-1 of Bromoxynil in a wide interval of concentrations, over the range 5 × 10^-3 - 1 mg l^-1; the detection limit was 5 × 10^-3 mg l^-1. The RSD (n = 24) at 0.25 mg l^-1 of the pesticide level was 2.3%. The method was applied to a water sample and to a formulation.

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An electrochemical cell coupled with disposable screen-printed electrodes (SPEs) that is specifically designed for use in flow injection analysis (FIA) is described in this study. The cell is made of foldable polyoxymethylene (acetal) thick platelets with the bottom portion consisting of a cavity track to drag the SPEs in position and the top portion having pre-drilled T-like holes to arrange the Ag/AgCl reference electrode and stainless steel inlet & outlet. An “O ring” is suitably fixed on the top of the working electrode to form a thin-layer space where the electrochemical reaction can take place. Hydrodynamic characterization was validated by using a benchmark hexacyanoferrate redox couple. The results of practical analysis of glucose in human plasma clearly demonstrate the characteristics and applicability of the proposed wall-jet electrochemical cell in FIA.

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Arsenic speciation analysis in marine samples was performed using high performance liquid chromatography (HPLC) with ICP-MS detection. The separation of eight arsenic species viz. arsenite (As^III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenate (As^V), arsenobetaine, trimethylarsine oxide (TMAO), arsenocholine and tetramethylarsonium ion (TeMAs) was achieved on a Shiseido Capcell Pak C₁₈ column by using an isocratic eluent (pH 3.0), in which condition As^III and MMA were co-eluted. The entire separation was accomplished in 15 min. The detection limits for 8 arsenic species by HPLC/ICP-MS were in the range of 0.02 - 0.10 µg L^-1 based on 3 σ of blank response (n = 9). The precision was calculated to be 3.1 - 7.3% (RSD) for all eight species. The method then successfully applied to several marine samples e.g., oyster, scallop, fish, and shrimps. For the extraction of arsenic species from seafood products, the low power microwave digestion was employed. The extraction efficiency was in the range of 52.9 - 112.3%. Total arsenic concentrations were analyzed by using the microwave acid digestion. The total arsenics in the certified reference materials (DORM-2 and TORT-2) were analyzed and agreed with the certified values. The concentrations of arsenics in marine samples were in the range 6.6 - 35.1 µg g^-1.

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A flow injection analysis (FIA) method for the determination of four residual chlorine species, namely combined available chlorine (CAC), free available chlorine (FAC), total available chlorine (TAC) and chlorite (ClO₂^-) was developed using a flow-through triiodide-selective electrode as a detector. An important strategy of speciation studies utilized the kinetic discrimination of reactions between the CAC and FAC with Fe²⁺, which was applied to the speciation of FAC, CAC and TAC. The speciation of available chlorine species and chlorite (an oxychlorine species) was achieved by using the same set-up, but using flow streams of different pH. The effects of the pH of the carrier stream, the flow rate and the sample volume were studied. The method exhibited linearity from 2.8 × 10^-6 to 2.8 × 10^-4 M active chlorine (expressed as OCl^-) with a detection limit of 1.4 × 10^-6 M. The selectivity of the method was studied by examining the minimum pH for the oxidation of iodide by other oxidants, and also by assessing the potentiometric selectivity coefficients. The proposed method was successfully applied to the determination of chlorine species in tap water, and disinfecting formulations where good agreement occurred between the proposed and standard methods were found.

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A simple field sampling-preconcentration method for zinc determination in seawater is described. Seawater was collected in situ by pumping it through a minicolumn packed with a chelating resin (Chelite P) connected to a field flow preconcentration system (FFPS). These packed minicolumns retain the dissolved zinc, and once are loaded with the analyte, they are returned to the laboratory where they are sequentially inserted into a flow injection system for on-line zinc elution with diluted hydrochloric acid and flame atomic absorption spectrometric detection. A factorial design has been used to optimize the FFPS and the flow injection elution process. The proposed method has a linear calibration range from 0.07 to at least 9.4 µg L^-1 of zinc, with a detection limit of 0.02 µg L^-1 and a throughput of 26 samples h^-1. Validation was carried out against certified reference water samples. This procedure has been successfully applied to the determination of Zn in seawater samples from Galicia (Spain).

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Incorporation of a liquid waveguide capillary flow cell into a flow injection instrument enhances the sensitivity of flow injection analysis with spectrophotometric detection by two orders of magnitude. Nitrite determination at nM levels has been used to demonstrate the feasibility of this novel technique for trace analysis. Combining the long pathlength spectrophotometry with flow injection analysis, this technique has advantages of low detection limit, good precision and high sample throughput.

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Accurate liquid flow control is important in most chemical analyses. In this work, the measurement of liquid flow in microliters per minute was performed, and feedback control of the flow rate was examined. The flow sensor was arranged on a channel made in a polydimethylsiloxane (PDMS) block. The center of the channel was cooled by a miniature Peltier device, and the change in temperature balance along the channel formed by the flow was measured by two temperature sensors. Using this flow sensor, feedback flow control was examined with two pumping methods. One was the electroosmotic flow method, made by applying a high voltage (HV) between the reagent and waste reservoirs; the other was the piezo valve method, in which a micro-valve-seat was fabricated in a PDMS cavity with a silicone diaphragm. The latter was adopted for a micro gas analysis system (μGAS) for measuring atmospheric H₂S and SO₂. The obtained baselines were stable, and better limits of detection were obtained.

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To eliminate the use of chlorinated hydrocarbons, we have improved the method for the flow-injection (FI) determination of iodine based on the chemiluminescence reaction of iodine with luminol in a chloroform-free reversed micellar medium of the surfactant cetyltrimethylammonium chloride (CTAC) using a mixture of 1-hexanol-cyclohexane as a bulk solvent. The FI procedure used simply involves the mixing of an iodine solution in cyclohexane with the chemiluminescent reagent solution of luminol in the reversed micellar medium of CTAC in 0.38 M 1-hexanol in cyclohexane/water (buffered with sodium carbonate). The optimum conditions for the iodine determination were evaluated and a detection limit (DL) of 0.05 ng cm^-3 iodine was achieved. The calibration graph obtained was linear with a dynamic range from the DL to 10 ng cm^-3 iodine. The relative standard deviations (n = 5) observed at all concentrations within the linear range were less than 2.5%. The improved FI method is rapid and equally sensitive like the original one and was found to be suitable for the determination of trace iodine.

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A sequential injection analysis (SIA) with chemiluminescence (CL) detection was developed for the measurement of antioxidative activity against singlet oxygen (¹O₂). Lactoperoxidase-hydrogen peroxide-bromide ion system was used for the generation of ¹O₂. When a 100 mM sodium acetate buffer (pH 4.5) was used as a carrier solution, the SIA-CL system could be optimized with respect to the flow-rate of the carrier, concentration of reagents and their aspiration order. The antioxidative activity was expressed as an attenuation of luminol CL due to the quenching of ¹O₂ by an antioxidant. The relative standard deviations of antioxidative activity (n = 3) against ¹O₂ for within- and between-day analyses were ≤ 1.6% (20 µM Trolox). The system was successfully applied to the assay of antioxidative activities of various antioxidants including vitamin supplements at a rate of 10 samples within 15 min. The proposed SIA-CL system was rapid and reproducible with minimum consumption of the sample and of reagents, and thus was useful for the screening of compounds possessing antioxidative activity against ¹O₂.

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A cyclic flow injection analysis (cyclic FIA) for the repetitive determination of chemical oxygen demand (COD) was developed. The acidic KMnO₄ method was carried out by adopting a single-line circulating flow system. The oxidant (KMnO₄) consumed by the oxidation of organic substances was regenerated and reused repeatedly, resulting in an extreme reduction of hazardous wastes. Only 50 ml of the reagent carrier solution containing 0.2 mM KMnO₄ and 1 mM HIO₄ in 0.8 M H₂SO₄ solution was continuously circulated through the system. The KMnO₄ could play two roles: acting as an oxidant of the organic substances and/or a spectrophotometric reagent. The co-existing HIO₄ acted as a regenerator of KMnO₄, which made it possible to recycle the system repeatedly. Under two different digestions (70 and 130°C), 50 repetitive determinations of standard sodium oxalate (6.5 mg COD L^-1) and D-glucose (7.2 mg COD L^-1) were skillfully carried out with a slightly decreased baseline. The analytical frequency was 30 samples per hour for COD determination. The proposed method saved consumption of the used reagents, KMnO₄ and H₂SO₄, and thus these wastes were extremely reduced. The obtained COD values with the proposed method were co-related with those provided by the manual standard method, but were fairly low owing to the insufficient digestion step.

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A rapid and sensitive immunoassay for the determination of vitellogenin (Vg) is described. The method involves a sequential injection analysis (SIA) system equipped with an amperometric detector and a neodymium magnet. Magnetic beads, onto which an antigen (Vg) was immobilized, were used as a solid support in an immunoassay. The introduction, trapping and release of magnetic beads in an immunoreaction cell were controlled by means of the neodymium magnet and by adjusting the flow of the carrier solution. The immunoassay was based on an indirect competitive immunoreaction of an alkaline phosphatase (ALP) labeled anti-Vg monoclonal antibody between the fraction of Vg immobilized on the magnetic beads and Vg in the sample solution. The immobilization of Vg on the beads involved coupling an amino group moiety of Vg with the magnetic beads after activation of a carboxylate moiety on the surface of magnetic beads that had been coated with a polylactate film. The Vg-immobilized magnetic beads were introduced and trapped in the immunoreaction cell equipped with the neodymium magnet; a Vg sample solution containing an ALP labeled anti-Vg antibody at a constant concentration and a p-aminophenyl phosphate (PAPP) solution were sequentially introduced into the immunoreaction cell. The product of the enzyme reaction of PAPP with ALP on the antibody, p-aminophenol, was transported to an amperometric detector, the applied voltage of which was set at +0.2 V vs. an Ag/AgCl reference electrode. A sigmoid calibration curve was obtained when the logarithm of the concentration of Vg was plotted against the peak current of the amperometric detector using various concentrations of standard Vg sample solutions (0 - 500 ppb). The time required for the analysis is less than 15 min.

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We developed a novel microbioassay system equipped with a gradient mixer of two solutions, and we applied the microfluidic system to an anti-cancer agent test using living animal cells on a microchip. A microchannel for the gradient mixing of two solutions and eight other microchannels for cell assay were fabricated on a poly(dimethylsiloxane) substrate using a soft-lithography method. The functions necessary for this bioassay, i.e., cell culturing, chemical stimulation, cell staining, and fluorescence determination, were integrated into the microfluidic chip. Eight gradient concentrations of the fluorescein solution, ranging from 1 to 98 µg/ml, were archived at 0.1 µl/min on a microchip. A stomach cancer cell line was cultured, and a cell viability assay was conducted using 5-Fluorouracil as an anti-cancer agent on the microchip. Cell viability changed according to the estimated concentration of the agent solution. With the microbioassay system, an anti-cancer agent test was conducted using living cells simultaneously in eight individual channels with the gradient concentration of the agent on a microchip.

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The electrochemical behavior and amperometric-FIA quantification of minoxidil at a glassy carbon electrode is described. The procedure is based on electrochemical oxidation at 0.800 V (vs. Ag/AgCl/NaCl(3 M) in a phosphate buffer solution. Minoxidil was determined over the range 1 × 10^-7 - 1 × 10^-4 M. Different analytical parameters and electrode stability were analyzed to obtain the best electrode performance. The optimal conditions were: working potentials, 0.800 V; flow rate, 0.74 mL min^-1; and solution pH 7.0. This system allowed a sampling rate of 120 samples per hour without any pretreatment. The proposed method was used for minoxidil quantification in pharmaceutical preparations with satisfactory results. The accuracy of FIA-amperometric method was established by a comparison with the conventional UV determination technique using a paired t-test indicating the absence of systematic errors.

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A chemiluminometric flow injection analytical system for the quantitation of L-histidine is described. Histidine oxidase (EC 1.4.3.—) from Brevibacillus borstelensis KAIT-B-022 was immobilized on tresylated poly(vinyl alcohol) beads and packed into a stainless-steel column. The hydrogen peroxide produced was detected chemiluminometrically by a flow-through sensor containing immobilized peroxidase (EC 1.11.1.7). The maximum sample throughput was 10 h^-1. The calibration graph was linear from 0.05 to 5 mM; the detection limit (signal to noise ratio = 3) was 0.01 mM. The activity of immobilized histidine oxidase reduced to 65% of the initial value after 350 injections. The system was applied to the determination of L-histidine in fish meat, such as salmon, tunny, bonito, and mackerel.

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A urinary glucose assay has been investigated, employing a micro flow injection analysis (μFIA) combined with a separation technique of glucose from the analyte. The adsorption part using activated alumina for the glucose in the analyte can be successively integrated onto a μFI chip. The selective adsorption-desorption of glucose in the artificial urine can progress on the adsorption part. Along with this selective preconcentration of glucose, the typical FI peak of glucose can be obtained just by feeding the sample and deionized water as an elutant sandwiched with the reagent on the carrier stream. The glucose concentration in artificial urine can be quantitatively determined with the present μFIA system, while the interference of other components coexisting in urine occurs in the case of the conventional FIA system without any separation part. The described method serves as a template for improving the selectivity for the analyte in the multi-component system.

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The enzyme xanthine oxidase (XOD) has been recognized as a key enzyme causing oxidative injury to tissues by ischemia-reperfusion. For this reason, XOD inhibitor, which effectively suppresses this enzyme, plays an important role in the inhibition of many diseases related to reactive oxygen species (ROS). In order to screen XOD inhibitors rapidly and conveniently, a novel assay using flow injection analysis (FIA) was proposed in the present investigation. To optimize the practical FIA system, we studied the effect of the reagent concentrations and the flow condition on the enzymatic reaction, and then selected the optimum condition as follows: 200-mU/ml XOD concentration, 0.5-mM xanthine concentration, 0.5-ml/min flow rate, and 2-m mixing coil length. Under this condition, a typical XOD inhibitor quercetin was determined in the concentration range 0.1 - 1.5 mM at a sampling frequency of 10 samples/h. Using the optimized FIA method, we determined the XOD inhibitory activity of some food samples: onions, apples and teas, which are the high sources of flavonoids known as the potential XOD inhibitors. Among these samples, tea leaves showed the highest activity, the second was onions and the lowest was apples. Based on the result of the assay, not only quercetin, but also other components in investigated samples, contributed to the XOD inhibitory activity.

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An electrooxidation and a cost-effective flow-based analysis of malachite green (MG) and leucomalachite green (LMG) were investigated at a boron-doped diamond thin-film (BDD) electrode. Cyclic voltammetry as a function of the pH of the supporting electrolyte solution was studied. Comparison experiments were performed with a glassy carbon electrode. A well-defined cyclic voltammogram, providing the highest peak current, was obtained when using phosphate buffer at pH 2. The potential sweep-rate dependence of MG and LMG oxidation (peak currents for 1 mM MG and LMG linearly proportional to v^1/2, within the range of 0.01 to 0.3 V/s) indicates that the oxidation current is a diffusion-controlled process on the BDD surface. In addition, hydrodynamic voltammetry and amperometric detection using the BDD electrode combined with a flow injection analysis system was also studied. A homemade flow cell was used, and the results were compared with a commercial flow cell. A detection potential of 0.85 V was selected when using a commercial flow cell, at which MG and LMG exhibited the highest signal-to-background ratios. For the homemade flow cell, a detection potential of 1.1 V was chosen because MG and LMG exhibited a steady response. The flow analysis results showed linear concentration ranges of 1 - 100 µM and 4 - 80 µM for MG and LMG, respectively. The detection limit for both compounds was 50 nM.

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The selective and simultaneous ion-exclusion chromatography (IEC) with UV-detection on a weakly acidic cation-exchange resin column in the H⁺-form (TSKgel Super IC-A/C) was developed and applied for the simultaneous determination of phosphate and silicate ions as the water quality parameters required for optimizing the water-leaching process for ceramics glaze raw materials of natural origin including feldspar, woods-ash, and straw-ash. Phosphate and silicate ions in these water-leaching process water samples were separated selectively from the coexisting anions such as sulfate, chloride, nitrate and carbonate ions, based on the ion-exclusion separation mechanism. They were detected selectively and simultaneously by a postcolumn derivatization with molybdenum-yellow using the UV-detector. Under the optimized separation and detection conditions (eluent, 0 - 1 mM sulfuric acid; reactant, 10 mM sodium molybdate-25 mM sulfuric acid; detector, UV at 370 nm; temperature, 45°C), the linearity of calibration was in the range 0.1 - 10 ppm for both phosphate and silicate ions, and the detection limits at S/N = 3 were 2.58 ppb for silicate ions and 4.75 ppb for phosphate ions. The effectiveness of this method was demonstrated in practical applications to the water-leaching process for some ceramics glaze raw materials.

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An intermittent on-line concentration and separation system coupled with HG-AFS was developed to eliminate serious interferences from Cu²⁺, Pb²⁺ and Zn²⁺ on the determination of cadmium. In the present method, the interferences from common coexisting ions, such as Cu²⁺, Pb²⁺, Zn²⁺, Fe³⁺ and Ni²⁺, were greatly reduced. Under the optimized conditions, a detection limit of 3 pg ml^-1 (3 σ, n = 11) and a precision of 1.9% RSD for 1 ng ml^-1 of Cd were obtained. The method was successfully applied to the determination of cadmium in a series of Chinese Geological Reference Materials (SRMs) and GBW01621 ferronickel alloy using simple aqueous standard calibration technique. The results obtained were in good agreement with the certified values.

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A single-channel flow injection (FI) manifold with spectrophotometric detection has been designed and fabricated for diazepam determination. A 100 µl 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 µg 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 σ) 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.

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In this paper, we report on a method for quantifying clavulanic acid and amoxicillin simultaneously in pharmaceuticals using sequential injection analysis (SIA) with a diode-array spectrophotometric detector and multivariate curve resolution with alternating least squares (MCR-ALS). We optimized the experimental parameters so that the analytical sequence could distinguish the concentrations and spectrum profiles of the species of interest with optimum resolution quality. After establishing the optimum conditions, we quantified clavulanic acid and amoxicillin in four pharmaceuticals. In most cases our results were slightly higher than those in the prospectus of the pharmaceutical. The relative standard deviations were below 5% for amoxicillin and below 7% for clavulanic acid. These results are acceptable because, to prevent degradation due to bacteriostatic activity, the concentration of the main reactant is usually higher.

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The development of instrumentation for sequential injection analysis with a “lab-at-valve” (SIA-LAV) micro-extraction system is presented. The extractive determination of an anionic surfactant using methylene blue was selected as a model. Sample, reagents and organic solvent were sequentially aspirated into an extraction coil connected to the center of a selection valve, where extraction took place by flow reversal. The aqueous and organic phases were separated in a LAV unit attached to one port of the valve. The LAV unit situated a fiber-optic spectrophotometer to monitor the absorbance change of the extract product in the organic phase. The developed SIA-LAV system offers an alternative micro-total analysis system for automated micro-extraction.

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A pneumatic flow injection-tandem spectrometer system, without a delivery pump was used for the speciation of iron. In this system, the suction force of a pneumatic nebulizer of a flame absorption spectrometer was used for solution delivery through the manifold. The Fe(III) and total Fe concentrations were determined using thiocyanate ion in a UV-Vis spectrometer and a FAAS, respectively. The Fe(II) was determined by the difference. The calibration curves were linear up to 18 µg mL^-1 and 25 µg mL^-1 with detection limits of 0.09 µg mL^-1 and 0.07 µg mL^-1 for Fe(III) and Fe(II), respectively. The mid-range precision and accuracy were <2.5% and ±3% for the two species, respectively, at a sampling rate of 120 h^-1. This system was applied for the determination of Fe(III) and Fe(II) in industrial water, natural water and spiked samples.

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The starane herbicide was spectrophotometrically determined by the diazotization method in a flow injection assembly. Since starane is a substituted pyridyl compound the NH₂ group at the p-position was exploited for diazotization. Starane was diazotized with nitrite and the diazotized product is coupled with β-naphthol. The absorbance of the resulting azo dye was measured at 395 nm with a molar absorptivity of 1.5 × 10⁴ L mol^-1 cm^-1. The calibration graph was linear over the range of 0.6 to 10 µg/mL, with a relative standard deviation (RSD) of 1.67% and a sampling through put of 60 samples h^-1. The % recovery for the determination of starane was found to be 96%. The method was successfully applied to the determination of the active ingredient of starane herbicide in its formulation as well as in food samples.

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Simple sequential injection analysis systems with DSTD (SIA/DSTD) have been developed. One was employed for the study of the effects of the ion contents in solutions to the dynamic surface pressure of ionic surfactants. The results from the studies show the possibility for an alternative simple fast screening, but also a sensitive procedure for water quality determination. Another simple SIA/DSTD system has been demonstrated for the quantification of an anionic surfactant using a single standard calibration.

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A simple spectrophotometric flow injection (FI) procedure for the determination of Cr(III) using ethylenediaminetetraacetic acid (EDTA) was developed. An FI system with a column packed with Amberlite IR-120(H) was employed for sample pretreatment. This leads to the possibility of a single standard calibration. A linear calibration in a range of 10 - 27 µg Cr(III) was obtained with a detection limit of 1 µg Cr(III) and RSD of 2% (18 µg Cr(III), n = 12). The proposed procedure was applied for determination of Cr(III) in leachate and dietary supplement samples. The results agreed with those obtained by the standard methods.

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A simple sequential injection analysis (SIA) with spectrophotometric detection for an assay of acidity in fruit juice was investigated. An alkaline reagent (sodium hydroxide), a sample and an indicator (phenolphthalein) were first aspirated and stacked as adjacent zones in a holding coil. With flow reversal through a reaction coil to the detector, zone penetration occurred, leading to a neutralization reaction that caused a decrease in the color intensity of the indicator being monitored for absorbance at 552 nm. The effects of various parameters were studied. Linear calibration graphs for acidities of 0.2 - 1.0 and 0.5 - 2.5% w/v citric acid as a standard, with a relative standard deviation of 1% (acidity of 0.3 - 0.6% w/v as citric acid, n = 11) and a sample throughput of 30 samples h^-1, were achieved. The developed method was validated by a standard titrimetric method for assaying the acidity of fruit juice samples.

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A method for the preconcentration and speciation of chromium in seawater was developed. On-line preconcentration and determination were carried out by using inductively coupled plasma atomic emission spectrometry (ICP-AES) with dual mini-columns containing a chelating resin. In this system, Cr(III) was collected on the first column. The effluent containing residual chromium from the first column was collected on the second column after passing through a reduction-switching unit, in which the reducing agent was introduced, or not, for the reduction of Cr(VI) to Cr(III). Cr(VI) was determined as the difference between the concentration of pre-reduced Cr(VI) and Cr(III) in the effluent from the first column. The detection limits for Cr(III) and Cr(VI) were 0.04 and 0.09 µg l^-1, respectively.

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A flow injection spectrophotometric method is proposed for the determination of bromoxynil herbicide. Bromoxynil was hydrolyzed with HCl and the resulting product, 3,5-dibromo-4-hydroxyaniline, was diazotized with nitrite and coupled with aniline. The absorbance of the azo dye was measured at 500 nm. The conditions were optimized for diazotization using FIA. The range of linearity was found to be 0.01 to 5 ppm with a molar absorptivity of 1.27 × 10⁵ L mol^-1 cm^-1. The % recovery for the determination of bromoxynil was found to be 91%. The sampling frequency was 80 samples per hour for FIA. The method is simple, fast, and has been successfully applied to the determination of bromoxynil in commercial formulations and food samples.

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A simple flow injection analysis (FIA) method is described for the sequential determination of iron and copper. The detection method for iron and copper is based on their catalytic activities in the oxidation reaction of N,N-dimethyl-p-phenylenediamine (DPD) with hydrogen peroxide. The sequential determination of iron and copper can be carried out by injecting two sample plugs into the FIA system, sequentially. One injection does not contain triethylenetetramine (TETA), and is used for the sum of iron and copper concentration; the other which contains TETA is used only for the iron concentration. For iron determination, TETA is used as a masking agent of copper. The difference in peak height can be used for the calculation of copper concentration. Under the optimal conditions, the detection limits (3 σ) of 0.01 and 0.07 µg L^-1 were obtained for iron and copper, respectively. The proposed method can be applied to the determination of iron and copper in tap water and bottled-drinking mineral water samples. Good recoveries of the method, 98 - 103% for iron and 98 - 106% for copper, were achieved.

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A novel determination method for urea using an acid urease column-FIA system was developed, and the system was applied to the determination of urea in rice wine. This novel FIA system was characterized by CO₂ detection due to the property of acid urease and by a microfluidic gas-diffusion device with the use of an ultra-thin hollow fiber membrane. A biosensing system fabricated in this study was assembled with a double-plunger pump, a sample-injection valve, an immobilized acid urease column as a recognition element for the assay of urea, a gas-diffusion unit, and a flow-type spectrophotometer. The gas-diffusion unit consisted of a double-tubing structure in which the outer tubing was made of PTFE (i.d. 1.0 mm; o.d. 1.5 mm) and the inner tubing was of porous PTFE (i.d. 0.19 mm; o.d. 0.25 mm). Standard urea solutions (20 µl) were measured through monitoring variations in the absorbance of a coloring agent solution resulting from a pH shift due to carbon dioxide molecules being enzymatically generated. A wide and linear relationship was obtained between the concentration of urea (16 µM - 1.0 mM) and the change in absorbance. This FIA system has great advantages that the system did not suffer from ammonia and ethanol in samples. This system, armed with a microfluidic gas-diffusion device, was applicable to the determination of various substrates of many kinds of decarboxylase, amino-acid oxidase, and amino-acid oxygenase, producing CO₂ and NH₃ molecules.

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Flow injection-solid phase spectrometry (FI-SPS) has been applied to the determination of cobalt(II) in water samples. The complex formed between cobalt and 5-Br-PADAB was on-line protonated and concentrated on an AG 50W-X2 cation-exchanger in a flow-through cell. The increase in absorbance caused by the accumulation of the complex in the resin was continuously measured. The interference by copper could be effectively eliminated by using EDDP as a masking agent. The detection limit was 40 ng dm^-3 with a 4.0 cm³ sample solution.

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Based on the chemiluminescence (CL) emission generated from the oxidation of ceftriaxone sodium alkali hydrolysate by potassium permanganate in polyphosphoric acid (PPA), a novel determination method for ceftriaxone sodium was developed by using a flow-injection technique. The calibration curve appears to be linear in the range between 0.05 and 100 µg mL^-1 with a detection limit (3 σ) of 25 ng mL^-1, and a relative standard deviation (RSD) of 0.6% for eleven replicate determinations of 5.0 µg mL^-1 ceftriaxone sodium. The proposed method has been successfully utilized for the determination of ceftriaxone sodium in pharmaceutical formulations, while the chemiluminescence reaction mechanisms were investigated.

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